CN101379637A - Lithium transition metal-based compound powder for positive electrode material in lithium rechargeable battery, method for manufacturing the powder, spray dried product of the powder, firing precursor - Google Patents
Lithium transition metal-based compound powder for positive electrode material in lithium rechargeable battery, method for manufacturing the powder, spray dried product of the powder, firing precursor Download PDFInfo
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- CN101379637A CN101379637A CNA2007800044243A CN200780004424A CN101379637A CN 101379637 A CN101379637 A CN 101379637A CN A2007800044243 A CNA2007800044243 A CN A2007800044243A CN 200780004424 A CN200780004424 A CN 200780004424A CN 101379637 A CN101379637 A CN 101379637A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
This invention provides a lithium transition metal-based compound powder for a positive electrode material in a lithium rechargeable battery, which, when used as a positive material for a lithium rechargeable battery, can simultaneously realize cost reduction, resistance to high voltage, high safety, and battery performance improvement. The lithium transition metal-based compound powder for a positive electrode material in a lithium rechargeable battery is characterized in that, in a mercury penetration curve obtained by a mercury penetration method, the mercury penetration level in a pressure rise from 3.86 kPa to 413 MPa is not less than 0.8 cm<3>/g and not more than 3 cm<3>/g.
Description
Technical field
The secondary lithium batteries that the present invention relates to a kind of lithium transition-metal based compound powder and manufacture method, spray drying body and calcining presoma that uses as positive electrode material of lithium secondary cell, uses this lithium transition-metal based compound powder is anodal and have a lithium secondary battery of this secondary lithium batteries positive pole.
Background technology
Because the energy density of lithium secondary battery and output power density etc. are good, can small-sized effectively, lightweight, so rapid growth appears in its demand as the power supply of the portable machine of notebook computer, mobile phone and hand-held camera etc.Lithium secondary battery also gets most of the attention as the power supply of the load adjustment of electric automobile and electric power etc. again, in recent years, is promptly enlarging as the demand of hybrid-electric car with power supply.Especially in the electric automobile purposes, low cost, fail safe, life-span (especially at high temperature) and part throttle characteristics are good to be required, wishes to improve to some extent aspect material.
In the material that constitutes lithium secondary battery,, can use to have and to take off the material that embedding embeds the lithium ion function as the positive electrode active material material.These positive active material material categorys are various, take on a different character respectively.Again, as towards improving the so common problem of performance, for example improve part throttle characteristics, strong hope improves aspect material to some extent.
Seek the good material of the also good performance balance of a kind of low cost, fail safe, life-span (especially at high temperature) again.
Now, as the positive electrode active material material of secondary lithium batteries, lithium manganese system complex oxide, layered lithium-nickel-based compound oxide, stratiform lithium-cobalt system composite oxides with spinel structure etc. is actually used.Used the lithium secondary battery of these lithium-contained composite oxides all aspect characteristic, to have merits and demerits.That is, it is cheap in and synthetic being easier to have a lithium manganese system complex oxide of spinel structure, when making battery fail safe good, but then, capacity is low, hot properties (circulation, preservation) is inferior.Layered lithium-nickel-based compound oxide capacity height, hot properties are good, but synthetic difficult, the fail safe when making battery is inferior, keeping also should be noted that etc. shortcoming is arranged.Stratiform lithium-cobalt system composite oxides since synthetic easily and battery performance reach good balance, so the power supply of using as portable machine is widely used but the shortcoming not enough and cost height that is fail safe.
In such present situation, as overcoming or do one's utmost to reduce shortcoming that these positive electrode active material materials are had and reaching the strong candidate of the active material of good balance, propose lithium-nickel-manganese-cobalt system complex oxide with layer structure as battery performance.Especially, under the raising that cost degradation requires, Towards Higher Voltage requires, safe requires in recent years, it is counted as the positive electrode active material material that is hopeful as satisfying any one requirement wherein.
Just, because the degree of its cost degradation, Towards Higher Voltage and fail safe changes with the variation of ratio of components, so, need to select to use with manganese/nickle atom than being set in more than 1 or the material of the qualification compositing range of reduction cobalt ratio etc. for cost degradation more, the use of setting higher upper voltage limit, the requirement of greater security.Yet, the lithium secondary battery that the lithium-nickel-manganese-cobalt system complex oxide of such compositing range is used as positive electrode since the part throttle characteristics of speed and characteristics of output power etc. reduce, so during practicability, need improvement further.
In the past, patent documentation 1～3, non-patent literature 1～24 disclose manganese/nickle atom than 1 or more and the cobalt ratio drop to the lithium-nickel-manganese-cobalt system complex oxide of compositing range such below the value that the present invention stipulates.
Yet, according to patent documentation 1～3, non-patent literature 1～24, the not record of controlling about the pore of active material particle given to this invention, the necessary condition of seeking to improve battery performance in the discontented unabridged version invention, only use these technology, the improvement of seeking battery performance shown in the present is very difficult.
On the other hand, patent documentation 4 discloses a kind of by being used for the anode for nonaqueous secondary cell active material with the particle that is selected from the porous matter that lithium composite xoide that element more than a kind among Co, Ni, the Mn and lithium be main component constitutes, the pore average grain diameter of passing through the pore measure of spread that mercury penetration method carries out of this particle is in the scope of 0.1～1 μ m, and the total measurement (volume) of pore in footpath with 0.01～1 μ m is at 0.01cm
3More than/the g, put down in writing and not damaged positive active material thus to the fillibility of positive pole and improve the part throttle characteristics of battery.
Yet, in the lithium composite xoide particle of patent documentation 4 records,, have the still insufficient such problem of part throttle characteristics though exist coating to be improved.
Yet, at the lithium composite xoide particle of patent documentation 5 record, improving effect though demonstrate with the many compositions of cobalt accounting example, still there is the not enough problem of part throttle characteristics in the compositing range with respect to the present invention stipulates.Again, patent documentation 6～30, non-patent literature 25～57 disclose manganese/nickle atom than near 1 and the cobalt ratio be reduced to the lithium-nickel-manganese-cobalt system complex oxide of the compositing range below the value of regulation of the present invention.
, patent documentation 6 discloses a kind of by general formula Li[Li
xCo
yA
1-x-y] O
2(in the formula, A represents [Mn
zNi
1-z], x represents the numerical value of 0.00～0.16 scope, and y represents the numerical value of 0.1～0.30 scope, and z represents the numerical value of 0.40～0.65 scope, Li
xBe included in the transition metal layer of above-mentioned tectosome) expression single-phase cathode material, put down in writing doping by making cobalt roughly greater than 10% of total transition metal, obtain having the cathode material of good electrochemical properties, in the negative electrode of the composition that the doping of cobalt is lacked than described regulation ratio, there is the problem that is difficult to obtain good electrochemical properties.Again, if at length have a look the compositing area of the regulation of patent documentation 1, then the amount of the contained lithium (x) of the lower limit of the molar ratio of cobalt (y) and transition metal layer is irrelevant, be 0.1, but in the present invention during Gui Ding compositing area (composition formula (1)), contained (z/ (2+z)) of transition metal layer measures if surpass 0, and then the molar ratio of cobalt does not satisfy compositing range of the present invention less than 10%.
Again, according to patent documentation 7～30, non-patent literature 25～57, record is not conceived to the specific half width of the active material crystallization in compositing area given to this invention, does not have record to have or not the heterogeneous peak of the high corner side that captures the summit that appears at specific diffraction maximum yet.And do not put down in writing the pore control as the particle of better feature, do not satisfy the necessary condition of the improvement of seeking battery performance among the present invention, only use these technology, it is very difficult seeking battery performance improvement shown in the present.
Patent documentation 31 discloses, and contains by composition formula Li
aMn
0.5-xNi
0.5-yM
X+yO
2(wherein, 0＜a＜1.3,-0.1 ≦ x-y ≦ 0.1, M is Li, Mn, element beyond the Ni) total pore volume of the positive active material of the composite oxides of expression is more than 0.001ml/g, 0.006ml/g below, and, use 2 θ of the powder X-ray ray diffraction diagram of CuK α line: diffraction maximum in 44.1 ± 1 ° and 2 θ: the relative intensity ratio of the diffraction maximum in 18.6 ± 1 ° is more than 0.65,1.05 below, described 2 θ: the half width of the diffraction maximum in 18.6 ± 1 ° is more than 0.05 ° below 0.20 °, described 2 θ: the half width of the diffraction maximum in 44.1 ± 1 ° is more than 0.10 ° below 0.20 °, put down in writing to make thus and had high energy density, the battery that charge-discharge performance is good.That is, admit that patent documentation 31 has in compositing area given to this invention, be conceived to the record of the specific half width of active material crystallization, as the record of the pore control of the particle of better necessary condition.
Again, according to patent documentation 32, patent documentation 33, be not documented in the specific half width that is conceived to the active material crystallization in the compositing area of the present invention regulation, do not mention yet and have or not the record of comparing the heterogeneous peak that appears at high corner side with the summit of specific diffraction maximum, but admit the record of the pore control of relevant particle as better necessary condition.Patent documentation 27 discloses a kind of positive active material for lithium secondary battery that is made of the Li-Mn-Ni composite oxides of element at least lithium, manganese and nickel conduct that contains, the pore total measurement (volume) of described Li-Mn-Ni composite oxides has been put down in writing can make thus and has been had than high discharge capacity, the good battery of cycle performance more than 0.0015ml/g.
Yet, the Li-Mn-Ni system complex oxide that the atomic ratio of being put down in writing for patent documentation 31 by Ni/Mn=1/1 constitutes, do not mention half width for (110) diffraction maximum that judges whether to find that higher performance is useful, even the value of total pore volume is compared with value given to this invention, be a minimum value, still have the insufficient such problem of part throttle characteristics.Yet, the Li-Mn-Ni system complex oxide that patent documentation 27 is put down in writing, though stipulated pore capability value big than patent documentation 31, it all is minimum that the value of total pore capacity of any embodiment is compared with the value that the present invention stipulates, still has an insufficient such problem of part throttle characteristics.
Patent documentation 33 has been put down in writing, when a kind of lithium composite xoide particle is utilized as the positive electrode of lithium secondary battery, can become suitable positive electrode material of lithium secondary cell, can improve the low temperature part throttle characteristics of lithium secondary battery, coating when making positive pole simultaneously is also good, above-mentioned lithium composite xoide particle is in the mensuration that mercury penetration method is carried out, the mercury amount of being pressed under specific high voltage load condition is below the set upper limit value, and the described mercury amount of being pressed into is more than the lower limit of regulation, perhaps the average pore radius within the limits prescribed, simultaneously in the pore distribution curve, except former main peak, has the submaximum that has summit in specific pore radius region.
Yet, in the lithium composite xoide particle of patent documentation 33 record, improving effect though demonstrate with the many compositions of cobalt accounting example, still there is the not enough problem of part throttle characteristics in the compositing range with respect to the present invention stipulates.
Again, patent documentation 34～65, non-patent literature 58～130 disclose manganese/nickle atom when the cobalt ratio be equivalent to the lithium-nickel-manganese-cobalt system complex oxide of compositing range of the value of the present invention's regulation.
; in patent documentation 34～65, non-patent literature 58～130; the record of the growth of the active material particle when in compositing area given to this invention, not being conceived to suppress to calcine and the additive of sintering; in the discontented unabridged version invention is the necessary condition of seeking the improvement of battery performance; only use these technology, the improvement of seeking battery performance shown in the present is very difficult.
Again, though do not put down in writing the document of " growth and the sintering of the active material particle when suppressing calcining " shown in the present, but as being purpose with improvement positive electrode active material material, the lithium-nickel-manganese-cobalt system complex oxide added with the compound etc. that contains W, Mo, Nb, Ta, Re handle or the known document of replacement Treatment, have following patent documentation 66～74 and non-patent literature 131 to disclose.
Patent documentation 71 discloses the embodiment that replaces W in the lithium-nickel-manganese-cobalt system complex oxide at the transition metal position.Yet because the composition in the transition metal position is that the Mn molar ratio seldom is 0.01, the Ni molar ratio utmost point mostly is 0.8, can not obtain the problem that various battery behaviors reach the active material of good balance so still exist.
Patent documentation 72 discloses the material that will be replaced at its transition metal position Nb, Mo, W as positive active material in the Li-mn-ni compound oxyde of monoclinic structure, put down in writing a kind of energy density height, voltage height, lithium secondary battery that reliability is high can be provided thus.Yet, according to embodiment and since calcining heat low be 950 ℃, so crystallization is very inflourishing, and since the molar ratio of this element too high be 5 moles of %, can not obtain the active material that various battery behaviors reach good balance so still exist.
Patent documentation 73 discloses on the surface at least of the lithium transition-metal oxide particle of layer structure has the compound that contains molybdenum, tungsten, also has good battery behavior thus even put down in writing under harsher environment for use.Yet according to embodiment, Co/ (Ni+Co+Mn) molar ratio is crossed and mostly is 0.33, and calcining heat is low in addition is 900 ℃, so crystallization is very inflourishing, can not obtain the active material that various battery behaviors reach good balance so still exist.
Patent documentation 74 discloses and has used the lithium-nickel-manganese-cobalt niobium molybdenum system complex oxide with layer structure.Yet Co/ (Ni+Co+Mn) mol ratio that embodiment forms is 0.34, and the Co ratio is higher, can not obtain the active material that various battery behaviors reach good balance so still exist.
Non-patent literature 131 discloses the LiNi with layer structure
1/3Mn
1/3Mo
1/3O
2Composite oxides.Yet, because the too high levels of Mo can not obtain the problem that various battery behaviors obtain the active material of good balance so still exist.
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Summary of the invention
The object of the present invention is to provide a kind of positive electrode material of lithium secondary cell with lithium transition-metal based compound powder and manufacture method thereof, use the lithium secondary battery that the secondary lithium batteries of this lithium transition-metal based compound powder is anodal and possess this secondary lithium batteries positive pole, described positive electrode material of lithium secondary cell is sought the raising of the such part throttle characteristics of in as the use of positive electrode material of lithium secondary cell speed characteristics of output power with lithium transition-metal based compound powder, and better is can coexist with cost degradation, high voltage withstandingization and high safe.
The inventor intently inquires into research in order to finish above-mentioned problem, found that by in the lithium transition-metal based compound, the mercury amount of controlling when the powder shape is feasible boosts by mercury penetration method of being pressed into is above-mentioned scope, and control and make the peak of pore distribution curve have above-mentioned such feature, can obtain a kind of lithium transition-metal based compound powder, described lithium transition-metal based compound powder is as positive electrode material of lithium secondary cell, cost degradation, high voltage withstandingization, high safe, and can coexist with the raising of the such part throttle characteristics of speed or characteristics of output power, so that finish the present invention.
Again, the inventor intently inquires into research in order to finish above-mentioned problem, found that by in the lithium-nickel-manganese-cobalt system complex oxide, the half width of the specific diffraction maximum during the control powder x-ray diffraction is measured, and composition is controlled at the specific region, can obtain a kind of lithium-nickel-manganese-cobalt system complex oxide powder, described lithium-nickel-manganese-cobalt system complex oxide powder is as positive electrode material of lithium secondary cell, cost degradation, high voltage withstandingization, high safe and can coexist with the raising of the such part throttle characteristics of speed or characteristics of output power are so that finish the present invention.
The inventor thinks the problem of the raising that be to solve the such part throttle characteristics of speed characteristics of output power, it is enough high and to suppress particle growth and sintering and obtain small particle be important to make crystallinity, intently inquire into research, found that particularly in the laminated Li-Ni-Mn co-containing mixed oxide, calcine behind the compound that grain when suppressing calcining by adding in the main component raw material is grown up, can obtain a kind of lithium transition-metal based compound powder, described lithium transition-metal based compound powder is as positive electrode material of lithium secondary cell, cost degradation, high voltage withstandingization, high safe, and can coexist with the raising of the such part throttle characteristics of speed or characteristics of output power, so that finish the present invention.
Just, main points of the present invention are as follows.
1. a positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powder the mercury that obtains in mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.8cm
3/ g is above, 3cm
3Below/the g.
2. 1 described lithium transition-metal based compound powder as described, it is characterized in that, the pore distribution curve that mercury penetration method obtains more than pore radius 300nm, locate to have the main peak that has summit below the 1000nm, and more than pore radius 80nm, less than the 300nm place, do not have the submaximum that has summit.
3. 1 or 2 described lithium transition-metal based compound powders as described is characterized in that, in the pore distribution curve that mercury penetration method obtains, more than pore radius 300nm, locate to exist pore capacity that the main peak of summit relates at 0.5cm below the 1000nm
3/ g is above, 1.5cm
3Below/the g.
4. each described lithium transition-metal based compound powder in 1～3 as described, it is characterized in that, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than the 0.6 μ m, below the 5 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
5. each described lithium transition-metal based compound powder in 1～4 as described is characterized in that, is the lithium-nickel-manganese-cobalt system complex oxide by following composition formula (I) expression,
Li[Li
Z/ (2+z){ (Li
xNi
(1-3x)/2Mn
(1+x)/2)
1-yCo
y}
2/ (2+z)] O
2... composition formula (I)
Wherein, in composition formula (I), 0 ≦ x ≦ 0.33,0 ≦ y ≦ 0.2 ,-0.02 ≦ z ≦ 0.2 (1-y) (1-3x).
6. each described lithium transition-metal based compound powder in 1～5 as described is characterized in that volume density is 0.5～1.5g/cm
3
7. each described lithium transition-metal based compound powder in 1～6 as described is characterized in that the BET specific area is 1.5～5m
2/ g.
8. each described lithium transition-metal based compound powder in 1～7 as described is characterized in that, in the time of will containing concentration of carbon and be made as C (weight %), the C value is more than the 0.005 weight %, below the 0.2 weight %.
9. the manufacture method of each the described lithium transition-metal based compound powder in a kind described 1～8, it is characterized in that, in liquid medium with lithium compound and at least a more than transistion metal compound pulverize, the spray drying body that obtains making its homodisperse slip carry out spray drying is calcined this spray drying body in oxygen-containing gas atmosphere.
10. 9 described manufacture methods as described is characterized in that, the spray drying body comprises interstitial compound in a kind of second particle that makes the spray drying body at least, uses as the calcining presoma.
11. 10 described manufacture methods is characterized in that as described, produce when the compound that the space is formed is calcining or are sublimed into decomposition gas and make interstitial compound in the second particle.
12. 11 described manufacture methods is characterized in that as described, one of decomposition gas is carbonic acid gas (CO
2).
13. the described manufacture method of any one of 9 to 12 is characterized in that as described, lithium compound is a lithium carbonate.
14. the spray drying body of a lithium transition-metal based compound, it is characterized in that, described spray drying body is by pulverizing lithium compound and at least a transistion metal compound in liquid medium, to making its homodisperse slip carry out spray drying and obtaining, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of this spray drying body of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.01 μ m, below the 4 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
15. 14 described spray drying bodies is characterized in that as described, the BET specific area is 10～70m
2/ g.
16. the calcining presoma of a lithium transition-metal based compound is characterized in that, at least also contains the interstitial compound in the second particle that makes more than a kind in described 14～15 described spray drying bodies.
17. a secondary lithium batteries positive pole is characterized in that, has on the collector to contain described 1～8 each the described lithium transition-metal based compound powder and the positive electrode active material layer of binding agent.
18. lithium secondary battery, it is characterized in that, described lithium secondary battery possess can embed (insertion) take off embedding (extraction) lithium negative pole, contain the nonaqueous electrolyte of lithium salts and can embed the positive pole of removal lithium embedded, use described 17 described secondary lithium batteries anodal as anodal.
19. positive electrode material of lithium secondary cell lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, compound by following composition formula (I ') expression constitutes, contain the crystalline texture that belongs to layer structure and constitute, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is made as FWHM (110), then use 0.01 ≦ FWHM (110) ≦ 0.2 expression
Li[Li
Z ＇/(2+z '){ (Ni
(1+y ')/2Mn
(1-y ')/2)
1-x 'Co
X '}
2/ (2+z ')] O
2... Group becomes (I ')
(wherein, in composition formula (I '), 0 ≦ x ′ ≦ 0.1 ,-0.1 ≦ y ′ ≦ 0.1, (1-x ') (0.05-0.98y ') ≦ z ′ ≦ (1-x ') (0.15-0.88y ').)
20. 19 described positive electrode material of lithium secondary cell are with lithium-nickel-manganese-cobalt system complex oxide powders as described, it is characterized in that, in composition formula (I '), 0.04 ≦ x ′ ≦ 0.099,-0.03 ≦ y ′ ≦ 0.03, (1-x ') (0.08-0.98y ') ≦ z ′ ≦ (1-x ') (0.13-0.88y ').
21. 19 or 20 described lithium transition metal-based compound powder for positive electrode material in lithium rechargeable batteries as described; It is characterized in that; In the powder x-ray diffraction that uses CuK α line is measured; The angle of diffraction 2 θ are near (018) diffraction maximum 64 °, near (110) diffraction maximum 64.5 ° and near (113) diffraction maximum 68 °; High corner side at separately summit does not have the heterogeneous diffraction maximum that causes; When perhaps having the heterogeneous diffraction maximum that causes; The integrated intensity of heterogeneous peak and the diffraction maximum of original crystalline phase is than respectively in following scope
0≦I
018*/I
018≦0.20
0≦I
110*/I
110≦0.25
0≦I
113*/I
113≦0.30
Here, I
018, I
110, I
113The integrated intensity of representing (018), (110), (113) diffraction maximum respectively, I
018*, I
110*, I
113*Express the integrated intensity of the heterogeneous diffraction maximum that causes of the high corner side of the summit of (018), (110), (113) diffraction maximum now respectively.
22. the described positive electrode material of lithium secondary cell of each in 19～21 is with lithium-nickel-manganese-cobalt system complex oxide powder as described, it is characterized in that, the mercury that obtains in mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.7cm
3/ g is above, 1.5cm
3Below/the g.
23. the described positive electrode material of lithium secondary cell of each in 19～22 is with lithium-nickel-manganese-cobalt system complex oxide powder as described, it is characterized in that, the pore distribution curve that mercury penetration method obtains more than pore radius 300nm, locate to have the main peak that has summit below the 1000nm, and more than pore radius 80nm, less than the 300nm place, do not have the submaximum that has summit.
24. as described in 19～23 each described positive electrode material of lithium secondary cell with lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, in the pore distribution curve that mercury penetration method obtains, more than pore radius 300nm, exist pore capacity that the main peak of summit relates to below the 1000nm more than the 0.3cm3/g, below the 1.0cm3/g.
25. the described positive electrode material of lithium secondary cell of each in 19～24 is with lithium-nickel-manganese-cobalt system complex oxide powder as described, it is characterized in that, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than the 1 μ m, below the 5 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
26. the described positive electrode material of lithium secondary cell of each in 19～25 is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder volume density is 0.5～1.7g/cm as described
3
27. the described positive electrode material of lithium secondary cell of each in 19～26 is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder the BET specific area is 1.4～3m as described
2/ g.
28. each described positive electrode material of lithium secondary cell is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder in 19～27 as described, in the time of will containing concentration of carbon and be made as C (weight %), the C value is more than the 0.005 weight %, below the 0.05 weight %.
29. each described positive electrode material of lithium secondary cell is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder the specific insulation when compressing with 40MPa pressure is 1 * 10 in 19～28 as described
3Ω cm is above, 1 * 10
6Below the Ω cm.
30. the described positive electrode material of lithium secondary cell of each in a kind described 19～29 manufacture method of lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, comprise: the slip preparation section, in liquid medium, lithium compound, nickel compound, manganese compound and cobalt compound are pulverized, obtained making its homodisperse slip; The spray drying operation is carried out spray drying to the slip that obtains; Calcination process, in oxygen-containing gas atmosphere, the temperature T of 940 ℃ ≦ T ≦ 1200 ℃ (℃) under, the spray drying body that obtains is calcined.
31. 30 described positive electrode material of lithium secondary cell is characterized in that with the manufacture method of lithium-nickel-manganese-cobalt system complex oxide powder lithium compound is a lithium carbonate as described.
32. manufacture method as claim 30 or 31 described positive electrode material of lithium secondary cell usefulness lithium-nickel-manganese-cobalt system complex oxide powders, it is characterized in that, in the slip preparation section, in liquid medium with lithium compound, nickel compound, manganese compound and cobalt compound are pulverized, be crushed to median particle diameter below 0.3 μ m, this median particle diameter is to disperse (power output 30W at the ultrasonic wave that carried out 5 minutes, frequency 22.5kHz) afterwards, measure by laser diffraction/diffuse transmission type particle size distribution device and to obtain, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference, in the spray drying operation, slip viscosity during with spray drying is made as V (cp), the slip quantity delivered is made as (L/min), when gas delivery volume is made as G (L/min), then at 50cp ≦ V ≦ 4000cp, carry out spray drying under the condition of 1500 ≦ G/S ≦ 5000.
33. the spray drying powder of a lithium-nickel-manganese-cobalt system complex oxide, it is characterized in that, pass through in liquid medium lithium compound as the spray drying powder of positive electrode material of lithium secondary cell with the presoma of lithium-nickel-manganese-cobalt system complex oxide powder, nickel compound, manganese compound and cobalt compound are pulverized, to making its homodisperse slip carry out spray drying and obtaining, the ultrasonic wave that described spray drying powder was carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of this spray drying powder of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.01 μ m, below the 4 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
34. 33 described spray drying powders is characterized in that as described, the BET specific area is 10～100m
2/ g.
35. a secondary lithium batteries positive pole is characterized in that, has on the collector to contain each described positive electrode material of lithium secondary cell of described 19～29 positive electrode active material layer with lithium-nickel-manganese-cobalt system complex oxide powder and binding agent.
36. a lithium secondary battery is characterized in that, described lithium secondary battery possesses negative pole, nonaqueous electrolyte that contains lithium salts that can embed removal lithium embedded and the positive pole that can embed removal lithium embedded, uses the described secondary lithium batteries of claim 35 anodal as anodal.
37. 36 described lithium secondary batteries is characterized in that as described, the charging potential that is designed to the positive pole in the fully charged state is more than 4.35V (vs.Li/Li+).
38. positive electrode material of lithium secondary cell lithium transition-metal based compound powder, it is characterized in that, with the lithium transition-metal based compound with the function that can embed the removal lithium embedded ion is main component, the grain growth when in this main component raw material, adding the inhibition calcining more than at least a kind and the additive of sintering, the ratio of the integral molar quantity of the transition metal in the addition of this additive and the main component raw material is at 0.01 mole more than the % and less than 2 moles of %, calcines then and obtains.
39. 38 described positive electrode material of lithium secondary cell are with lithium transition-metal based compound powders as described, it is characterized in that, described additive is the oxide that contains at least a above element that is selected from Mo, W, Nb, Ta and Re (below, be called " interpolation element ").
40. as claim 38 or 39 described positive electrode material of lithium secondary cell lithium transition-metal based compound powder, it is characterized in that the atomic ratio of the summation of the summation of this interpolation element of the surface portion of primary particle and the metallic element except that Li and described interpolation element is more than 5 times of this atomic ratio of whole particle.
41. the described positive electrode material of lithium secondary cell of each in 38～40 is with lithium transition-metal based compound powder as described, it is characterized in that, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.1 μ m, less than 3 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
42. each described positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powder the average grain diameter of primary particle is more than the 0.1 μ m, below the 0.9 μ m in 38～41 as described.
43. it is characterized in that with lithium transition-metal based compound powder the BET specific area is at 1.5m as each described positive electrode material of lithium secondary cell in the claim 38～42
2/ g is above, 5m
2Below/the g.
44. the described positive electrode material of lithium secondary cell of each in 38～43 is with lithium transition-metal based compound powder as described, it is characterized in that, the mercury that obtains in mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.7cm
3/ g is above, 1.5cm
3Below/the g.
45. the described positive electrode material of lithium secondary cell of each in 38～44 is with lithium transition-metal based compound powder as described, it is characterized in that, the pore distribution curve that mercury penetration method obtains has the main peak that has summit more than 1 at least more than pore radius 300nm, below the 1000nm, and does not have the submaximum that has summit more than pore radius 80nm, less than 300nm.
46. as described in 38～45 each described positive electrode material of lithium secondary cell with lithium transition-metal based compound powder, it is characterized in that, in the pore distribution curve that mercury penetration method obtains, more than pore radius 300nm, exist pore capacity that the peak of summit relates to below the 1000nm at 0.4cm
3/ g is above, 1cm
3Below/the g.
47. it is characterized in that with lithium transition-metal based compound powder volume density is at 0.5g/cm as each described positive electrode material of lithium secondary cell in the claim 38～46
3More than, 1.7g/cm
3Below.
48. each described positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powder the specific insulation when compressing with 40MPa pressure is 1 * 10 in 38～47 as described
3Ω cm is above, 1 * 10
6Below the Ω cm.
49. each described positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powder the lithium-nickel-manganese-cobalt system complex oxide that constitutes is main component to contain the crystalline texture that belongs to layer structure in 38～48 as described.
50. positive electrode material of lithium secondary cell as claimed in claim 49 lithium transition-metal based compound powder is characterized in that, row composition formula composed as follows (I ") shown in,
LiMO
2 (I”)
Wherein, in the above-mentioned formula (I "), M is the element that is made of Li, Ni and Mn or Li, Ni, Mn and Co, and the Mn/Ni mol ratio is more than 0.8, below 5; Co/ (Mn+Ni+Co) mol ratio is more than 0, below 0.30, and the Li mol ratio is more than 0.001, below 0.2 among the M.
51. 49 or 50 described positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powder as described, are under oxygen-containing gas atmosphere, are that calcining obtains more than 970 ℃ in calcining heat.
52. each described positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powder in 49～51 as described, in the time of will containing concentration of carbon and be made as C (weight %), the C value is more than the 0.005 weight %, below the 0.05 weight %.
53. 50～52 described positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powders as described, the M in the described composition formula (I ") is by following formula (II ") expression,
M＝Li
z′’/(2+z′’){(Ni
(1+y′’)/2Mn
(1-y’′)/2)
1-x’′Co
x”}
2/(2+z’′)...(II”)
Wherein, in above-mentioned formula (II "), 0 ≦ x ′ ’ ≦ 0.1 ,-0.1 ≦ y ’ ′ ≦ 0.1, (1-x ' ') (0.05-0.98y ' ') ≦ z ′ ’ ≦ (1-x ' ') (0.20-0.88y ' ').
55. 53 described positive electrode material of lithium secondary cell are with lithium transition-metal based compound powders as described, it is characterized in that, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is made as FWHM (110), then use 0.01 ≦ FWHM (110) ≦ 0.2 expression.
55. 53 or 54 described lithium transition metal-based compound powder for positive electrode material in lithium rechargeable batteries as described; It is characterized in that; In the powder x-ray diffraction that uses CuK α line is measured; At the angle of diffraction 2 θ near (018) diffraction maximum 64 °, near (110) diffraction maximum 64.5 ° and near 68 ° (113) diffraction maximum; Do not have the heterogeneous diffraction maximum that causes at separately the high corner side that binds; When perhaps having the heterogeneous diffraction maximum that causes; The integrated intensity of heterogeneous peak and the diffraction maximum of original crystalline phase is than respectively in following scope
0≦I
018*/I
018≦0.20
0≦I
110*/I
110≦0.25
0≦I
113*/I
113≦0.30
Here, I
018, I
110, I
113The integrated intensity of representing (018), (110), (113) diffraction maximum respectively, I
018*, I
110*, I
113*Express the integrated intensity of the heterogeneous diffraction maximum that causes of the high corner side of the summit of (018), (110), (113) diffraction maximum now respectively.
56. the described positive electrode material of lithium secondary cell of each in a kind described 38～55 manufacture method of lithium transition-metal based compound powder, it is characterized in that, comprise: the slip preparation section, in liquid medium with lithium compound, be selected from the transistion metal compound more than a kind among V, Cr, Mn, Fe, Co, Ni and the Cu, particle when suppressing calcining is grown up and the additive of sintering is pulverized, and obtains making its homodisperse slip; The spray drying operation is carried out spray drying to the slip that obtains; Calcination process is calcined the spray drying powder that obtains.
57. 56 described positive electrode material of lithium secondary cell are with the manufacture method of lithium transition-metal based compound powders as described, it is characterized in that, in the slip preparation section, in liquid medium with lithium compound, transistion metal compound and additive are pulverized, be crushed to median particle diameter below 0.4 μ m, this median particle diameter is to disperse (power output 30W at the ultrasonic wave that carried out 5 minutes, frequency 22.5kHz) afterwards, measure by laser diffraction/diffuse transmission type particle size distribution device and to obtain, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference, in the spray drying operation, slip viscosity during with spray drying is made as V (cp), the slip quantity delivered is made as S (L/min), when gas delivery volume is made as G (L/min), then at 50cp ≦ V ≦ 4000cp, carry out spray drying under the condition of 1500 ≦ G/S ≦ 5000.
58. 56 or 57 described positive electrode material of lithium secondary cell are with the manufacture method of lithium transition-metal based compound powders as described, it is characterized in that, at least comprise nickel compound, manganese compound and cobalt compound as transistion metal compound, in calcination process, under oxygen-containing gas atmosphere, more than 970 ℃, the spray drying powder is calcined.
59. each described positive electrode material of lithium secondary cell is characterized in that with the manufacture method of lithium transition-metal based compound powder lithium compound is a lithium carbonate in 56～58 as described.
60. spray drying body, it is characterized in that, pass through in liquid medium lithium compound as the spray drying body of positive electrode material of lithium secondary cell with the presoma of lithium transition-metal based compound powder, be selected from V, Cr, Mn, Fe, Co, the transistion metal compound more than at least a kind among Ni and the Cu, particle when suppressing calcining is grown up and the additive of sintering is pulverized, to making its homodisperse slip carry out spray drying and obtaining, the ultrasonic wave that described spray drying body was carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of this spray drying powder of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.01 μ m, below the 4 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
61. 60 described spray drying bodies is characterized in that as described, the BET specific area is 10m
2/ g is above, 100m
2Below/the g.
62. a secondary lithium batteries positive pole is characterized in that, has on the collector to contain each described positive electrode material of lithium secondary cell of described 38～55 positive electrode active material layer with lithium transition-metal based compound powder and binding agent.
63. a lithium secondary battery is characterized in that, described lithium secondary battery possesses negative pole, nonaqueous electrolyte that contains lithium salts that can embed removal lithium embedded and the positive pole that can embed removal lithium embedded, uses described 62 described secondary lithium batteries anodal as anodal.
Positive electrode material of lithium secondary cell of the present invention as the positive electrode material of lithium secondary cell time spent, can make the raising of cost degradation and high safe and part throttle characteristics reach coexistence with the lithium transition-metal based compound.Therefore,, can provide a kind of cheapness and safe lithium secondary battery according to the present invention, even and this lithium secondary battery under high charge voltage, use, performance is also good.
Description of drawings
Fig. 1 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression embodiment 1.
Fig. 2 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression embodiment 2.
Fig. 3 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression embodiment 3.
Fig. 4 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression embodiment 4.
Fig. 5 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 5.
Fig. 6 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression comparative example 1.
Fig. 7 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression comparative example 2.
Fig. 8 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression comparative example 3.
Fig. 9 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression comparative example 4.
Figure 10 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression comparative example 5.
Figure 11 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing among the embodiment 1.
Figure 12 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing among the embodiment 2.
Figure 13 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing among the embodiment 3.
Figure 14 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing among the embodiment 4.
Figure 15 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 5.
Figure 16 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing in the comparative example 1.
Figure 17 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing in the comparative example 2.
Figure 18 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing in the comparative example 3.
Figure 19 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing in the comparative example 4.
Figure 20 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing in the comparative example 5.
Figure 21 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression embodiment 1.
Figure 22 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression embodiment 2.
Figure 23 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression embodiment 3.
Figure 24 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression embodiment 4.
Figure 25 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 5.
Figure 26 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression comparative example 1.
Figure 27 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression comparative example 2.
Figure 28 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression comparative example 3.
Figure 29 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression comparative example 4.
Figure 30 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression comparative example 5.
Figure 31 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 6.
Figure 32 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression embodiment 7.
Figure 33 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression comparative example 6.
Figure 34 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 6.
Figure 35 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing among the embodiment 7.
Figure 36 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing in the comparative example 6.
Figure 37 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 6.
Figure 38 is the chart of the XRD figure picture of the lithium nickel manganese composite oxide made of expression embodiment 7.
Figure 39 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression comparative example 6.
Figure 40 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 8.
Figure 41 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 9.
Figure 42 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 10.
Figure 43 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 11.
Figure 44 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression comparative example 7.
Figure 45 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression comparative example 8.
Figure 46 is the chart of the pore distribution curve of the lithium nickel manganese composite oxide powder body made of expression comparative example 9.
Figure 47 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 8.
Figure 48 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 9.
Figure 49 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 10.
Figure 50 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 11.
Figure 51 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing in the comparative example 7.
Figure 52 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing in the comparative example 8.
Figure 53 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese composite oxide of manufacturing in the comparative example 9.
Figure 54 is the chart of the x-ray diffractogram of powder picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 8.
Figure 55 is the chart of the x-ray diffractogram of powder picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 9.
Figure 56 is the chart of the x-ray diffractogram of powder picture of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 10.
Figure 57 is the chart of the x-ray diffractogram of powder picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 11.
Figure 58 is the chart of the x-ray diffractogram of powder picture of the lithium nickel manganese cobalt composite oxide made of expression comparative example 7.
Figure 59 is the chart of the x-ray diffractogram of powder picture of the lithium nickel manganese composite oxide made of expression comparative example 8.
Figure 60 is the chart of the x-ray diffractogram of powder picture of the lithium nickel manganese composite oxide made of expression comparative example 9.
Figure 61 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 12.
Figure 62 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 13.
Figure 63 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 14.
Figure 64 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 15.
Figure 65 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression embodiment 16.
Figure 66 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression comparative example 10.
Figure 67 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression comparative example 11.
Figure 68 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression comparative example 12.
Figure 69 is the chart of the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder made of expression comparative example 13.
Figure 70 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 12.
Figure 71 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 13.
Figure 72 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 14.
Figure 73 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 15.
Figure 74 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing among the embodiment 16.
Figure 75 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing in the comparative example 10.
Figure 76 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing in the comparative example 11.
Figure 77 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing in the comparative example 12.
Figure 78 is the SEM image (photo) (magnification ratio * 10,000) of the lithium nickel manganese cobalt composite oxide of manufacturing in the comparative example 13.
Figure 79 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 12.
Figure 80 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 13.
Figure 81 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 14.
Figure 82 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 15.
Figure 83 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression embodiment 16.
Figure 84 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression comparative example 10.
Figure 85 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression comparative example 11.
Figure 86 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression comparative example 12.
Figure 87 is the chart of the XRD figure picture of the lithium nickel manganese cobalt composite oxide made of expression comparative example 13.
Embodiment
Below, embodiments of the present invention are described in detail, but the explanation to constitutive requirements of the following stated is an example (typical example) of embodiments of the present invention that not special provision becomes these contents.
At first, positive electrode material of lithium secondary cell among the present invention is described in detail with lithium transition-metal based compound powder, this lithium transition-metal based compound powder is characterised in that, the mercury that obtains in mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.8cm
3/ g is above, 3cm
3Below/the g.
[lithium transition-metal based compound powder]
Positive electrode material of lithium secondary cell of the present invention is characterized in that with lithium transition-metal based compound powder the mercury that obtains in mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.8cm
3/ g is above, 3cm
3Below/the g.
＜mercury penetration method 〉
Positive electrode material of lithium secondary cell of the present invention is characterized in that with lithium transition-metal based compound powder, by in the mensuration of mercury penetration method, satisfies certain conditions.Therefore, before particle of the present invention is described, at first mercury penetration method is carried out simple explanation.
Mercury penetration method is a kind of like this gimmick, and promptly exert pressure to the sample of porous matter particle etc. in the limit, and the limit makes its pore immerse mercury, from the relation of pressure and the amount of mercury that is pressed into, obtains the information of specific area and fine pore distribution etc.
Specifically, at first, vacuumize, on this basis, make to be full of mercury in the container being placed with in the container of sample.The surface tension of mercury is big, and mercury can't immerse in the pore of specimen surface like this, but if mercury is exerted pressure, gently boosts, and then mercury is gently according to being dipped into the pore to the such order in the little hole of diameter from the big pore of diameter.Increase pressure continuously on one side Yi Bian detect mercury liquid level variation (being the mercury amount of being pressed into of pore), then can obtain representing the mercury of the relation of mercury applied pressure and the mercury amount of being pressed into is pressed into curve.
, suppose that being shaped as of pore is cylindric here, its radius is made as r, the surface tension of mercury is made as δ, and contact angle is made as θ, and then the size of extruding this direction of mercury from pore is represented (if θ〉90 °, then this is worth for just) by-2 π r δ (cos θ).Again because the size of power that under pressure P, mercury is pressed into this direction of pore by π r
2Expression is so derive following formula (1), formula (2) by these equilibrium of forces.
-2πrδ(cosθ)＝πr
2P (1)
Pr＝--2δ(cosθ) (2)
Mercury generally can use the value of surface tension δ=480dyn/cm degree, contact angle θ=140 ° degree.When using these values, the radius that is pushed down into the pore of mercury in pressure P is represented by following formula (3).
r(nm)＝7.5×10
8/P(Pa) (3)
That is, be related between the radius r of the pore that mercury applied pressure P and mercury are immersed, be pressed into curve according to the mercury that obtains thus, can obtain showing the pore distribution curve of the relation of the size of pore radius of sample and its volume.For example, make pressure P change to 100MPa, then can measure to the pore of the scope of about 7.5nm about 7500nm from 0.1MPa.
In addition, about mensuration boundary of the pore radius of measuring by mercury penetration method is that more than 2nm, the upper limit is greatly below 200 μ m greatly for lower limit, compare with nitrogen adsorption method described later, can be described as the analysis that distributes towards the pore of the bigger scope of pore radius ratio.
Can use the device of mercury porosimeter etc. to carry out by the mensuration that mercury penetration method is carried out.As the concrete example of mercury porosimeter, Autopore, the Poremaster that Quantachrome company makes etc. that can have Micromeritics company to make for example.
Particle characteristic of the present invention is that the mercury that obtains in this mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.8cm
3/ g is above, 3cm
3Below/the g.The mercury amount of being pressed into is usually at 0.8cm
3More than/the g, it is desirable at 0.85cm
3More than/the g, better is at 0.9cm
3More than/the g, it would be desirable at 1.0cm
3More than/the g, usually at 3cm
3Below/the g, it is desirable at 2.5cm
3Below/the g, better is at 2cm
3Below/the g, it would be desirable at 1.8cm
3Below/the g.If surpass the upper limit of this scope, then the space is excessive, and when particle of the present invention was used as positive electrode, positive active material reduced the filling rate of positive plate, and battery capacity is restricted.On the other hand, because if be lower than the lower limit of this scope, then intergranular space becomes too small, so particle of the present invention is made positive electrode when making battery, can hinder intergranular lithium diffusion, part throttle characteristics can descend.
When particle of the present invention was measured the pore distribution curve by mercury penetration method described later, the specific main peak of following explanation appearred usually.
In addition, in this manual, so-called " pore distribution curve " is that the radius with pore is a transverse axis, the value of total pore volume of the per unit weight (being generally 1g) of pore with its radius more than radius being carried out differential with the logarithm of pore radius is the longitudinal axis, mapping obtains, and is usually expressed as the chart of the point that links mapping.Especially below in the narration, will measure the pore distribution curve that obtains to particle of the present invention by mercury penetration method and suitably be called " the pore distribution curve that the present invention relates to ".
Again, " main peak " in this specification is meant the peak of the maximum in the peak that the pore distribution curve had, the peak except that main peak that " submaximum " expression pore distribution curve is had.
Again, " summit " in this specification is meant that the coordinate figure of the longitudinal axis in each peak that the pore distribution curve has obtains peaked point.
＜main peak 〉
The summit of the main peak that the pore distribution curve that the present invention relates to has is present in following scope, the pore radius is usually more than 300nm, it is desirable to more than 310nm, it would be desirable more than the 325nm, usually below 1000nm, it is desirable to below the 950nm, better is below the 900nm, better is below the 850nm, it would be desirable the scope that 800nm is following.If surpass the upper limit of this scope, when then porous matter particle of the present invention being made positive electrode manufacturing battery, might hinder the lithium diffusion in the anodal material, or conductive path is not enough, part throttle characteristics can descend.
On the other hand, if be lower than the lower limit of this scope, when then making positive pole with porous matter particle of the present invention, the requirement of possible electric conducting material and binding agent increases, and the restriction active material restricts battery capacity to the filling rate of positive plate (anodal collector).Again, along with micronize, the engineering properties of filming during coating is hard or crisp, and that films easily in then might the coiling operation when battery is assembled peels off.
What the pore capacity of the main peak that the pore distribution curve that the present invention relates to has was suitable is usually at 0.5cm
3More than/the g, it is desirable at 0.52cm
3More than/the g, better is at 0.55cm
3More than/the g, it would be desirable at 0.57cm
3More than/the g, again, usually at 1.5cm
3Below/the g, it is desirable at 1cm
3Below/the g, better is at 0.8cm
3Below/the g, it would be desirable at 0.7cm
3Below/the g.If surpass the upper limit of this scope, then the space is excessive, and when particle of the present invention was used as positive electrode, possible positive active material reduced the filling rate of positive plate, and battery capacity is restricted.On the other hand, because if be lower than the lower limit of this scope, then intergranular space becomes too small, so particle of the present invention is made positive electrode when making battery, might hinder intergranular lithium diffusion, part throttle characteristics can descend.
＜submaximum 〉
The pore distribution curve that the present invention relates to is characterised in that except above-mentioned main peak, also can have a plurality of submaximums, but is not present in the scope of the pore radius that 80nm is above, 300nm is following.
＜form
Lithium transition-metal based compound of the present invention is to have the compound that can take off embedding, embed the structure of Li ion, and sulfide, phosphate compounds, lithium-transition metal composite oxide etc. are arranged for example.As sulfide, have for example to have TiS
2Or MoS
2Deng two-dimensional layered structure compound, by formula M e
xMo
6S
8The Chevrel compound of the firm three-dimensional framework structure of (Me is to be the various transition metal of representative with Pb, Ag, Cu) expression etc.As phosphate compounds, the compound that belongs to olivine structural is arranged for example, generally by LiMePO
4(Me is the transition metal more than at least a kind) expression has LiFePO particularly for example
4, LiCoPO
4, LiNiPO
4, LiMnPO
4Deng.As lithium-transition metal composite oxide, there is the diffusible spinel structure that belongs to three-dimensional maybe can make the oxide of layer structure of diffusion of the two dimension of lithium ion for example.Compound with spinel structure is generally by LiMe
2O
4(Me is the transition metal more than at least a kind) expression has LiMn particularly for example
2O
4, LiCoMnO
4, LiNi
0.5Mn
1.5O
4, CoLiVO
4Deng.Compound with layer structure is generally by LiMeO
2(Me is the transition metal more than at least a kind) expression has LiCoO particularly for example
2, LiNiO
2, LiNi
1-xCo
xO
2, LiNi
1-x-yCo
xMn
yO
2, LiNi
0.5Mn
0.5O
2, Li
1.2Cr
0.4Mn
0.4O
2, Li
1.2Cr
0.4Ti
0.4O
2, LiMnO
2Deng.
Consider that from lithium ion diffusion aspect the desirable structure of lithium transition-metal based compound of the present invention is to comprise the crystalline texture that belongs to olivine structural, spinel structure, layer structure.Wherein desirable especially structure is to comprise the crystalline texture that belongs to layer structure.
Layer structure is carried out more detailed description here.Representational system of crystallization as having layer structure has LiCoO
2, LiNiO
2Like this belong to α-NaFeO
2The compound of type, they are hexagonal crystal systems, from its symmetry, belong to space group
[several 1]
R3m
(below, also note is made " stratiform R (3) m structure " sometimes).
Just, stratiform LiMeO2 is not limited to stratiform R (3) m structure.In addition the so-called LiMnO2 that is known as stratiform Mn is an orthorhombic system, is the lamellar compound of space group Pm2m, again, and the so-called Li that is known as 213 phases
2MnO
3Also can remember and make Li[Li
1/3Mn
2/3] O
2, be monoclinic space group C2/m structure, but still be by Li layer, [Li
1/3Mn
2/3] layer and the oxygen lamellar compound of pressing layer by layer.
Here, the chemical sense for the Li in the lithium transition-metal based compound of the present invention forms (z and x) is described in detail according to following.
Aforesaid layer structure may not be limited to R (3) m structure, but from electrochemical aspect of performance, it is desirable to belong to the compound of R (3) m structure.For ease of being described in detail, following layer structure being assumed to R (3) m structure describing.
In the present invention, even in having the lithium transition-metal of layer structure, it is desirable to supposition
With Li[Ni
1/2Mn
1/2] O
2Ratio be (1-3x) (1-y),
Li[Li
1/3Mn
2/3] O
2Ratio be 3x (1-y),
LiCoO
2Ratio be y
The stratiform lithium-transition metal composite oxide of solid solution, just with
[Li]
(3a)[Li
xNi
(1-3x)/2Mn
(1+x)/2)
(1-y)Co
y]
(3b)O
2(II)
Compound for basic structure.
Here, (3a), (3b) represents the different metal in stratiform R (3) the m structure respectively.
Just, in the present invention, the composition that better is with respect to (II) formula only excessively adds the Li of z mole and the compound of solid solution, by
[Li]
(3a)[Li
z/(2+z){(Li
xNi
(1-3x)/2Mn
(1+x)/2)
(1-y)Co
y}
2/(2+z)]
(3b)O
2 (I)
The lithium transition-metal of expression.
Wherein, 0 ≦ x ≦ 0.33,0 ≦ y ≦ 0.2 ,-0.02 ≦ z ≦ 0.2 (1-y) (1-3x), again, (3a), (3b) represent the different metal position in stratiform R (3) the m structure respectively.
In addition, this statement is identical with following statement, and in the stratiform lithium-transition metal composite oxide with LiMeO2 (Me is a transition metal) expression, the excessive Li solid solution of z molar part, is expressed as when (3b position) in the transition metal position
[Li]
(3a)[Li
z/(2+z)Me
2/(2+z)]
(3b)O
2。
With inductively coupled plasma emission spectroanalysis device (ICP-AES) each transition metal and Li are analyzed, tried to achieve the ratio of Li/Ni/Mn/Co, thereby calculate x, y, the z of the composition formula of above-mentioned lithium transition-metal based compound.Just, x, y can try to achieve by Ni/Mn and Co/Ni ratio, and z can try to achieve by the Li/Ni mol ratio, the Li/Ni mol ratio by
Li/Ni＝{2+2z+2x(1-y)}/{(1-3x)(1-y)}
Expression.
From the viewpoint of structure, we think that Li, the Li that x relates to that z relates to enter in identical transition metal position displacement.Here, the difference of the Li that relates to of the Li that relates to of x and z is whether whether the valence mumber of Ni is than 2 big (generating the Ni of 3 valencys).Just, x is and the value of Mn/Ni than (Mn enriches degree) interlock, and the Ni valence mumber can be only along with this x value change, and Ni is a divalent.On the other hand, z can catch the Li that the Ni valence mumber is risen, and z is the index of Ni valence mumber (ratio of Ni (III)).
In addition, if calculate the Ni valence mumber (m) that changes along with the variation of z, be 3 valencys then at the Co valence mumber by above-mentioned composition formula, the Mn valence mumber is under the prerequisite of 4 valencys, m=2z/{ (1-y) is (1-3x) }+2.This result of calculation means the Ni valence mumber not merely by the z decision, but the function of x and y.If z=0, then the valence mumber of Ni and x and y are irrelevant, are divalent.If z is a negative value, then mean the also not enough stoichiometric amount of Li amount that contains in the active material, the compound with excessive negative value might can not be brought into play effect of the present invention.On the other hand, even also mean identical z value, the composition of Mn abundant more (the x value is big more) and/or Co abundant more (the y value is big more), the Ni valence mumber is high more, and when being used for battery, speed characteristic and characteristics of output power uprise, but capacity descends easily.It can be said that to the upper limit of z value better be to stipulate as the function of x and y as mentioned above.
Again, if the y value is 0 ≦ y ≦ 0.2, is in the few scope of Co amount that then except cost reduced, also when using as the lithium secondary battery that is designed to charge at the high charge current potential, cycle characteristics and fail safe improved.
Like this, the lithium transition-metal based compound powder of above-mentioned composition was existed speed or the inferior shortcoming of power output performance in the past as the battery that positive active material uses, but lithium Ni-Co series composite oxides of the present invention, because the mercury amount of being pressed into when mercury is pressed into boosting in the curve is many, the pore capacity between crystalline particle is big, so when making battery with these composite oxides, owing to can increase the contact area between positive active material surface and the electrolyte, so can improve as positive active material necessary load characteristic.
＜lithium-nickel-manganese-cobalt system complex oxide 〉
Again, positive electrode material of lithium secondary cell of the present invention it is desirable to the lithium-nickel-manganese-cobalt system complex oxide with the lithium transition-metal based compound, and better is that structure is to contain the crystalline texture that belongs to layer structure, the composite oxides that composition is represented by following (I) formula.
Li[Li
Z/ (2+z){ (Li
xNi
(1-3x)/2Mn
(1+x)/2)
(1-y)Co
y}
2/ (2+z)] O
2Composition formula (I)
Wherein, 0 ≦ x ≦ 0.33
0≦y≦0.2
-0.02≦z≦0.2(1-y)(1-3x)
In above-mentioned composition formula (I), the value of z is more than-0.02, it is desirable to more than-0.01, better is more than 0, it is desirable to more 0.01 (1-y) (1-3x) more than, it would be desirable 0.02 (1-y) (1-3x) more than, 0.2 (1-y) (1-3x) below, it is desirable to 0.19 (1-y) (1-3x) below, better is 0.18 (1-y) (1-3x) below, it would be desirable 0.17 (1-y) (1-3x) below.If be lower than this lower limit, then conductivity descends, if surpass the upper limit, then might be too much in the amount of transition metal position displacement, and battery capacity reductions etc. cause using the decreased performance of the lithium secondary battery of this compound.
Again, if z is excessive, because the carbonic acid gas absorbability of active material powder increases, the easy carbonic acid gas that absorbs in the atmosphere then becomes.The result infers that containing concentration of carbon becomes big.
On the other hand, we infer if z is too small, then since be used to form based on the Li amount of the layer of layer structure obviously not enough, so occur that spinelle equates heterogeneous.
The value of x it is desirable to below 0.30 more than 0, below 0.33, and better is below 0.25, it would be desirable below 0.20.If be lower than this lower limit, the stability decreases under the high pressure then, degradation is descended in fail safe easily.If surpass the upper limit, then might be easy to generate heterogeneously, cause battery performance to descend easily.
The value of y it is desirable to more than 0.01 more than 0, below 0.2, it is desirable to below 0.18, and better is below 0.15, it would be desirable below 0.1.
As can be seen, in the compositing range of above-mentioned (I) formula, the lower limit of ratio is decided in the approaching more conduct of z value, speed characteristic when making battery and characteristics of output power are often low more, on the contrary, the z value is more near the upper limit, and speed characteristic when making battery and characteristics of output power are often high more, but then, capacity often descends.Again, as can be seen, the x value is more near lower limit, and promptly manganese/nickle atom then can increase capacity than more near 1 under low charging voltage, but cycle characteristics and fail safe that the battery of high charge voltage is set often descend, on the contrary, the x value is more near the upper limit, and cycle characteristics and fail safe that the battery of high charge voltage is set improve, but then, discharge capacity, speed characteristic and characteristics of output power often descend.As can be seen, the y value is more near lower limit, the such part throttle characteristics of speed characteristic when making battery and characteristics of output power is often low more, on the contrary, the y value is more near the upper limit, and speed characteristic when making battery and characteristics of output power are often high more, but then, cycle characteristics and fail safe when being arranged on high charge voltage often descend, and cost of material improves.Particularly through intently inquiring into research, break this opposite tendency, the result finishes the present invention, and described composition parameter x, y, z are in prescribed limit, and this is very important.
In addition, in the composition of described formula (I), the atomic ratio of oxygen amount is for conveniently being designated as 2, and indefinite for example the atomic ratio of oxygen can be in 2 ± 0.1 scope than property but a little also have.
When lithium transition-metal based compound of the present invention is lithium-nickel-manganese-cobalt system complex oxide powder, also can in its structure, import substitutional element again.As substitutional element, can select more than any among Al, Fe, Ti, Mg, Cr, Ca, Cu, Zn, Nb, Zr, Mo, W, the Sn.The scope of these substitutional elements below 20 atom % suitably replaced with Ni, Mn, Co element.
＜particle of the present invention brings the reason of above-mentioned effect 〉
We infer, because the pore volume appropriateness of lithium composite xoide particle of the present invention, more, so when making battery with this lithium composite xoide particle, can increase the contact area of positive active material surface and electrolyte, therefore, improved as the essential part throttle characteristics of positive active material.
＜other desirable modes 〉
In the record below, other characteristic of the present invention is also had been described in detail, but above be enough desirable mode, as long as possess above-mentioned feature, do not do special restriction for other characteristics of particle of the present invention.＜median particle diameter and 90% accumulation particle diameter (D
90)
The median particle diameter of lithium transition-metal based compound powder of the present invention is usually more than 0.6 μ m, it is desirable to more than 0.8 μ m, better is more than the 1 μ m, it would be desirable more than 1.1 μ m, usually below 5 μ m, it is desirable to below 4.5 μ m, better is below 4 μ m, better is below 3.5 μ m, it would be desirable below 3 μ m.If be lower than lower limit, then coating may have problems when positive active material forms, if surpass the upper limit, then may cause battery performance to descend.
Again, 90% of the second particle of lithium transition-metal based compound powder of the present invention accumulation particle diameter (D
90) usually below 10 μ m, it is desirable to below 9 μ m, better is below 8 μ m, it would be desirable below 7 μ m, more than 1 μ m, it is desirable to more than 2 μ m usually, better is more than the 3 μ m, it would be desirable more than 3.5 μ m.If surpass the above-mentioned upper limit, then may cause battery performance to descend, if be lower than lower limit, then coating may have problems when positive active material forms.
In addition, in the present invention, as the median particle diameter and the 90% accumulation particle diameter (D of average grain diameter
90) measure by known laser diffraction/diffuse transmission type particle size distribution device and to obtain, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.In the present invention, be to disperse (power output 30W, frequency 22.5kHz) afterwards, to measure at the ultrasonic wave that the dispersant that uses 0.1 weight % sodium hexametaphosphate solution to use when measuring carried out 5 minutes.
＜volume density 〉
The volume density of positive electrode material of lithium secondary cell usefulness lithium transition-metal based compound powder of the present invention more than 0.5g/cc, it is desirable to more than 0.6g/cc usually, and better is more than 0.7g/cc, it would be desirable more than 0.8g/cc.If be lower than this lower limit, bring bad influence then may for powder filled property and electrode preparation, again, with its as the positive pole of active material usually below 1.5g/cc, it is desirable to below 1.4g/cc, better is below 1.3g/cc, it would be desirable below 1.2g/cc.Volume density is desirable to improving powder filled property and electrode density then if surpass this upper limit, but then, might make specific area low excessively, and battery performance descends.
In addition, in the present invention, volume density is tried to achieve like this, as the lithium transition-metal based compound, the lithium-nickel-manganese-cobalt system complex oxide powder of 5～10g is put into the glass cylinder of 10ml, powder filled density (drawing liquid density) g/cc when obtaining with the stroke drawing liquid of about 20mm 200 times.
＜BET specific area 〉
The BET specific area of lithium nickel manganese composite oxide powder body of the present invention is usually at 1.5m
2More than/the g, it is desirable at 1.7m
2More than/the g, that better is 2m
2More than/the g, it would be desirable 2.5m
2More than/the g, usually at 5m
2Below/the g, it is desirable at 4.5m
2Below/the g, better is at 4m
2Below/the g, it would be desirable at 3.5m
2Below/the g.If the BET specific area is less than this scope, and then battery performance descends easily, if greater than, then being difficult to improve volume density, positive active material may be easy to generate the problem of coating when forming.
In addition, the BET specific area can be measured by known BET formula powder specific area measuring device.In the present invention, use the AMS8000 type automatic powder specific area measuring device of big storehouse reason development, nitrogen is used in adsorbed gas, and helium is used in carrier gas, measures by the BET1 point type method that continuous flow method carries out.Specifically, pass through mist, under 150 ℃ temperature, the powder sample is carried out heat de-airing, then, be cooled to the liquid nitrogen temperature, after absorption nitrogen/helium mix gas, utilize water that it is heated to room temperature, slough the nitrogen of absorption, utilize thermal conductivity detector to detect its amount, calculate the specific area of sample thus.
＜carbon containing concentration C 〉
The C value of lithium transition-metal based compound powder of the present invention is usually more than 0.005 weight %, it is desirable to more than 0.01 weight %, better is more than the 0.015 weight %, it would be desirable more than the 0.02 weight %, usually below 0.2 weight %, it is desirable to below the 0.15 weight %, better is below the 0.12 weight %, it would be desirable below the 0.1 weight %.If be lower than lower limit, then battery performance may descend, if surpass the upper limit, produces the expansion increase that gas causes in the time of then may making battery, degradation under the battery performance.
In the present invention, shown in the project of embodiment, measure as described later, try to achieve the carbon containing concentration C of lithium transition-metal based compound powder by burning (dielectric heating oven formula) infrared absorption method in the Oxygen Flow.
In addition, the concentration of carbon that contains from the lithium lithium transition-metal based compound powder of trying to achieve by carbon analysis described later, can be considered as the information of the adhesion amount of C value representation relevant carbonate compound, particularly lithium carbonate, this is because this carbon of supposition all roughly exists as carbonate from the numerical value of carbon ion, carbon in the lithium transition-metal based compound powder of ion chromatography analysis.
On the other hand, as lithium ferric phosphate based compound (general formula: LiFePO
4) like this, make the electrical conductance of active material itself extremely low compound and carbon compound, give conductivity, even perhaps electrical conductance is than higher transition metal based compound, as the gimmick of further raising electrical conductance, also carry out compoundization processing, in these cases with conductive carbon, sometimes detect the C amount that surpasses described prescribed limit, but be not limited to described prescribed limit through the C value of the lithium transition-metal based compound powder of such processing.
On the other hand, in the lithium transition-metal based compound powder of the present invention's regulation, the lithium that exists as carbonate is a minute quantity, and the lithium that does not influence The composite oxide powder regulation is formed (x, z).
＜average primary particle diameter 〉
The average primary particle diameter of lithium transition-metal based compound body of the present invention it is desirable to more than the 0.05 μ m, below the 1 μ m.What lower limit was better is more than the 0.1 μ m, and better is more than the 0.15 μ m, it would be desirable more than the 0.2 μ m, and again, what the upper limit was better is below the 0.8 μ m, and better is below the 0.7 μ m, it would be desirable below the 0.6 μ m.As if surpassing the above-mentioned upper limit, bring bad influence can for powder filled property, specific area descends, and therefore might improve the possibility of the battery performance decline of speed characteristic and characteristics of output power etc.If be lower than above-mentioned lower limit, then crystallization is undeveloped, therefore might produce the low of inferior quality problem of the invertibity that discharges and recharges.
In addition, the average grain diameter of the primary particle among the present invention is with the observed average diameter of scanning electron microscope (SEM), uses 30,000 times SEM image, and the mean value that can be used as the particle diameter of about 10～30 primary particle is tried to achieve.
＜specific insulation 〉
The lower limit of the value of the specific insulation when compressing lithium transition-metal based compound of the present invention with the pressure of 40MPa it is desirable to 1 * 10
3More than the Ω cm, better is 5 * 10
3More than the Ω cm, it is desirable to 1 * 10 more
4More than the Ω cm.The upper limit it is desirable to 5 * 10
7Below the Ω cm, better is 1 * 10
7Below the Ω cm, it is desirable to 5 * 10 more
6Below the Ω cm.This specific insulation is if surpass this upper limit, and the part throttle characteristics when then making battery might descend.On the other hand, if specific insulation is lower than this lower limit, the fail safe when then making battery might descend.
In addition, in the present invention, the specific insulation of lithium transition-metal based compound powder is to measure under following condition, use the four point probe ring electrode, electrode gap 5.0mm, electrode radius 1.0mm, radius of specimen 12.5mm, applying voltage clipper is 90V, measures under the state that compresses lithium transition-metal based compound powder with 40MPa pressure.For example use powder resistance determinator (for example, the ロ レ ス that DIA INSTRUMENTS company makes-GP powder resistance is measured system), by the powder testing apparatus, can be to add the mensuration that the powder of depressing carries out specific insulation in regulation.
＜powder x-ray diffraction peak 〉
Lithium transition-metal based compound powder of the present invention it is desirable in the x-ray diffractogram of powder picture that uses CuK α line, does not have the diffraction maximum in 2 θ=31 ± 1 °.Here, " do not have " to comprise yet and have not the meaning of bringing the diffraction maximum of bad influence for battery performance of the present invention.Just, this diffraction maximum derives from the spinelle phase, and if comprise the spinelle phase, the capacity when then making battery, speed characteristic, high temperature preservation characteristics or high-temperature cycle descend.Therefore can have for diffraction maximum brings the diffraction maximum of bad influence for the battery performance of the present application, but (003) peak area that it is desirable to 2 θ=18.5 ± 1 ° is a benchmark, the ratio of the diffraction maximum area in 2 θ=31 ± 1 ° is below 0.5%, better is below 0.2%, and it is desirable to this diffraction maximum does not especially have fully.Just, this diffraction maximum derives from the spinelle phase, and if comprise the spinelle phase, the capacity when then making battery, speed characteristic, high temperature preservation characteristics or high-temperature cycle often descend, and therefore it is desirable to not this diffraction maximum.
Then, the positive electrode material of lithium secondary cell with following characteristics among the present invention is narrated in further detail with lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, compound by following composition formula (I ') expression constitutes, contain the crystalline texture that belongs to layer structure, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is FWHM (110), with 0.01 ≦ FWHM (110) ≦ 0.2 expression.
Li[Li
z′/(2+z′){(Ni
(1+y′)/2Mn
(1-y′)/2)
1-x′Co
x’}
2/(2+z＇)]O
2...(I′)
Wherein, in composition formula (I '), 0 ≦ x ′ ≦ 0.1 ,-0.1 ≦ y ′ ≦ 0.1, (1-x ') (0.05-0.98y ') ≦ z ′ ≦ (1-x ') (0.15-0.88y ')
[lithium-nickel-manganese-cobalt system complex oxide powder]
Positive electrode material of lithium secondary cell of the present invention lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, compound by following composition formula (I ') expression constitutes, and contain the crystalline texture that belongs to layer structure, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is FWHM (110), with 0.01 ≦ FWHM (110) ≦ 0.2 expression.
Li[Li
z′/(2+z′){(Ni
(1+y′)/2Mn
(1-y′)/2)
1-x′Co
x’}
2/(2+z′)]O
2...(I′)
Wherein, in composition formula (I '),
0≦x′≦0.1，
-0.1≦y′≦0.1，
(1-x′)(0.05-0.98y′)≦z′≦(1—x′)(0.15-0.88y′)。
＜form and crystalline texture
In above-mentioned (I ') formula, the value of x it is desirable to more than 0.01 more than 0, and better is more than 0.02, and better is more than 0.03, it would be desirable more than 0.04, below 0.1, it is desirable to below 0.099.
The value of y ' it is desirable to more than-0.08 more than-0.1, and better is more than-0.05, it would be desirable more than-0.03, below 0.1, it is desirable to below 0.08, and better is below 0.05, it would be desirable below 0.03.
Z ' value is more than (1-x ') (0.05-0.98y '), it is desirable to more than (1-x ') (0.06-0.98y '), better is more than (1-x ') (0.07-0.98y '), it would be desirable more than (1-x ') (0.08-0.98y '), below (1-x ') (0.15-0.88y '), it is desirable to below (1-x ') (0.145-0.88y '), better is below (1-x ') (0.14-0.88y '), it would be desirable below (1-x ') (0.13-0.88y ').If z ' is lower than this lower limit, then conductivity descends, if surpass the upper limit, then might be too much and battery capacity reduction etc. in the amount of transition metal position displacement, and cause using the decreased performance of the lithium secondary battery of this compound.Again, if z ' is excessive, because the carbonic acid gas absorbability of active material powder increases, the easy carbonic acid gas that absorbs in the atmosphere then becomes.The result infers that containing concentration of carbon becomes big.
As can be seen, in the compositing range of above-mentioned (I ') formula, the lower limit of ratio is decided in the approaching more conduct of z value, speed characteristic when making battery and characteristics of output power are often low more, on the contrary, z ' is worth more near the upper limit, and speed characteristic when making battery and characteristics of output power are often high more, but then, capacity often descends.Again, as can be seen, y ' value is more near lower limit, and promptly manganese/nickle atom is then hanging down increase capacity under the charging voltage than more little, but cycle characteristics and fail safe that the battery of high charge voltage is set often descend, on the contrary, y ' value is more near the upper limit, and cycle characteristics and fail safe that the battery of high charge voltage is set improve, but then, discharge capacity, speed characteristic and characteristics of output power often descend.As can be seen, x ' value is more near lower limit, the such part throttle characteristics of speed characteristic when making battery and characteristics of output power is often low more, on the contrary, x ' value is more near the upper limit, and speed characteristic when making battery and characteristics of output power are often high more, but if surpass this upper limit, cycle characteristics and fail safe when then being arranged on high charge voltage often descend, and cost of material improves.This is an important inscape of the present invention in prescribed limit for above-mentioned composition parameter x ', y ', z '.
In addition, in the composition of described formula (I '), the atomic ratio of oxygen amount does 2 for convenient note, but indefinite ratio property a little also can be arranged.For example, the atomic ratio of oxygen can be in 2 ± 0.1 scope.
Again, lithium-nickel-manganese-cobalt system complex oxide powder of the present invention can import different elements.As different elements, can be from B, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Ba, Ta, W, Ir, Pt, Au, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, N, F, P, S, Cl, Br, I any more than in select.These different elements can enter in the crystalline texture of lithium-nickel-manganese-cobalt system complex oxide, perhaps also can not enter in the crystalline texture of lithium-nickel-manganese-cobalt system complex oxide, are present in unevenly on its particle surface or the grain boundary etc. as monomer or compound.
The formation of lithium-nickel-manganese-cobalt system complex oxide of the present invention is to contain the crystalline texture that belongs to layer structure.
Here, layer structure is narrated in further detail.Representational system of crystallization as having layer structure has LiCoO
2, LiNiO
2Like this belong to α-NaFeO
2The compound of type, these are hexagonal crystal systems, see from its symmetry to belong to space group " stratiform R (3) m structure " (, R (3) m structure and above-mentioned formula (4) synonym on the layer) here.
Just, stratiform LiMeO
2Be not limited to stratiform R (3) m structure.In addition the so-called LiMnO that is known as stratiform Mn
2Be orthorhombic system, be the lamellar compound of space group Pm2m, again, the so-called Li that is known as 213 phases
2MnO
3Also can remember and make Li[Li
1/3Mn
2/3] O
2, be monoclinic space group C2/m structure, but still be by Li layer, [Li
1/3Mn
2/3] layer and oxygen press the lamellar compound that forms layer by layer.
Here, the chemical sense for the Li in the lithium-nickel-manganese-cobalt system complex oxide of the present invention forms (z ' and x ') is described in detail by following.
Aforesaid layer structure may not be limited to R (3) m structure, but considers from electrochemical aspect of performance, it is desirable to belong to the compound of R (3) m structure.
With inductively coupled plasma emission spectroanalysis device (ICP-AES) each transition metal and Li are analyzed, tried to achieve the ratio of Li/Ni/Mn/Co, thereby calculate x ', y ', the z ' of the composition formula of above-mentioned lithium-nickel-manganese-cobalt system complex oxide.
From the viewpoint of structure, we think that the Li that z ' relates to enters in identical transition metal position displacement.Here, the Li related according to z ', according to the principle of neutral charge, the average valence mumber of Ni is than 2 big (producing the Ni of 3 valencys).Z ' rises the average valence mumber of Ni, so z ' is the index of Ni valence mumber (ratio of Ni (III)).
In addition, if calculate the Ni valence mumber (m) that changes along with the variation of z, be that 3 valencys, Mn valence mumber are under the prerequisite of 4 valencys then at the Co valence mumber from above-mentioned composition formula, m=2z '/{ (1-y ') (1-3x ') }+2.This result of calculation means the Ni valence mumber not merely by z ' decision, but the function of x ' and y '.If z '=0 and y '=0, then the valence mumber of Ni and x ' are irrelevant, are divalent.If z ' is a negative value, then mean the also not enough stoichiometric amount of Li amount that contains in the active material, the compound with excessive negative value might can not be brought into play effect of the present invention.On the other hand, even mean that also z ' value is identical, the composition of Ni abundant more (y ' value is big more) and/or Co abundant more (x ' value is big more), the Ni valence mumber is high more, and when being used for battery, speed characteristic and characteristics of output power uprise, but capacity descends easily.It can be said that to the upper and lower bound of z ' value better be to stipulate as the function of x ' and y '.
Again, if to be worth be 0 ≦ x ’ ≦ 0.1 to x ', be in the few scope of Co amount, then except cost reduced, also when using as the lithium secondary battery that is designed to charge at the high charge current potential, charge/discharge capacity, cycle characteristics and fail safe improved.
Like this, the lithium-nickel-manganese-cobalt system complex oxide powder of above-mentioned composition was existed speed or the inferior shortcoming of power output performance in the past as the battery that positive active material uses, but lithium-nickel-manganese-cobalt system complex oxide of the present invention, owing to be high crystallization, it is few suppressing the heterogeneous ratio that exists again, and the mercury amount of being pressed into when mercury is pressed into boosting in the curve is many, pore capacity between crystalline particle is big, so when making battery with these composite oxides, owing to can increase the contact area between positive active material surface and electrolyte or conductive auxiliary agent, so can improve as positive active material necessary load characteristic.
＜powder x-ray diffraction peak 〉
Lithium lithium-nickel-manganese-cobalt system complex oxide powder of the present invention, it is characterized in that, in the powder X-ray ray image that uses CuK α line, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is FWHM (110), be in 0.01 ≦ FWHM (scope of 110) ≦ 0.2.
Because the half width of generally using the X-ray diffraction peak is as crystalline yardstick, so the inventor has intently carried out inquiring into research to crystallinity and battery performance related.The material that the value that found that near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is in the scope of regulation shows good battery performance.
In the present invention, FWHM (110) is usually more than 0.01, it is desirable to more than 0.05, better is more than 0.10, and better is more than 0.12, it would be desirable more than 0.14, below 0.2, better is below 0.196, and better is below 0.19, it would be desirable below 0.185.
Again, lithium-nickel-manganese-cobalt system complex oxide powder of the present invention, it is desirable to, in the powder x-ray diffraction that uses CuK α line is measured, the angle of diffraction 2 θ are near (018) diffraction maximum 64 °, near (110) diffraction maximum 64.5 ° and near (113) diffraction maximum 68 °, high corner side at separately summit does not have the heterogeneous diffraction maximum that causes, when perhaps having the heterogeneous diffraction maximum that causes, the integrated intensity of heterogeneous peak and the diffraction maximum of original crystalline phase is than respectively in following scope.
0≦I
018*/I
018≦0.20
0≦I
110*/I
110≦0.25
0≦I
113*/I
113≦0.30
Here, I
018, I
110, I
113The integrated intensity of representing (018), (110), (113) diffraction maximum respectively, I
018*, I
110*, I
113*Express the integrated intensity of the heterogeneous diffraction maximum that causes of the high corner side of the summit of (018), (110), (113) diffraction maximum now respectively.
This derives from the details of reason material of heterogeneous diffraction maximum and unclear, but if comprises declines such as heterogeneous, the capacity when then making battery, speed characteristic, cycle characteristics.Therefore can have for diffraction maximum and bring the diffraction maximum of bad influence for the battery performance of the present application, but the ratio that it is desirable to is in described scope, the heterogeneous diffraction maximum that causes is generally I with the integrated intensity ratio of separately diffraction maximum
018*/ I
018≦ 0.20, I
110*/ I
110≦ 0.25, I
113*/ I
113≦ 0.30, it is desirable to I
018*/ I
018≦ 0.15, I
110*/ I
110≦ 0.20, I
113*/ I
113≦ 0.25, that better is I
018*/ I
018≦ 0.10, I
110*/ I
110≦ 0.16, I
113*/ I
113≦ 0.20, that better is I
018*/ I
018≦ 0.05, I
110*/ I
110≦ 0.10, I
113*/ I
113≦ 0.15, it would be desirable does not have the heterogeneous diffraction maximum that causes.
The pore characteristics that＜mercury penetration method obtains 〉
Positive electrode material of lithium secondary cell of the present invention it is desirable to satisfy certain conditions in the mensuration that mercury penetration method is carried out with lithium-nickel-manganese-cobalt system complex oxide powder.
The mercury penetration method that the evaluation of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention is adopted as previously mentioned.
Particle of the present invention it is desirable to, and the mercury that obtains in this mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.7cm
3/ g is above, 1.5cm
3Below/the g.What the mercury amount of being pressed into was better is at 0.74cm
3More than/the g, better is at 0.8cm
3More than/the g, it would be desirable at 0.9cm
3More than/the g, better is at 1.4cm
3Below/the g, better is at 1.3cm
3Below/the g, it would be desirable at 1.2cm
3Below/the g.If surpass the upper limit of this scope, then the space is excessive, and when lithium-nickel-manganese-cobalt system complex oxide powder of the present invention was used as positive electrode, positive active material reduced at the filling rate of positive plate (anodal collector), and battery capacity is restricted.On the other hand, if be lower than the lower limit of this scope, then intergranular space is too small, when therefore lithium-nickel-manganese-cobalt system complex oxide powder of the present invention being made battery as positive electrode, can hinder intergranular lithium diffusion, and part throttle characteristics descends.
Again, when with above-mentioned mercury penetration method lithium-nickel-manganese-cobalt system complex oxide powder of the present invention being carried out pore distribution curve mensuration, usually, the specific main peak of following explanation appears.
In addition, so-called " pore distribution curve ", " main peak ", " submaximum ", " summit " are as mentioned above.
＜main peak 〉
It is the above scope of 300nm that the main peak that pore distribution curve involved in the present invention has is present in the pore radius usually, it is desirable to more than 350nm, it would be desirable more than 400nm, again, usually below 1000nm, it is desirable to below 980nm, better is below 970nm, better is below 960nm, it would be desirable below 950nm.If surpass the upper limit of this scope, when lithium-nickel-manganese-cobalt system complex oxide powder then of the present invention is made battery as positive electrode, might hinder the lithium diffusion in the positive electrode, perhaps conductive path is not enough, and part throttle characteristics descends.On the other hand, if be lower than the lower limit of this scope, when then making positive pole with lithium-nickel-manganese-cobalt system complex oxide powder of the present invention, the necessary amounts of possible electric conducting material and binding agent increases, positive active material reduces at the filling rate of positive plate (anodal collector), and battery capacity is restricted.Again, along with micronize, the engineering properties of filming during coating is hard or crisp, films easily in then might the coiling operation when battery is assembled and peels off.
The pore distribution curve that the present invention relates to have more than pore radius 300nm, exist below the 1000nm summit main peak the pore capacity suitable be usually at 0.3cm
3More than/the g, it is desirable at 0.35cm
3More than/the g, better is at 0.4cm
3More than/the g, it would be desirable at 0.5cm
3More than/the g, again, usually at 1.0cm
3Below/the g, it is desirable at 0.8cm
3Below/the g, better is at 0.7cm
3Below/the g, it would be desirable at 0.6cm
3Below/the g.If surpass the upper limit of this scope, then the space is excessive, when lithium-nickel-manganese-cobalt system complex oxide powder of the present invention is used as positive electrode, might reduce at the filling rate of positive plate by positive active material, and battery capacity is restricted.On the other hand, if be lower than the lower limit of this scope, then intergranular space is too small, when therefore lithium-nickel-manganese-cobalt system complex oxide powder of the present invention being made battery as positive electrode, might hinder the lithium diffusion between second particle, and part throttle characteristics descends.
＜submaximum 〉
The pore distribution curve that the present invention relates to also can have some submaximums except above-mentioned main peak, but it is desirable to not be present in the scope of pore radius more than 80nm, below the 300nm.
＜lithium-nickel-manganese-cobalt system complex oxide powder of the present invention brings the reason of above-mentioned effect 〉
Lithium-nickel-manganese-cobalt system complex oxide powder of the present invention brings the detailed reason of above-mentioned effect also unclear, but we infer, be because crystallinity is highly developed, and the composition aspect is also in only zone, and pore volume is suitably many, so when making battery with this, can increase the contact area of positive active material surface and electrolyte, therefore, improved as the essential part throttle characteristics of positive active material.
[mode that other are desirable]
In the record below, other suitable characteristics to lithium-nickel-manganese-cobalt system complex oxide powder of the present invention are illustrated, but be enough desirable mode below, as long as possess above-mentioned feature, do not do special restriction for other characteristics of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention.
＜median particle diameter and 90% accumulation particle diameter (D
90)
The median particle diameter of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention is usually more than 1 μ m, it is desirable to more than 1.2 μ m, better is more than the 1.5 μ m, it would be desirable more than 2 μ m, usually below 5 μ m, it is desirable to below 4.5 μ m, better is below 4 μ m, better is below 3.8 μ m, it would be desirable that below 3.5 μ m if be lower than this lower limit, then the coating when positive active material forms may have problems, if surpass the upper limit, then may cause battery performance to descend.
Again, 90% of the second particle of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention accumulation particle diameter (D
90) usually below 10 μ m, it is desirable to below 9 μ m, better is below 8 μ m, it would be desirable below 7 μ m, more than 1 μ m, it is desirable to more than 2 μ m usually, better is more than the 3 μ m, it would be desirable more than 3.5 μ m.If surpass the above-mentioned upper limit, then may cause battery performance to descend, if be lower than lower limit, then when positive active material formed, coating may have problems.
In addition, accumulate particle diameter (D as the median particle diameter and 90% of average grain diameter
90) can be with measuring with aforementioned the same method.
＜volume density 〉
The volume density of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention is usually more than 0.5g/cc, it is desirable to more than 0.6g/cc, better is more than 0.7g/cc, it would be desirable more than 0.8g/cc, usually below 1.7g/cc, it is desirable to below 1.6g/cc, better is below 1.5g/cc, it would be desirable below 1.3g/cc.Volume density is desirable to improving powder filled property and electrode density then if surpass this upper limit, but then, might make specific area low excessively, and battery performance descends.Volume density brings bad influence then might for powder filled property and electrode preparation if be lower than this lower limit.
Volume density can be measured with method as hereinbefore.
＜BET specific area 〉
The BET specific area of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention is usually at 1.4m
2More than/the g, it is desirable at 1.5m
2More than/the g, that better is 1.6m
2More than/the g, it would be desirable 1.7m
2More than/the g, usually at 3m
2Below/the g, it is desirable at 2.8m
2Below/the g, better is at 2.5m
2Below/the g, it would be desirable at 2.3m
2Below/the g.If the BET specific area is less than this scope, and then battery performance descends easily, if greater than, then being difficult to improve volume density, positive active material may be easy to generate the problem of coating when forming.
The BET specific area can be measured with method as hereinbefore.
＜carbon containing concentration C 〉
Carbon containing concentration C (weight %) value of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention is usually more than 0.005 weight %, it is desirable to more than 0.01 weight %, better is more than the 0.015 weight %, it would be desirable more than the 0.02 weight %, usually below 0.05 weight %, it is desirable to below the 0.045 weight %, better is below the 0.04 weight %, it would be desirable below the 0.035 weight %.If be lower than lower limit, then battery performance may descend, if surpass the upper limit, gas produces and the expansion that causes increases degradation under the battery performance in the time of then might making battery.
The carbon containing concentration C of lithium-nickel-manganese-cobalt system complex oxide powder can be with measuring with above-mentioned same method.
On the other hand, gimmick as further raising electrical conductance, when carrying out the compoundization processing with conductive carbon, detect the C amount that surpasses described prescribed limit sometimes, but the C value of the lithium-nickel-manganese-cobalt system complex oxide powder in the situation of implementing such processing is not limited to described prescribed limit.
On the other hand, in the lithium-nickel-manganese-cobalt system complex oxide powder of the present invention's regulation, the lithium that exists as carbonate is a minute quantity, and the lithium that does not influence The composite oxide powder regulation is formed (z).
＜average primary particle diameter 〉
The average primary particle diameter of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention it is desirable to more than the 0.05 μ m, below the 1 μ m.What lower limit was better is more than the 0.1 μ m, and better is more than the 0.15 μ m, it would be desirable more than the 0.2 μ m, and again, what the upper limit was better is below the 0.8 μ m, and better is below the 0.7 μ m, it would be desirable below the 0.5 μ m.
If average primary particle diameter surpasses the above-mentioned upper limit, bring bad influence then can for powder filled property, degradation under the specific area, so the possibility that the battery performance of speed characteristic and characteristics of output power etc. descends might improve.If be lower than above-mentioned lower limit, then crystallization is undeveloped, therefore might produce the low of inferior quality problem of the invertibity that discharges and recharges.
Average primary particle diameter (average grain diameter of primary particle) can be with measuring with aforementioned the same method.
＜specific insulation 〉
The lower limit of the value of the specific insulation when compressing lithium-nickel-manganese-cobalt system complex oxide powder of the present invention with the pressure of 40MPa it is desirable to 1 * 10
3More than the Ω cm, better is 5 * 10
3More than the Ω cm, it is desirable to 1 * 10 more
4More than the Ω cm.The upper limit it is desirable to 1 * 10
6Below the Ω cm, better is 5 * 10
5Below the Ω cm, it is desirable to 1 * 10 more
6Below the Ω cm.This specific insulation is if surpass this upper limit, and the part throttle characteristics when then making battery might descend.On the other hand, if specific insulation is lower than this lower limit, the fail safe when then making battery might descend.
Specific insulation can be measured with method as hereinbefore.
Then, positive electrode material of lithium secondary cell with following feature is described in detail with lithium transition-metal based compound powder, it is characterized in that, with the lithium transition-metal based compound with the function that can embed the removal lithium embedded ion is main component, the grain growth when in this main component raw material, adding the inhibition calcining more than at least a kind and the additive of sintering, the ratio of the integral molar quantity of the transition metal in the addition of this additive and the main component raw material is at 0.01 mole more than the % and less than 2 moles of %, calcines then and obtains.
[lithium transition-metal based compound powder]
Positive electrode material of lithium secondary cell of the present invention is with lithium transition-metal based compound powder (following be called sometimes " positive active material "), it is characterized in that, with the transistion metal compound with the function that can embed the removal lithium embedded ion is main component, the grain growth when in this main component raw material, adding the inhibition calcining more than at least a kind and the additive of sintering, the ratio of the integral molar quantity of the transition metal in the addition of this additive and the main component raw material is at 0.01 mole more than the % and less than 2 moles of %, calcines then and obtains.
＜lithium transition-metal based compound 〉
In the present invention, so-called " lithium transition-metal based compound " is to have the compound that can take off embedding, embed the structure of Li ion, for example, sulfide, phosphate compounds and lithium-transition metal composite oxide etc. arranged for example.As sulfide, phosphate compounds and lithium-transition metal composite oxide, material is as mentioned above arranged for example.
Consider that from lithium ion diffusion aspect lithium transition-metal based compound powder of the present invention it is desirable to contain the crystalline texture that belongs to olivine structural, spinel structure, layer structure and constitutes.Wherein it is desirable to especially comprise the crystalline texture that belongs to layer structure and constitute.
Again, lithium transition-metal based compound powder of the present invention can import different elements.As different elements, can be from B, Na, Mg, Al, Si, K, Ca, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Ru, Rh, Pd, Ag, In, Sn, Sb, Te, Ba, Os, Ir, Pt, Au, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, N, F, P, S, Cl, Br, I any more than in select.These different elements can enter in the crystalline texture of lithium transition-metal based compound, perhaps also can not enter in the crystalline texture of lithium transition-metal based compound, are present in unevenly on its particle surface or the grain boundary etc. as monomer or compound.
Grain growth during＜inhibition calcining and the additive of sintering 〉
In the present invention, so-called " the grain growth when suppressing calcining and the additive of sintering " is meant the material with following effect, between the primary particle of the positive active material when promptly suppressing high-temperature calcination or the sintering between second particle etc., suppress the growth of active material particle, reach high crystallization, obtain having the powder properties in many small spaces.
For example, when manufacturing is suitable for the lithium-nickel-manganese-cobalt system complex oxide powder of compositing area with composition formula (I ＂) regulation of the present invention, under the temperature more than 970 ℃, aggregate to the pressed powder raw material is calcined, thus, can obtain crystallinity positive active material highly developed, desirable crystalline texture concerning battery performance., on the other hand,, therefore become the unfavorable powder properties of battery performance because grain is grown up, sintering also carries out significantly easily.That is, improving both simultaneously is situation of difficult very, but calcines by adding " grain when suppressing calcining is grown up and the additive of sintering ", can overcome this balance and concern.
In the present invention, grain when suppressing calcining is grown up and the additive of sintering and the specific compound that adds manifest that grain when suppressing calcining is grown up and the mechanism of the effect of sintering is also unclear, but from as embodiment, by obtaining valence is that the compound that the metallic element of 5 valencys or 6 valencys constitutes manifests effect jointly, these are that any one of cation element that constitutes the lithium transition-metal based compound all can stably obtain the high price state of 5～7 different valencys, by solid phase reaction solid solution hardly, be present in to heterogeneity the surface or the grain circle of lithium transition-metal based compound particle as a result.Therefore, infer that the material that the contact to each other of obstruction active substances in cathode materials particle causes moves, and suppresses the growth and the sintering of particle.
Kind as additive, get final product so long as manifest the material of above-mentioned effect, its kind is had no particular limits, but it is desirable to contain the compound of the element that is selected from stable condition Mo, the W of high price, Nb, Ta, Re etc., also being used in combination more than 2 kinds suitably these elements.Usually, the compound that contains these elements uses oxide material usually.
As the exemplary compounds of additive, MoO, MoO are arranged for example
2, MoO
3, MoO
x, Mo
2O
3, Mo
2O
5, Li
2MoO
4, WO, WO
2, WO
3, WO
x, W
2O
3, W
18O
49, W
20O
58, W
24O
70, W
25O
73, W
40O
118, Li
2WO
4, NbO, NbO
2, Nb
2O, Nb
2O
5, Nb
4O, Nb
6O, LiNbO
3, TaO, TaO
2, Ta
2O
5, LiTaO
3, ReO
2, ReO
3, Re
2O
3Deng, desirable have MoO for example
3, Li
2MoO
4, WO
3, Li
2WO
4, LiNbO
3, Ta
2O
5, LiTaO
3, ReO
3, desirable especially have WO for example
3, Li
2WO
4, ReO
3
Scope as the addition of these additives, usually 0.01 mole of integral molar quantity that accounts for the transition metal that constitutes the main component raw material is more than the %, it is desirable to account for 0.03 mole more than the %, better is to account for 0.04 mole more than the %, it is desirable to account for 0.05 mole especially more than the %,, it is desirable at 1.8 moles below the % usually less than 2 moles of %, better is at 1.5 moles below the %, it is desirable at 1.3 moles below the % especially.If be lower than this lower limit, then might can not get above-mentioned effect, if surpass this upper limit, then battery performance might descend.
Lithium transition-metal based compound powder of the present invention is characterised in that, at denseization of the surface portion existence of its primary particle element (interpolation element) from additive, promptly has the element more than at least a kind that is selected from Mo, W, Nb, Ta and Re.Particularly, the mol ratio of the summation of the summation of the interpolation element of the surface portion of primary particle and the metallic element except that Li and interpolation element (being the metallic element outside Li and the interpolation element) is generally more than 5 times of this atomic ratio of whole particle.The lower limit of this ratio it is desirable to more than 7 times, and better is more than 8 times, it is desirable to especially more than 9 times.The upper limit has no particular limits usually, but it is desirable to below 150 times, and better is below 100 times, it is desirable to especially it would be desirable below 30 times below 50 times.If if this ratio is too small, then the effect of improving of battery performance reduces sometimes, and is opposite excessive, then causes battery performance to worsen sometimes.
The composition analysis of the surface portion of the primary particle of lithium transition-metal based compound powder by X-ray photoelectron spectroscopy (XPS), uses monochromatic light AlK α at x-ray source, analyzes area 0.8mm footpath, takes out under the condition at 65 ° at angle and carry out.Analyzable scope (degree of depth) is according to the difference of the composition of primary particle and difference, but usually more than the 0.1nm, below the 50nm, especially in positive active material, usually more than the 1nm, below the 10nm.Therefore, in the present invention, the surface portion of the primary particle of lithium transition-metal based compound powder demonstrates the scope that can measure in this condition.
＜median particle diameter and 90% accumulation particle diameter (D
90)
The median particle diameter of lithium transition-metal based compound powder of the present invention is usually more than 0.1 μ m, it is desirable to more than 0.3 μ m, better is more than the 0.6 μ m, better is more than the 0.8 μ m, it would be desirable more than 1.2 μ m, usually below 5 μ m, it is desirable to below 4 μ m, better is below 3 μ m, and better is below 2.8 μ m, it would be desirable below 2.5 μ m.If median particle diameter is lower than lower limit, then when positive active material formed, coating may have problems, if surpass the upper limit, then may cause battery performance to descend.
Again, 90% of the second particle of lithium transition-metal based compound powder of the present invention accumulation particle diameter (D
90) usually below 10 μ m, it is desirable to below 8 μ m, better is below 6 μ m, it would be desirable below 5 μ m, more than 0.5 μ m, it is desirable to more than 0.8 μ m usually, better is more than the 1 μ m, it would be desirable more than 1.5 μ m.90% accumulation particle diameter (D
90) if surpass the above-mentioned upper limit, then may cause battery performance to descend, if be lower than lower limit, then when positive active material formed, coating may have problems.
In addition, accumulate particle diameter (D as the median particle diameter and 90% of average grain diameter
90) can be with measuring with aforementioned the same method.
＜average primary particle diameter 〉
Average diameter (average primary particle diameter) to the primary particle of lithium transition-metal based compound powder of the present invention does not limit especially, but as lower limit, it is desirable to more than 0.1 μ m, better is more than the 0.15 μ m, better is more than the 0.2 μ m, it would be desirable more than 0.25 μ m, again, as the upper limit, it is desirable to below 0.9 μ m, better is below 0.8 μ m, and better is below 0.7 μ m, it would be desirable below 0.5 μ m.If average primary particle diameter surpasses the above-mentioned upper limit, bring bad influence then can for powder filled property, degradation under the specific area, so the possibility that the battery performance of speed characteristic and characteristics of output power etc. descends might improve.If be lower than above-mentioned lower limit, then crystallization is undeveloped, therefore might produce the low of inferior quality problem of the invertibity that discharges and recharges.
In addition, the average primary particle diameter among the present invention can carry out with above-mentioned the samely.
＜BET specific area 〉
The BET specific area of lithium transition-metal based compound powder of the present invention is usually at 1.5m
2More than/the g, it is desirable at 1.6m
2More than/the g, that better is 1.7m
2More than/the g, it would be desirable 1.8m
2More than/the g, usually at 5m
2Below/the g, it is desirable at 4m
2Below/the g, better is at 3.5m
2Below/the g, it would be desirable at 3m
2Below/the g.If the BET specific area is less than this scope, and then battery performance descends easily, if greater than, then being difficult to improve volume density, positive active material may be easy to generate the problem of coating when forming.
In addition, the BET specific area can be with measure with aforementioned the samely.
The pore characteristics that＜mercury penetration method is carried out 〉
Positive electrode material of lithium secondary cell of the present invention it is desirable to satisfy certain conditions in the mensuration of mercury penetration method with lithium transition-metal based compound powder.In addition, the mercury penetration method that adopts of the evaluation of lithium transition-metal based compound powder of the present invention as previously mentioned.
Lithium transition-metal based compound powder of the present invention it is desirable to, and the mercury that obtains in this mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.7cm
3/ g is above, 1.5cm
3Below/the g.What the mercury amount of being pressed into was better is at 0.74cm
3More than/the g, better is at 0.8cm
3More than/the g, it would be desirable at 0.9cm
3More than/the g, better is at 1.4cm
3Below/the g, better is at 1.3cm
3Below/the g, it would be desirable at 1.2cm
3Below/the g.If surpass the upper limit of this scope, then the space is excessive, and when lithium transition-metal based compound powder of the present invention was used as positive electrode, positive active material reduced at the filling rate of positive plate (anodal collector), and battery capacity is restricted.On the other hand, if be lower than the lower limit of this scope, then intergranular space is too small, when therefore lithium transition-metal based compound powder of the present invention being made battery as positive electrode, can hinder intergranular lithium diffusion, and part throttle characteristics descends.
Again, when with above-mentioned mercury penetration method lithium transition-metal based compound powder of the present invention being carried out pore distribution curve mensuration, usually, the specific main peak of following explanation appears.
In addition, " pore distribution curve ", " the pore distribution curve that the present invention relates to ", " main peak ", " submaximum " reach " summit " definition as mentioned above.
＜main peak 〉
It is the above scope of 300nm that the summit of the main peak that pore distribution curve involved in the present invention has is present in the pore radius usually, it is desirable to more than 350nm, it would be desirable more than 400nm, again, usually below 1000nm, it is desirable to below 980nm, better is below 970nm, better is below 960nm, it would be desirable below 950nm.If surpass the upper limit of this scope, when lithium transition-metal based compound powder then of the present invention is made battery as positive electrode, might hinder the lithium diffusion in the positive electrode, perhaps conductive path is not enough, and part throttle characteristics descends.On the other hand, if be lower than the lower limit of this scope, when then making positive pole with lithium transition-metal based compound powder of the present invention, the necessary amounts of possible electric conducting material and binding agent increases, positive active material is restricted at the filling rate of positive plate (anodal collector), and battery capacity is restricted.Again, along with micronize, the engineering properties of filming during coating becomes hard or crisp, films easily in then might the coiling operation when battery is assembled and peels off.
Again, the pore distribution curve that the present invention relates to have more than pore radius 300nm, exist below the 1000nm summit the peak the pore capacity suitable be usually at 0.4cm
3More than/the g, it is desirable at 0.41cm
3More than/the g, better is at 0.42cm
3More than/the g, it would be desirable at 0.43cm
3More than/the g, again, usually at 1cm
3Below/the g, it is desirable at 0.8cm
3Below/the g, better is at 0.7cm
3Below/the g, it would be desirable at 0.6cm
3Below/the g.If surpass the upper limit of this scope, then the space is excessive, when lithium transition-metal based compound powder of the present invention is used as positive electrode, might reduce at the filling rate of positive plate by positive active material, and battery capacity is restricted.On the other hand, if be lower than the lower limit of this scope, then intergranular space is too small, when therefore lithium transition-metal based compound powder of the present invention being made battery as positive electrode, might hinder the lithium diffusion between second particle, and part throttle characteristics descends.
＜submaximum 〉
The pore distribution curve that the present invention relates to also can have some submaximums except above-mentioned main peak, but it is desirable to not be present in the scope of pore radius more than 80nm, below the 300nm.
＜volume density 〉
The volume density of lithium transition-metal based compound powder of the present invention is usually more than 0.5g/cc, it is desirable to more than 0.6g/cc, better is more than 0.7g/cc, it would be desirable more than 0.8g/cc, usually below 1.7g/cc, it is desirable to below 1.6g/cc, better is below 1.5g/cc, it would be desirable below 1.3g/cc.Volume density is desirable to improving powder filled property and electrode density then if surpass this upper limit, but then, might make specific area low excessively, and battery performance descends.Volume density brings bad influence then might for powder filled property and electrode preparation if be lower than this lower limit.
In addition, volume density can be tried to achieve with above-mentioned the samely.
＜specific insulation 〉
The lower limit of the value of the specific insulation when compressing lithium transition-metal based compound of the present invention with the pressure of 40MPa it is desirable to 1 * 10
3More than the Ω cm, better is 5 * 10
3More than the Ω cm, it is desirable to 1 * 10 more
4More than the Ω cm.The upper limit it is desirable to 1 * 10
6Below the Ω cm, better is 5 * 10
5Below the Ω cm, it is desirable to 1 * 10 more
6Below the Ω cm.This specific insulation is if surpass this upper limit, and the part throttle characteristics when then making battery might descend.On the other hand, if specific insulation is lower than this lower limit, the fail safe when then making battery might descend.
In addition, specific insulation can be measured with above-mentioned the samely.
＜crystalline texture 〉
Lithium transition-metal based compound powder of the present invention it is desirable to that the lithium-nickel-manganese-cobalt system complex oxide that constitutes is main component to contain the crystalline texture that belongs to layer structure.
As representational system of crystallization, have to belong to aforesaid α-NaFeO with layer structure
2The material of type, these are hexagonal crystal systems, from its symmetry, belong to space group " stratiform R (3) m structure ".
Just, stratiform LiMeO
2As mentioned above, be not limited to stratiform R (3) m structure.
＜form
Lithium transition-metal based compound powder of the present invention it is desirable to the lithium transition-metal based compound powder by following composition formula (I ＂) expression.
LiMO
2 (I＂)
Wherein, M is the element that is made of Li, Ni and Mn or Li, Ni, Mn and Co, the Mn/Ni mol ratio is usually more than 0.8, it is desirable to more than 0.82, better be more than 0.85, better is more than 0.88, it would be desirable more than 0.9, usually below 5, it is desirable to below 4, better is below 3, better is below 2.5, it would be desirable below 1.5.Co/ (Mn+Ni+Co) mol ratio is usually more than 0, it is desirable to more than 0.01, better is more than 0.02, better is more than 0.03, it would be desirable more than 0.05, usually below 0.30, it is desirable to below 0.20, better is below 0.15, and better is below 0.10, it would be desirable below 0.099.Li mol ratio among the M is more than 0.001, it is desirable to more than 0.01, better is more than 0.02, better is more than 0.03, it would be desirable more than 0.05, usually below 0.2, it is desirable to below 0.19, better is below 0.18, and better is below 0.17, it would be desirable below 0.15.
In addition, in described composition formula (I ＂), the atomic ratio of oxygen amount does 2 for convenient note, but indefinite ratio property a little also can be arranged.Indefinite situation than property is arranged, and the atomic ratio of oxygen in 2 ± 0.2 scope, it is desirable to the scope 2 ± 0.15 usually, the scope that better is 2 ± 0.12, and the scope that better is 2 ± 0.10 it is desirable to the scope 2 ± 0.05 especially.
Again, in order to improve the crystallinity of positive active material, lithium transition-metal based compound powder of the present invention it is desirable to carry out high-temperature calcination and forms under oxygen-containing gas atmosphere.Especially, in the lithium-nickel-manganese-cobalt system complex oxide of composition with above-mentioned composition formula (I ＂) expression, the lower limit of calcining heat it is desirable to more than 975 ℃ usually more than 970 ℃, and better is more than 980 ℃, better is more than 985 ℃, it would be desirable that more than 990 ℃ the upper limit it is desirable to below 1175 ℃ usually below 1200 ℃, better is below 1150 ℃, it would be desirable below 1125 ℃.If calcining heat is low excessively, then heterogeneous mixing, and crystalline texture is undeveloped, and lattice deformability increases.And it is excessive that specific area becomes.Otherwise if calcining heat is too high, then primary particle is excessively grown up, and exceedingly carries out sintering between particle, and it is too small that specific area becomes.
＜carbon containing concentration C 〉
Carbon containing concentration C (weight %) value of lithium transition-metal based compound powder of the present invention is usually more than 0.005 weight %, it is desirable to more than 0.01 weight %, better is more than the 0.015 weight %, it would be desirable more than the 0.02 weight %, usually below 0.05 weight %, it is desirable to below the 0.045 weight %, better is below the 0.04 weight %, it would be desirable below the 0.035 weight %.If be lower than lower limit, then battery performance may descend, if surpass the upper limit, gas produces and the expansion that causes increases degradation under the battery performance in the time of then might making battery.
In the present invention, the carbon containing concentration C of lithium transition-metal based compound powder is tried to achieve with above-mentioned the samely.
In addition, the carbonaceous component of the lithium transition-metal based compound powder of trying to achieve by carbon analysis described later can be regarded as the information of the adhesion amount of expression relevant carbonate compound, especially lithium carbonate.This is because the carbon amount that supposition is tried to achieve by the carbon analysis is all roughly consistent with the carbonic acid ion concentration of passing through ion chromatography analysis from the numerical value of carbonate.
On the other hand, as the gimmick of further raising electrical conductance, when carrying out the compoundization processing with conductive carbon, detect the C amount that surpasses described prescribed limit sometimes, but the C value in the situation of implementing such processing is not limited to described prescribed limit.
＜suitable composition the
It is desirable to positive electrode material of lithium secondary cell of the present invention especially represents with atomic building in the M position in above-mentioned composition formula (I ＂) of lithium transition-metal based compound powder such as following formula (II ＂).
M＝Li
z＂/(2+z′′){(N
i(1+y＂)/2”M
n(1-y＂)/2)
1-x＂Co
x＂}
2/(2+z＇) ...(II＂)
Wherein, in above-mentioned formula (II ＂),
0≦x＂≦0.1，
-0.1≦y＂≦0.1，
(1-x＂)(0.05-0.98y＂)≦z＂≦(1—x＂)(0.15-0.88y＂)。
In above-mentioned (II ＂) formula, the value of x ＂ it is desirable to more than 0.01 more than 0, better is more than 0.02, and better is more than 0.03, it would be desirable more than 0.04, usually below 0.1, it is desirable to it would be desirable below 0.098 below 0.099.
The value of y ＂ it is desirable to more than-0.05 usually more than-0.1, and better is more than-0.03, it would be desirable more than-0.02,, it is desirable to below 0.05 usually below 0.1, better is below 0.03, it would be desirable below 0.02.
Z ＂ value is usually more than (1-x ＂) (0.05-0.98y ＂), it is desirable to more than (1-x ＂) (0.06-0.98y ＂), better is more than (1-x ＂) (0.07-0.98y ＂), better is more than (1-x ＂) (0.08-0.98y ＂), it would be desirable more than (1-x ＂) (0.10-0.98y ＂), usually at (1-x ＂) below (0.20-0.98y '), it is desirable to below (1-x ＂) (0.18-0.88y ＂), better is below (1-x ＂) (0.17-0.88y ＂), it would be desirable below (1-x ＂) (0.16-0.88y ＂).If z ＂ is lower than this lower limit, then conductivity descends, if surpass the upper limit, then might be too much and battery capacity reduction etc. in the amount of transition metal position displacement, and cause using the decreased performance of the lithium secondary battery of this compound.Again, if z is excessive, because the carbonic acid gas absorbability of active material powder increases, the easy carbonic acid gas that absorbs in the atmosphere then becomes.Infer that its result contains concentration of carbon and becomes big.
As can be seen, in the compositing range of above-mentioned (II ＂) formula, the lower limit of ratio is decided in the approaching more conduct of z ＂ value, speed characteristic when making battery and characteristics of output power are often low more, on the contrary, z ＂ value is more near the upper limit, and speed characteristic when making battery and characteristics of output power are often high more, but then, capacity often descends.Again, as can be seen, y ＂ value is more near lower limit, and promptly manganese/nickle atom is then hanging down increase capacity under the charging voltage than more little, but cycle characteristics and fail safe that the battery of high charge voltage is set often descend, on the contrary, y ＂ value is more near the upper limit, and cycle characteristics and fail safe that the battery of high charge voltage is set improve, but then, discharge capacity, speed characteristic and characteristics of output power often descend.As can be seen, x ＂ value is more near lower limit, the such part throttle characteristics of speed characteristic when making battery and characteristics of output power is often low more, on the contrary, x ＂ value is more near the upper limit, and speed characteristic when making battery and characteristics of output power are often high more, but if surpass this upper limit, cycle characteristics and fail safe when then being arranged on high charge voltage often descend, and cost of material improves.This is an important inscape of the present invention in prescribed limit for above-mentioned composition parameter x ＂, y ＂, z ＂.
Here, the chemical sense for the Li in the lithium-nickel-manganese-cobalt system complex oxide of the suitable composition as the lithium transition metal compound powder of the present invention forms (z ＂ and x ＂) is described in detail by following.
Aforesaid layer structure may not be limited to R (3) m structure, but considers from electrochemical aspect of performance, it is desirable to belong to the compound of R (3) m structure.
With inductively coupled plasma emission spectroanalysis device (ICP-AES) each transition metal and Li are analyzed, tried to achieve the ratio of Li/Ni/Mn/Co, thereby calculate x ＂, y ＂, the z ＂ of the composition formula of above-mentioned lithium-nickel-manganese-cobalt system complex oxide.
From the viewpoint of structure, we think that the Li that z ＂ relates to enters in identical transition metal position displacement.Here, the Li related according to z ＂, according to the principle of neutral charge, the average valence mumber of Ni is than 2 big (producing the Ni of 3 valencys).Z ＂ rises the average valence mumber of Ni, so z ' is the index of Ni valence mumber (ratio of Ni (III)).
In addition, if calculate the Ni valence mumber (m) that changes along with the variation of z ＂, be that 3 valencys, Mn valence mumber are under the prerequisite of 4 valencys then at the Co valence mumber from above-mentioned composition formula,
m＝2[2-{(1-x＂-z＂)/(1-x＂)(1+y＂)}]。
This result of calculation means the Ni valence mumber not merely by z ＂ decision, but the function of x ＂ and y ＂.If z ＂=0 and y ＂=0, then the value of the valence mumber of Ni and x ＂ is irrelevant, is divalent.If z ＂ is a negative value, then mean the also not enough stoichiometric amount of Li amount that contains in the active material, the compound with excessive negative value might can not be brought into play effect of the present invention.On the other hand, even also mean identical z " value, the composition of Ni abundant more (y ＂ value is big more) and/or Co abundant more (x ＂ value is big more), the Ni valence mumber is high more, and when being used for battery, speed characteristic and characteristics of output power uprise, but capacity descends easily.It can be said that better is that the upper and lower bound of z ' value is stipulated as the function of x ' and y '.
Again, if x ＂ value is 0 ≦ x ＂ ≦ 0.1, is in the few scope of Co amount that then except cost reduced, also when using as the lithium secondary battery that is designed to charge at the high charge current potential, charge/discharge capacity, cycle characteristics and fail safe improved.
＜powder x-ray diffraction peak 〉
In the present invention, lithium-nickel-manganese-cobalt system complex oxide powder with the composition that satisfies above-mentioned composition formula (I ＂) and (II ＂), it is characterized in that, in the powder X-ray ray image that uses CuK α line, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is made as FWHM (110), be in 0.01 ≦ FWHM (scope of 110) ≦ 0.2.
In addition, about the powder x-ray diffraction peak, the content of being recorded and narrated at the lithium-nickel-manganese-cobalt system complex oxide powder of the compound formation of being represented by above-mentioned composition formula (I ') here also is suitable for.
＜lithium transition-metal based compound powder of the present invention brings the reason of above-mentioned effect 〉
Bring the reason of above-mentioned effect as lithium transition-metal based compound powder of the present invention, consider as follows.
Promptly, infer because the crystalline particle microminiaturization of lithium transition-metal based compound powder of the present invention, the mercury amount of being pressed into when mercury is pressed into boosting in the curve is many, pore capacity between crystalline particle is big, so when making battery with this powder, contact area between positive active material surface and electrolyte is increased, and crystallinity is highly developed, and suppress heterogeneous existence, make its ratio few, as a result, thus improved as positive active material necessary load characteristic and to be reached realistic scale.
Then, the manufacture method to lithium transition-metal based compound of the present invention is described in detail.
The manufacture method of the lithium transition-metal based compound among the present invention is not defined as specific method for making, but if will illustrate the lithium-nickel-manganese-cobalt system complex oxide, lithium compound, nickel compound, manganese compound, cobalt compound are scattered in the liquid medium and obtain slip, after this slip spray drying, this mixture is calcined, made.
Again, suitably make with the manufacture method of lithium transition-metal based compound powder by following positive electrode material of lithium secondary cell, this manufacture method comprises: the slip preparation section, promptly in liquid medium with lithium compound, be selected from the transistion metal compound more than at least a kind among V, Cr, Mn, Fe, Co, Ni and the Cu, particle when suppressing calcining is grown up and the additive of sintering is pulverized, and obtains making its homodisperse slip; The spray drying operation is promptly carried out spray drying to the slip that obtains; Calcination process is promptly calcined the spray drying powder that obtains.
Below, the manufacture method as the lithium-nickel-manganese-cobalt system complex oxide powder of lithium transition-metal based compound of the present invention is described in detail for example.
＜slip preparation section 〉
The method according to this invention is equivalent to make the lithium-nickel-manganese-cobalt system complex oxide, at the starting compound that is used for preparing slip, as lithium compound, Li is arranged for example
2CO
3, LiNO
3, LiNO
2, LiOH, LiOHH
2O, LiH, LiF, LiCl, LiBr, LiI, CH
3OOLi, Li
2O, Li
2SO
4, dicarboxylic acids lithium, citric acid reason, fatty acid lithium, lithium alkylide etc.It is desirable in these lithium compounds, do not produce SO during from calcination processing
x, NO
xDeng the harmful substance this point see, the lithium compound that does not contain nitrogen-atoms, sulphur atom, halogen atom, be again to produce in when calcining in the second particle of decomposition gas etc., spray drying powder to produce decomposition gas and easy interstitial compound, if consider from these points, Li wherein
2CO
3, LiOH, LiOHH
2O uses especially easily, from less expensive consideration, it is desirable to Li
2CO
3, these compounds can a kind use separately, also can be used in combination more than 2 kinds.
As nickel compound, Ni (OH) is arranged for example again,
2, NiO, NiOOH, NiCO
3, 2NiCO
33Ni (OH)
24H
2O, NiC
2O
42H
2O, Ni (NO
3)
26H
2O, NiSO
4, NiSO
46H
2O, aliphatic acid nickel, nickel halide etc.Do not produce SO during wherein, from calcination processing
x, NOx etc. the harmful substance this point see, it is desirable to Ni (OH)
2, NiO, NiOOH, NiCO
3, 2NiCO
33Ni (OH)
24H
2O, NiC
2O
42H
2The nickel compound that O is such.Again, the further viewpoint from obtaining at an easy rate as the raw material of industry, and reactive high such viewpoint it is desirable to Ni (OH)
2, NiO, NiOOH, NiCO
3, further produce decomposition gas etc., in the second particle of spray drying powder, form the such viewpoint in space easily from when calcining, it is desirable to Ni (OH) especially
2, NiOOH, NiCO
3These nickel compounds can independent a kind of use, also can be used in combination more than 2 kinds.
As manganese compound, Mn is arranged for example again,
2O
3, MnO
2, Mn
3O
4Deng Mn oxide, MnCO
3, Mn (NO
3)
2, MnSO
4, manganese acetate, dicarboxylic acids manganese, manganese citrate, aliphatic acid manganese etc. the halide etc. of manganese salt, alkali formula hydroxide, manganese chloride etc.In these manganese compounds, MnO
2, Mn
2O
3, Mn
3O
4, MnCO
3Do not produce the gas of SOx, NOx etc. during because of calcination processing, and can obtain at an easy rate, so desirable as the raw material of industry.And these manganese compounds can independent a kind of use, also can be used in combination more than 2 kinds.
As cobalt compound, Co (OH) is arranged for example again,
2, CoOOH, CoO, Co
2O
3, Co
3O
4, Co (OCOCH
3)
24H
2O, CoCl
2, Co (NO
3)
26H
2O, Co (SO
4)
27H
2O, CoCO
3Deng.Wherein, from calcination process, not producing SO
x, NOx etc. the harmful substance this point see, it is desirable to Co (OH)
2, CoOOH, CoO, Co
2O
3, Co
3O
4, CoCO
3, from can obtaining at an easy rate and reactive high these 2 industrial, that better is Co (OH)
2, CoOOH.And, produce decomposition gas and interstitial viewpoint in the second particle of spray drying powder easily from when calcining, it is desirable to Co (OH) especially
2, CoOOH, CoCO
3These cobalt compounds can independent a kind of use, also can be used in combination more than 2 kinds.
Again, except above-mentioned Li, Ni, Mn, Co starting compound, can also use following compound group, the purpose of this compound group is to carry out other element substitutions and imports above-mentioned different elements, forms the space effectively in the second particle that perhaps uses spray drying described later to form.In addition, the interpolation step of the compound that uses as purpose with the space that forms second particle effectively that here uses, according to its character, can select raw material to mix before or mixed any step.Especially, by mixed processes, apply mechanical shearing stress and the compound that decomposes easily it is desirable to add behind mixed processes.
The grain growth during as the inhibition calcining and the additive of sintering, as mentioned above, get final product so long as manifest the material of purpose effect, its kind is had no particular limits, but it is desirable to contain the compound of the element that is selected from high price in stable condition Mo, W, Nb, Re etc., use oxide material usually.
Grain when suppressing calcining grow up and the exemplary compounds of the additive of sintering as mentioned above, these additives can a kind of use separately, also can be used in combination more than 2 kinds.
The mixed method of raw material is restriction especially not, and the wet type dry type can.The method that the device that uses ball mill, vibration mill, porose bead grinding machine etc. for example, is arranged for example.The wet mixed that starting compound mixes in the liquid medium of water, alcohol etc. can be mixed more equably, and in calcination process, can improve the reactivity of mixture, thus desirable.
The time of mixing is according to the difference of mixed method and difference, but raw material gets final product by mixing equably in particle level, for example, with ball mill (wet type or dry type), common about 1 hour to 2 days,, stop and hour to be generally about 0.1 hour to 6 hours with porose bead grinding machine (wet type continuity method).
In addition, in the blend step of raw material, it is desirable to the parallel pulverizing of raw material of carrying out.As the degree of pulverizing, be index with the particle diameter of the feed particles after pulverizing, average grain diameter (median particle diameter) below 0.4 μ m, it is desirable to below 0.3 μ m usually, and better is below 0.25 μ m, it would be desirable below 0.2 μ m.If the average grain diameter of the feed particles after pulverizing is excessive, then the reactivity in calcination process descends, and composition is difficult to homogenization.Just, rise because be related to the cost of pulverizing, so about the granuleization more than the needs, being crushed to average grain diameter usually is more than the 0.01 μ m, it is desirable to more than 0.02 μ m, better is more than 0.05 μ m, gets final product like this.The means that realize such degree of grinding are not limited especially, but it is desirable to the case of wet attrition method.Particularly, the pearl mill etc. of can giving an example.
In addition, the median particle diameter of the pulverized particles in the slip of embodiments of the invention records as described above method measure.For the median particle diameter of spray drying body described later, through passing through it that measure again after 0,1,3,5 minute the ultrasonic wave dispersion, other conditions are identical except respectively.
＜spray drying operation 〉
After the wet mixed, then feed to drying process usually.Method is not limited especially, but from homogeneity, powder fluidity, the powder operating characteristics of the granular substance that produces, can make the viewpoint of dried particles etc. effectively, it is desirable to spray drying.
In the manufacture method of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention, after pulverizing by case of wet attrition, carry out spray drying, primary particle aggegation and form second particle thus, thus obtain powder.Primary particle aggegation and form second particle and the spray drying powder that obtains is the shape facility of spray drying powder of the present invention.As the confirmation method of shape, for example, there are SEM observation, section SEM to observe for example.
As the median particle diameter (here being value) that passes through the powder that spray drying obtains of the calcining presoma of lithium-nickel-manganese-cobalt system complex oxide powder of the present invention without the ultrasonic wave dispersion measurement usually below 15 μ m, better is below 12 μ m, better is below 9 μ m, it would be desirable below 7 μ m.Just, because too small particle diameter often is difficult to obtain, therefore usually more than 3 μ m, it is desirable to more than 4 μ m, better is more than 5 μ m.During with spray drying manufactured granular substance, can control its particle diameter by suitably selecting Sprayable, forced air feed speed, slip feed speed, baking temperature etc.
For example, lithium compound, nickel compound, manganese compound and cobalt compound are dispersed in obtain slip in the liquid medium, after this slip carried out spray drying, the powder that obtains is calcined, when making lithium-nickel-manganese-cobalt system complex oxide powder, slip viscosity during with spray drying is made as V (cp), the slip quantity delivered is made as S (L/min), when gas delivery volume is made as G (L/min), be that 50cp ≦ V ≦ 4000cp and gas liquid ratio G/S are under the condition of 1500 ≦ G/S ≦ 5000 then, carry out spray drying at slip viscosity V.
If slip viscosity V (cp) is low excessively, then might be difficult to obtain the primary particle aggegation and form the powder that second particle forms, if too high, then might break down by supply pump, or the nozzle obturation.Therefore, the lower limit of slip viscosity V (cp) is generally more than the 50cp, it is desirable to more than 100cp, better is more than the 300cp, it would be desirable 500cp, higher limit below 4000cp, it is desirable to below 3500cp usually, better is below 3000cp, it would be desirable below 2500cp.
Again, if gas liquid ratio G/S is lower than above-mentioned lower limit, thickization of second particle then, drying property descends easily, if surpass the upper limit, then might productivity ratio descend.Therefore, the lower limit of gas liquid ratio G/S is generally more than 1500, it is desirable to more than 1600, better is more than 1700, it would be desirable more than 1800, and higher limit is usually below 5000, it is desirable to below 4700, better is below 4500, it would be desirable below 4200.
For slip quantity delivered S and gas delivery volume G, suitably set according to the specification of the spray-drying installation of the viscosity of the slip of supplying with to spray drying or use etc.
In the method for the invention, as long as control slip quantity delivered and gas delivery volume, the specification of the spray-drying installation that makes it satisfy above-mentioned slip viscosity V (cp) and be suitable for using, carrying out spray drying in the scope that satisfies above-mentioned gas liquid ratio G/S gets final product, for other condition, be provided with aptly according to the kind of the device that uses etc., but better be to select following condition.
Promptly, the spray drying of slip it is desirable to carry out under following temperature, be that temperature is usually more than 50 ℃, it is desirable to more than 70 ℃, better is more than 120 ℃, it would be desirable more than 140 ℃, usually below 300 ℃, it is desirable to below 250 ℃, better is below 200 ℃, it would be desirable below 180 ℃.If this temperature is too high, then the hollow structure of possible resulting granulated pellet is many, and the packed density of powder descends.On the other hand, if low excessively, then might produce the problem that powder adhesion that the moisture dewfall of powder exit portion causes is blocked etc.
Again, the feature of the spray drying powder of the lithium-nickel-manganese-cobalt system complex oxide powder that the present invention relates to is the cohesive force deficiency between primary particle, this by to median particle diameter along with variation research that ultrasonic wave disperses can be confirmed.Here, disperse " Ultra Sonic " (power output 30W through 5 minutes ultrasonic waves, frequency 22.5kHz) upper limit of the median particle diameter of the spray-dried granules of measuring again below 4 μ m, it is desirable to below 3.5 μ m usually, and better is below 3 μ m, better is below 2.5 μ m, it would be desirable that below 2 μ m lower limit more than 0.01 μ m, it is desirable to more than 0.05 μ m usually, better is more than the 0.1 μ m, it would be desirable more than 0.2 μ m.Use the intergranular space of the lithium-nickel-manganese-cobalt system complex oxide particle that the median particle diameter spray-dried granules bigger than above-mentioned value after this ultrasonic wave disperses calcine to lack, part throttle characteristics does not improve.On the other hand, use the intergranular space of the lithium-nickel-manganese-cobalt system complex oxide particle that the median particle diameter spray-dried granules littler than above-mentioned value after this ultrasonic wave disperses calcine too much, the problem that might produce that volume density descends, coating characteristics is bad etc.
Again, the volume density of the spray drying powder of positive electrode material of lithium secondary cell usefulness lithium nickel manganese cobalt composite oxide powder of the present invention is usually more than 0.1g/cc, it is desirable to more than 0.3g/cc, better is more than 0.5g/cc, it would be desirable more than 0.7g/cc.If be lower than this lower limit, bring bad influence then may for the processing of powder filled property and powder, again, below 1.7g/cc, it is desirable to below 1.6g/cc usually, better is below 1.5g/cc, it would be desirable below 1.4g/cc.Volume density is if surpass this upper limit, and then the processing to powder filled property and powder is desirable, but then, might make specific area low excessively, and the reactivity in the calcination process descends.
Again, little as if the specific area of the powder that obtains by spray drying, then in the next procedure calcination process, reactivity between starting compound descends, and therefore, it is desirable to, as previously mentioned, by the means of the raw material pulverizing of before spray drying, will setting out etc., increasing specific surface areaization as far as possible.On the other hand, if increasing specific surface areaization exceedingly is then not only unfavorable to industrialization, and might be able to not obtain lithium transition-metal based compound of the present invention.Therefore, the BET specific area of the spray-dried granules that obtains thus it is desirable to, usually at 10m
2More than/the g, it is desirable at 20m
2More than/the g, better is at 30m
2More than/the g, it would be desirable at 35m
2More than/the g, usually at 70m
2Below/the g, it is desirable at 65m
2Below/the g, it would be desirable at 60m
2Below/the g.
In addition, when making positive electrode material of lithium secondary cell with lithium-nickel-manganese-cobalt system complex oxide powder, this powder is characterised in that, the compound of expression constitutes by (1 '), and contain the crystalline texture that belongs to layer structure and constitute, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is made as FWHM (110), with 0.01 ≦ FWHM (110) ≦ 0.2 expression, the BET specific area of the powder that obtains by spray drying it is desirable to, usually at 10m
2More than/the g, it is desirable at 20m
2More than/the g, better is at 30m
2More than/the g, it would be desirable at 50m
2More than/the g, usually at 100m
2Below/the g, it is desirable at 80m
2Below/the g, better is at 70m
2Below/the g, it would be desirable at 65m
2Below/the g.
＜calcination process 〉
Then, the calcining presoma that obtains is like this carried out calcination processing.
Here, in the present invention, the meaning of " calcining presoma " is that the spray drying body is handled lithium transition-metal based compound presoma before the calcining that obtains.For example, produce decomposition gas or decomposition gas distillation when making the spray drying body contain above-mentioned calcining and in second particle interstitial compound, also can be used as the calcining presoma.
This calcination condition also depends on the lithium compound raw material of forming or using, but as tendency, if calcining heat is too high, then primary particle is excessively grown up, otherwise if low excessively, then crystalline texture is undeveloped, and specific area is excessive.As calcining heat,, it is desirable to more than 850 ℃ usually more than 800 ℃, better is more than 900 ℃, it would be desirable more than 950 ℃, usually below 1100 ℃, it is desirable to below 1075 ℃, better is below 1050 ℃, it would be desirable below 1025 ℃.
When making positive electrode material of lithium secondary cell with lithium-nickel-manganese-cobalt system complex oxide powder, this powder is characterised in that, compound by composition formula (1 ') expression constitutes, and contain the crystalline texture that belongs to layer structure and constitute, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is made as FWHM (110), with 0.01 ≦ FWHM (110) ≦ 0.2 expression, as calcining heat T (℃), usually in 940 ℃ ≦ T ≦ 1200 ℃, it is desirable to more than 950 ℃, better is more than 960 ℃, it would be desirable more than 970 ℃, usually below 1200 ℃, it is desirable to below 1175 ℃, better is below 1150 ℃, it would be desirable below 1125 ℃.
Again, when making positive electrode material of lithium secondary cell with lithium transition-metal based compound powder, this powder is characterised in that, with the transistion metal compound with the function that can embed the removal lithium embedded ion is main component, the grain growth when in this main component raw material, adding the inhibition calcining more than at least a kind and the additive of sintering, the ratio of the integral molar quantity of the transition metal in the addition of this additive and the main component raw material is at 0.01 mole more than the % and less than 2 moles of %, calcine then and obtain, as its calcining heat, usually more than 700 ℃, but in the manufacturing of the lithium-nickel-manganese-cobalt system complex oxide powder of composition with above-mentioned composition formula (I ＂) and (II ＂) expression, usually it is desirable to more than 970 ℃, better is more than 975 ℃, and better is more than 980 ℃, it would be desirable more than 990 ℃, usually below 1200 ℃, it is desirable to below 1175 ℃, better is below 1150 ℃, it would be desirable below 1125 ℃.
Calcining can be used box furnace, tube furnace, continuous tunnel furnace, rotary furnace etc.Calcination process is divided into intensification, maintenance maximum temperature, cooling three parts usually.Second portion keeps maximum temperature may not be a step; also can be according to purpose; be divided into two steps or its above step; also can clip and be used for eliminating aggegation and do not destroy the broken operation of separating of second particle again or be used for pulverizing primary particle or further be crushed to the pulverizing process of micro powder, carry out twice repeatedly or intensification that it is above, keep the operation of maximum temperature, cooling.
Heating process makes in the stove with the programming rate more than 1 ℃/minute, below 10 ℃/minute usually and heats up.This programming rate is slow excessively, and is then time-consuming and industrial unfavorable, and too fast, and temperature can not be followed design temperature in the stove of the stove that then has.Programming rate it is desirable to more than 2 ℃/minute, and better is more than 3 ℃/minute, it is desirable to below 7 ℃/minute, and better is below 5 ℃/minute.
Keep retention time in the maximum temperature operation according to the difference of temperature and difference, but if in above-mentioned temperature range, then usually more than 30 minutes, it is desirable to more than 3 hours, better is more than 5 hours, it would be desirable more than 6 hours, below 50 hours, it is desirable to below 25 hours, better is below 20 hours, it would be desirable below 15 hours.If calcination time is too short, then be difficult to obtain the good lithium-nickel-manganese-cobalt system complex oxide powder of crystallinity, if long, then there is not practicality.If calcination time is long,, separates and brokenly become difficult and unfavorable then because of pulverizing thereafter.
In cooling process, usually make descent of temperature with the cooling rate more than 0.1 ℃/minute, below 10 ℃/minute.Cross slow, then time-consuming industrial unfavorable, too fast then often object lack homogeneity, container worsens fast.Cooling rate it is desirable to more than 1 ℃/minute, and better is more than 3 ℃/minute, it is desirable to below 7 ℃/minute, and better is below 5 ℃/minute.
Atmosphere during calcining can be used the oxygen-containing gas atmosphere of air etc.Be generally the atmosphere of oxygen concentration more than 1 volume %, it is desirable to more than 10 volume %, better is more than 15 volume %, below 100 volume %, it is desirable to below 50 volume %, and better is below 25 volume %.
In such manufacture method, in the manufacture method of the lithium transition-metal based compound powder with above-mentioned specific composition of the present invention, creating conditions is a timing, when preparation makes lithium compound, nickel compound, manganese compound and cobalt compound be scattered in slip in the liquid medium, by adjusting the mixing ratio of above-mentioned each compound, can control mol ratio as the Li/Ni/Mn/M of purpose.
In addition, in the situation of the powder growth when adding the inhibition calcining and the additive of sintering, the lithium-nickel-manganese-cobalt system complex oxide powder that for example has above-mentioned specific composition for manufacturing, creating conditions is a timing, grain when preparation makes lithium compound, nickel compound, manganese compound and cobalt compound and inhibition calcining is grown up and sintering when getting additive and being scattered in slip in the liquid medium, by adjusting the mixing ratio of above-mentioned each compound, can control mol ratio as the Li/Ni/Mn/Co of purpose.
Utilize the lithium transition-metal based compound that obtains like this, a kind of anode materials for lithium secondary cells is provided, this positive electrode is because the expansion that gas produces is few, the capacity height, the part throttle characteristics of speed output (power) etc. is good, and low temperature characteristics of output power, preservation characteristics are also good, and performance balance is good.
[secondary lithium batteries positive pole]
Below, secondary lithium batteries positive pole of the present invention is described in detail.
Cathode plate for lithium secondary battery of the present invention forms on collector and contains positive electrode material of lithium secondary cell of the present invention and constitute with the positive electrode active material layer of lithium-nickel-manganese-cobalt system complex oxide powder and binding agent.
The electric conducting material that uses with positive electrode, binding agent and according to further needs and tackifier etc. mix with dry type, do slabbing, this sheet is pressed on the plus plate current-collecting body, perhaps, with these material dissolves or be dispersed in the liquid medium, make the slip shape, be coated on plus plate current-collecting body, carry out drying, make positive electrode active material layer thus.
As the material of plus plate current-collecting body, use the material with carbon element of the metal material, carbon fabric, carbon paper etc. of aluminium, stainless steel, nickel plating, titanium, tantalum etc. usually.Wherein it is desirable to metal material, it is desirable to aluminium especially.Again, as shape, metal material has metal forming, metal cylinder, metal coiled material, metallic plate, metallic film, porous metals, perforated metal, foaming metal etc. for example, and material with carbon element has carbon plate, carbon film, carbon cylinder etc. for example.Wherein, metallic film is using in the industrialization goods now, thereby desirable.In addition, film also can suitably form latticed.
When using film as plus plate current-collecting body, its thickness is any, but suitable be usually more than 1 μ m, it is desirable to more than 3 μ m, better is more than the 5 μ m, again, usually below 100mm, it is desirable to below 1mm the scope that better is below 50 μ m.If thin than above-mentioned scope, then might be as the necessary insufficient strength of collector, on the other hand, if thick than above-mentioned scope then might diminish operability.
As the binding agent that is used to make positive electrode active material layer, not restriction especially, the occasion of rubbing method, as long as the liquid medium that uses during with respect to the manufacturing electrode is stable material, as object lesson, polyethylene is arranged for example, polypropylene, PETG, polymethyl methacrylate, aromatic polyamide, cellulose, the resin system macromolecule of NC Nitroncellulose etc., SBR (butadiene-styrene rubber), NBR (acrylonitrile-butadiene rubber), fluorubber, isoprene rubber, polybutadiene rubber, the rubber-like macromolecule of ethylene-propylene rubber etc., styrene butadiene styrene block copolymer and hydride thereof, EPDM (ethylene propylene diene terpolymers), styrene ethylene butadiene ethylene copolymer, the thermoplastic elastomer (TPE) shape macromolecule of styrene isoprene styrene block copolymer and hydride thereof etc., between advise 1, the 2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymer, the soft resin shape macromolecule of propylene α-alkene copolymer etc., Kynoar, polytetrafluoroethylene, the fluoro Kynoar, the fluorine of polytetrafluoroethylene ethylene copolymer etc. is a macromolecule, has the polymeric composition etc. of the ionic conductance of alkali metal ion (particularly lithium ion).In addition, these materials can independent a kind of use, also can be used in combination more than 2 kinds, with combination in any and ratio.
The ratio of the binding agent in the positive electrode active material layer is usually more than 0.1 weight %, it is desirable to more than 1 weight %, better is more than 5 weight %, usually below 80 weight %, it is desirable to below 60 weight %, better is below 40 weight %, it would be desirable below 10 weight %.If the ratio of binding agent is low excessively, then can not keep the then anodal mechanical strength of positive active material not enough fully, the battery performance of cycle characteristics etc. is worsened, on the other hand,, then might be related to the decline of battery capacity or conductivity if too high.
In order to improve conductivity, positive electrode active material layer contains electric conducting material usually.Its kind is not limited especially, but, the metal material of copper, nickel etc. is arranged for example, the material with carbon element of the amorphous carbon of the carbon black of the graphite of native graphite, Delanium etc. (graphite), acetylene carbon black etc., needle coke etc. etc. etc. as object lesson.In addition, these materials can independent a kind of use, also can be used in combination more than 2 kinds, with combination in any and ratio.The ratio of the electric conducting material in the positive electrode active material layer more than 0.01 weight %, it is desirable to more than 0.1 weight % usually, and better is more than 1 weight %, again, usually below 50 weight %, it is desirable to below 30 weight %, better is below 20 weight %.If the ratio of electric conducting material is low excessively, then conductivity is not enough sometimes, otherwise if too high, then battery capacity descends sometimes.
As the liquid medium that is used to form slip, so long as can dissolve or disperse lithium nickel manganese system complex oxide powder, binding agent as positive electrode and the electric conducting material that uses as required and the solvent of tackifier to get final product, its kind is not limited especially, and water solvent and organic system solvent can use.Example as water solvent, water, alcohol etc. are arranged for example, example as the organic system solvent, N-methyl pyrrolidone (NMP), dimethyl formamide, dimethylacetylamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl triamine, N can be arranged for example, N-dimethylamino propylamine, oxirane, oxolane (THF), toluene, acetone, dimethyl ether, dimethylacetylamide, hexamethyl ホ ス Off ァ Le acid amides, methyl-sulfoxide, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc.When especially using water solvent, add dispersant in the lump, carry out slipization with the latex of SBR etc. with tackifier.In addition, these solvents can independent a kind of use, also can be used in combination more than 2 kinds, with combination and ratio arbitrarily.
Proportional usually more than 10 weight % in the positive electrode active material layer as containing of the lithium transition-metal based compound powder of the present invention of positive electrode, it is desirable to more than 30 weight %, better is more than 50 weight %, usually below 99.9 weight %, it is desirable to below 99 weight %.If the ratio of lithium transition-metal based compound powder is too much in the positive electrode active material layer, then often anodal insufficient strength, if very few, then the capacity aspect is not enough sometimes.
Again, the thickness of positive electrode active material layer is usually about 10～200 μ m.
In addition, in order to improve the packed density of positive active material, it is desirable to utilize the compressing of positive electrode active material layer to obtaining such as roll squeezer by coating, drying.
Like this, can adjust secondary lithium batteries positive pole of the present invention.
[lithium secondary battery]
Then, lithium secondary battery of the present invention is described in detail.
Lithium secondary battery of the present invention possesses the above-mentioned secondary lithium batteries positive pole of the present invention that can embed removal lithium embedded, can embed the negative pole of removal lithium embedded and be the nonaqueous electrolyte of electrolytic salt with the lithium salts.Further, also can between positive pole and negative pole, possess the barrier film that keeps nonaqueous electrolyte.In order to prevent the anodal short circuit that causes with contacting of negative pole effectively, preferably there is barrier film so like this.
＜negative pole 〉
Negative pole is usually with anodal the same, formation negative electrode active material layer on negative current collector and constituting.
As the material of negative current collector, the material with carbon element of the metal material of use copper, nickel, stainless steel, nickel plating, steel etc., carbon fabric, carbon paper etc.Wherein, metal material has metal forming, metal cylinder, metal coiled material, metallic plate, metallic film etc. for example, and material with carbon element has carbon plate, carbon film, carbon cylinder etc. for example.Wherein, metallic film is using in the industrialization goods now, thereby desirable.In addition, film also can suitably form latticed.When using metallic film as negative current collector, the scope of the thickness that it is suitable is the same with the above-mentioned scope of plus plate current-collecting body.
Negative electrode active material layer contains negative electrode active material and constitutes.As negative electrode active material, as long as on electrochemistry, can embed the removal lithium embedded ion, do not have other restriction, but the height that stands in fail safe usually sees that use can embed the material with carbon element of removal lithium embedded for its kind.
As material with carbon element,, but the graphite (graphite) or the organic pyrolysate under various thermal decomposition conditions of Delanium, native graphite etc. are arranged for example to the restriction especially of its kind.As organic pyrolysate, coal measures coke, oil are arranged for example is the carbide of coke, carbobitumen or the carbide that these pitches is carried out carbide, needle coke, pitch coke, phenolic resin, avicel cellulose etc. after the oxidation processes etc. and these are carried out material with carbon element, furnace black, acetylene carbon black, pitch-based carbon fiber etc. after a part of graphitization.Wherein, it is desirable to graphite, special is graphite material etc. by the easy graphite pitch that obtains being carried out contain in Delanium, refined natural graphite or these graphite that high-temperature heat treatment manufacturing obtains pitch from various raw materials aptly, the main use through various surface-treated materials.These material with carbon elements can be distinguished independent a kind of use, also can be used in combination more than 2 kinds.
When using graphite material as negative electrode active material, utilize the method for shaking of learning, the d value (interfloor distance) of the lattice plane (002 face) of trying to achieve with X-ray diffraction more than 0.335nm, again, below 0.34nm, it is desirable to below 0.337 usually usually.
Again, the ash content of graphite material accounts for below the 1 weight % of weight of graphite material usually, wherein it is desirable to it is desirable to especially below 0.1 weight % below 0.5 weight %.
Again, utilize to learn the method for shaking, the crystallite size (Lc) of the graphite material of trying to achieve with X-ray diffraction more than 30nm, wherein it is desirable to it is desirable to more than 100nm especially more than 50nm usually.
Again, the median particle diameter of the graphite material of trying to achieve by the laser diffraction and scattering method it is desirable to usually more than 1 μ m, especially it is desirable to more than 3 μ m, better is more than 5 μ m, it is desirable to especially more than 7 μ m, again, usually below 100 μ m, especially it is desirable to below 50 μ m, better is below 40 μ m, it is desirable to especially below 30 μ m.
Again, the BET specific area of graphite material is usually at 0.5m
2More than/the g, it is desirable at 0.7m
2More than/the g, that better is 1.0m
2More than/the g, that better is 1.5m
2More than/the g, usually at 25.0m
2Below/the g, it is desirable at 20.0m
2Below/the g, better is at 15.0m
2Below/the g, better is at 10.0m
2Below/the g.
When graphite material is carried out Raman spectrum analysis with argon laser, it is desirable at 1580～1620cm again,
-1The peak P that range detection goes out
AIntensity I
AWith at 1350～1370cm
-1The peak P that range detection goes out
BIntensity I
BStrength ratio I
A/ I
BMore than 0, below 0.5.Again, peak P
AHalf width it is desirable at 26cm
-1Below, better is at 25cm
-1Below.
In addition, except above-mentioned various material with carbon elements, also can use other embed and the material of removal lithium embedded as negative electrode active material.As the object lesson of the negative electrode active material outside the material, metal oxide, the Li of tin oxide and silica etc. arranged for example
2.6Co
0.4The lithium alloy of the nitride of N etc., lithium monomer or lithium-aluminium alloy etc. etc.Material outside these material with carbon elements can be distinguished independent a kind of use, also can be used in combination more than 2 kinds.Also can be used in combination with above-mentioned material with carbon element again.
Negative electrode active material layer is the same with the situation of positive electrode active material layer usually, can be by electric conducting material and tackifier liquid medium slipization with above-mentioned negative electrode active material, binding agent, interpolation as required, the material of this slipization is coated on the negative current collector, carry out drying, make.As the liquid medium that forms slip, binding agent, tackifier, electric conducting material etc., can use and the same material described in positive electrode active material layer.
＜nonaqueous electrolyte 〉
As nonaqueous electrolyte, can use for example known organic electrolyte, polymer solid electrolyte, gel-like electrolyte, inorganic solid electrolyte etc., but it is desirable to organic electrolyte.Organic electrolyte is dissolved in the organic solvent solute (electrolyte) and constitutes.
Here, the kind of organic solvent is not limited especially, for example, can use carbonates, ethers, ketone, sulfolane based compound, lactone, nitrile, chlorinated hydrocarbon, ethers, amine, ester class, amide-type, phosphate compound etc.If will exemplify representational, dimethyl carbonate is arranged for example, diethyl carbonate, carbonic acid ethyl methyl esters, propene carbonate, ethylene carbonate, vinylene carbonate, ethylene thiazolinyl vinyl acetate, oxolane, the 2-methyltetrahydrofuran, 1, the 4-diox, 4-methyl-2-valeric acid, 1, the 2-dimethoxy-ethane, 1, the 2-diethoxyethane, gamma-butyrolacton, 1,3-two oxa-s penta ring, the 4-methyl isophthalic acid, 3-two oxa-s penta ring, (2) ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, the benzo nitrile, butyronitrile, valeronitrile, 1, the 2-dichloroethanes, dimethyl formamide, methyl-sulfoxide, trimethyl phosphate, triethyl phosphates etc., the part of the hydrogen atom of these compounds also can replace with halogen atom.Can use these independent or mixed solvents more than 2 kinds again.
In order to make the electrolytic salt disassociation, it is desirable to the solvent that above-mentioned organic solvent contains high-k.Here, so-called high dielectric constant solvent is meant that permittivity in 25 ℃ is at the compound more than 20.In high dielectric constant solvent, it is desirable to comprise in the electrolyte compound that ethylene carbonate, propene carbonate and these hydrogen atom are replaced by other element of halogen etc. or alkyl etc.High dielectric constant solvent accounts for the ratio of electrolyte, it is desirable to more than 20 weight %, and better is more than 25 weight %, it would be desirable more than 30 weight %.
The content of high dielectric constant solvent is if than the lacking of above-mentioned scope, then can not obtain desired battery behavior sometimes.Can in organic electrolyte, add CO with arbitrary proportion again,
2, N
2O, CO, SO
2Deng gas or vinylene carbonate, polysulfide Sx
2-Deng additive, this additive forms the film that discharges and recharges can carry out lithium ion effectively in negative terminal surface.Wherein it is desirable to vinylene carbonate especially.
The kind of electrolytic salt does not limit especially yet, known solute arbitrarily before can using.As object lesson, LiClO is arranged for example
4, LiAsF
6, LiPF
6, LiPF
4, LiB (C
6H
5)
4, LiBOB, LiCl, LiBr, CH
3SO
3Li, CF
3SO
3Li, LiN (SO
2CF
3)
2, LiN (SO
2C
2F
5)
2, LiC (SO
2CF
3)
3, LiN (SO
3CF
3)
2Deng.These electrolytic salts can any separately a kind of use, also can be used in combination more than 2 kinds, with combination and ratio arbitrarily.Can add CO with arbitrary proportion again,
2, N
2O, CO, SO
2Deng gas or polysulfide Sx
2-Deng additive, this additive forms the film that discharges and recharges can carry out lithium ion effectively in negative terminal surface.
Usually contain the lithium salts that 0.5mol/L is above, 1.5mol/L is following in the electrolyte as electrolytic salt.Less than 0.5mol/L or above 1.5mol/L conductivity is descended, bring bad influence to battery behavior.With regard to lower limit, it is desirable to more than 0.75mol/L, with regard to the upper limit, it is desirable to below 1.25mol/L.
Use the situation of polymer solid electrolyte, there is no particular limitation for its kind, as solid electrolyte, can use the amorphous inorganic matter of known crystalline arbitrarily.As the inorganic solid electrolyte of crystalline, for example LiI, Li are arranged for example
3N, Li
1+xJ
xTi
2-x(PO
4)
3(J=Al, Sc, Y, La), Li
0.5-3xRE
0.5+xTiO
3(RE=La, Pr, Nd, Sm) etc.As amorphous inorganic solid electrolyte, for example 4.9LiI-34.1Li is arranged for example again,
2O-61B
2O
5, 33.3Li
2O-66.7SiO
2Deng oxide glass etc.These can any separately a kind of use, also can be used in combination more than 2 kinds, with combination and ratio arbitrarily.
＜barrier film 〉
When using above-mentioned organic electrolyte,, between positive pole and negative pole, clamp barrier film in order to prevent the short circuit between the electrode as electrolyte.Material or shape to barrier film have no particular limits, but it is desirable to stable for the organic electrolyte that uses, to protect fluidity good, and can prevent electrode short circuit to each other reliably.As desirable example, the little porous film that is made of various macromolecular materials, thin slice, bonded fabric etc. are arranged for example.As the object lesson of macromolecular material, use the polyene macromolecule of nylon, cellulose ethanoate, NC Nitroncellulose, polysulfones, polyacrylonitrile, Kynoar, polypropylene, polyethylene, polybutene etc.Especially, from as the chemistry of the key factor of barrier film and the viewpoint of electrochemical stability, it is desirable to polyene is macromolecule, from self the blocking temperature this point as one of application target battery of barrier film, especially wishes it is polyethylene.
During barrier film that use is made of polyethylene, from high temperature shape maintains this point, it is desirable to use ultra high molecular polyethylene, the lower limit of its molecular weight it is desirable to 500,000, and better is 1,000,000, it would be desirable 1,500,000.On the other hand, the upper limit of molecular weight it is desirable to 5,000,000, and better is 4,000,000, it would be desirable 3,000,000.If molecular weight is excessive, then flowability is low excessively because during heating sometimes the hole of barrier film do not block.
＜cell shapes 〉
Lithium secondary battery of the present invention forms by above-mentioned secondary lithium batteries positive pole of the present invention, negative pole, electrolyte and the barrier film that uses as required are assembled into suitable shape manufacturing.Also can use other inscapes of Package casing etc. further as required.
The shape of lithium secondary battery of the present invention is restriction especially not, can suitably select to use from the different shape of common employing according to its purposes.As the example of the shape of common employing, have for example with thin electrode and barrier film make spiral helicine cylinder type, with the coin shape of cylinder type, lamination electrode wafer and the barrier film of the structure Outside in of electrode wafer and barrier film combination etc.Again, the method for assembled battery is restriction especially also, can suitably select from normally used the whole bag of tricks according to the shape as the battery of purpose.
The charging potential of the positive pole the in＜fully charged state 〉
Again, lithium secondary battery of the present invention it is desirable to be designed to the primary charging current potential of the positive pole under fully charged state at 4.5 (vs.Li/Li
+) more than.Just, by above-mentioned specific composition, positive electrode material of lithium secondary cell of the present invention when being designed to the high charge current potential 4.5V (vs.Li/Li+) more than for the first time the lithium secondary battery of charging uses down, is brought into play the effect of raising cycle characteristics and fail safe with lithium transition-metal based compound powder effectively.Just, also can use during less than 4.5V at above-mentioned charging potential.
More than, the general execution mode of lithium secondary battery of the present invention is illustrated, but lithium secondary battery of the present invention is not limited to above-mentioned execution mode, as long as be no more than its main points, can add various distortion and implement.
Embodiment
Below, by embodiment, the present invention will be described in more detail, but the present invention is only otherwise exceed its main points just, is not to carry out any restriction by these embodiment.
[assay method of rerum natura]
Rerum natura of the lithium transition-metal based compound powder made in each embodiment described later and the comparative example etc. is carried out following various mensuration.
Form (Li/Ni/Mn/Co):
Try to achieve by the ICP-AES analysis.
Utilize the mensuration of the various rerum naturas of mercury penetration method:
As the determinator of mercury penetration method, AutoPore III 9420 types that use Micromeritics company to make.Again, as the condition determination of mercury penetration method, at room temperature, the limit boosts to the 413MPa limit from 3.86kPa and measures.In addition, with regard to the capillary value of mercury, use 480dyn/cm, with regard to the value of contact angle, use 141.3 °.
Average primary particle diameter:
SEM image by 30,000 times is tried to achieve.
The median particle diameter of second particle:
After disperseing 5 minutes, ultrasonic wave measures.
Volume density:
4～10g sample powder is put in the glass cylinder of 10ml, extracts 200 times powder filled density as stroke and try to achieve with about 20mm.
Specific area:
Try to achieve by the BET method.
The carbon containing concentration C:
Use (strain) hole field factory to make EMIA-520 analysis of carbon and sulfur meter.Take by weighing tens of samples and be placed in the empty magnetic crucible that burns, add combustion-supporting gas, in oxygen flow, with dielectric heating oven burning extraction carbon to 100mg.With the non-dispersion infrared absorption photometry CO2 in the burning gases is carried out quantitatively.No. 1 (C guarantee value: 0.469 weight %) of 150-15 low-alloy steel that sensitivity correction uses Japan Steel Union to make.
Specific insulation:
(DIA INSTRUMENTS company makes: the inefficient mensuration PD-41 of system of LorestaGP powder) to use powder resistance rate determinator, sample weight is 3g, by powder testing apparatus (four point probe ring electrode, electrode gap 5.0mm, electrode radius 1.0mm, radius of specimen 12.5mm), applying voltage clipper is 90V, measure the various specific insulations [Ω cm] that add the powder of depressing, the value of the specific insulation under the pressure of 40MPa is compared.
Crystalline phase:
Look like to try to achieve by the x-ray diffractogram of powder that uses CuK α line.
[powder x-ray diffraction determinator] PANalytical PW 1700
[condition determination] X ray output: 40kV, 30mA, scan axis: θ/2 θ
Sweep limits (2 θ): 10.0～90.0 °
Mode determination: Continuous
Read in width: 0.05 °, sweep speed: 3.0 °/min.
Slit: DS1 °, SS1 °, RS 0.2mm
The median particle diameter of the pulverized particles in the slip:
Use known laser diffraction/diffuse transmission type particle size distribution device, refractive index is arranged on 1.24, the particle diameter benchmark is measured as volume reference.Disperse (power output 30W, frequency 22.5kHz) afterwards, to measure at the ultrasonic wave that uses 0.1 weight % sodium hexametaphosphate solution to carry out 5 minutes as dispersant again.
As raw material Li
2CO
3The median particle diameter of the average grain diameter of powder:
(hole field manufactory makes, and LA-920), refractive index is arranged on 1.24, and the particle diameter benchmark is measured as volume reference to use known laser diffraction/diffuse transmission type particle size distribution device.Disperse (power output 30W, frequency 22.5kHz) afterwards, to measure at the ultrasonic wave that uses ethanol to carry out 5 minutes as dispersant again.
The rerum natura of the particulate powder that obtains by spray drying:
Form is observed by SEM and section SEM observation is confirmed.Median particle diameter and 90% accumulation particle diameter (D90) as average grain diameter, (hole field manufactory makes to use known laser diffraction/diffuse transmission type particle size distribution device, LA-920), refractive index is arranged on 1.24, the particle diameter benchmark is measured as volume reference.Disperse (power output 30W, frequency 22.5kHz) afterwards, to measure at the ultrasonic wave that uses 0.1 weight % sodium hexametaphosphate solution to carry out 0 minute, 1 minute, 3 minutes, 5 minutes as dispersant again.Specific area is tried to achieve by the BET method.Volume density is that 4～6g sample powder is put in the glass cylinder of 10ml, and the powder filled density when extracting 200 times as the stroke with about 20mm is tried to achieve.
The mensuration of the affirmation of crystalline phase (layer structure), half width FWHM (110):
(018) affirmation that has or not at the heterogeneous peak in the diffraction maximum of (110) (113) and the heterogeneous peak/original integrated intensity at crystalline phase peak and calculating of integrated intensity ratio:
The x-ray diffractogram of powder of the use CuK α line by following record looks like to try to achieve.(018), (110) that the hexagonal crystal system R-3m (No.166) that observes for each sample causes, (113) diffraction maximum are implemented profile match (profile fitting), calculate integrated intensity, integrated intensity and compare etc.
Diffraction image when the fixedly slit pattern of calculating the use concentric method of half width, area is measured.
Actual XRD determining (embodiment, comparative example) is measured with the changeable gap pattern, implements variable → fixing data conversion.
The calculating formula of intensity (fixing)=intensity (variable)/sin θ is passed through in variable → fixing conversion.
＜powder x-ray diffraction determinator specification 〉
Device name: the Dutch PANalytical manufacturing X ' Pert Pro MPD of company
Optical system: concentric method optical system
＜optical system specification 〉
Light incident side: loading type X-ray tube ball (CuK α)
Soller?Slit(0.04rad)
Divergence?Slit(Variable?Slit)
Sample bench: rotate sample bench (Spinner)
Sensitive side: the semiconductor array detector (X ' Celerator)
Ni-filter
Gonio radius: 243mm
＜condition determination 〉
As mentioned above.
＜add element (Mo, W, Nb, B, Sn) quantitatively
Try to achieve by the ICP-AES analysis.
＜the composition analysis on primary particle surface by x-ray photoelectron optical spectroscopy (XPS) 〉
The x-ray photoelectron light-dividing device " ESCA-5700 " that uses Physical electronics, inc. to make carries out under following condition.
X-ray source: monochromatization AlK α
Analyze area: 0.8mm footpath
Take out the angle: 65 °
Quantitative approach: with sensitivity coefficient to Bls, Mn
2p
1/2, Co
2p
3/2, Ni
2p
3/2, Nb
3D, Mo
3D, Sn
3d
5/2, each peak of W4f area carry out revisal.
[manufacturing of lithium transition-metal based compound powder (embodiment and comparative example)]
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, mol ratio is Li:Ni:Mn=1.267:0.250:0.583, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 950 ℃, calcine 12 hours (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 3.7 * 10
6Ω cm, to contain concentration of carbon be 0.092 weight %, consists of Li
1.088(Li
0.167Ni
0.254Mn
0.579) O
2Lithium nickel manganese composite oxide (x=0.167, y=0, z=0.088).Its average primary particle diameter is 0.2 μ m, and median particle diameter is 1.7 μ m, 90% accumulation particle diameter (below, be also referred to as D sometimes
90) be 3.6 μ m, volume density is 0.8g/cc, the BET specific area is 3.1m
2/ g.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, mol ratio is Li:Ni:Mn=1.267:0.250:0.583, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid branch in the slip.
The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 12 hours (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 9.2 * 10
5Ω cm, to contain concentration of carbon be 0.059 weight %, consists of Li
1.067(Li
0.167Ni
0.254Mn
0.579) O
2Lithium nickel manganese composite oxide (x=0.167, y=0, z=0.067).Its average primary particle diameter is 0.5 μ m, and median particle diameter is 3.6 μ m, D
90Be 4.6 μ m, volume density is 1.0g/cc, and the BET specific area is 2.1m
2/ g.
Embodiment 3
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, mol ratio is Li:Ni:Mn=1.211:0.333:0.556, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.17 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 900 ℃, calcine 12 hours (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 2.0 * 10
5Ω cm, to contain concentration of carbon be 0.084 weight %, consists of Li
1.066(Li
0.111Ni
0.334Mn
0.555) O
2Lithium nickel manganese composite oxide (x=0.111, y=0, z=0.066).Confirm that its crystalline texture constitutes by containing stratiform R (3) m structure again.Its average primary particle diameter is 0.2 μ m, and median particle diameter is 2.7 μ m, D
90Be 5.1 μ m, volume density is 0.8g/cc, and the BET specific area is 3.0m
2/ g.
Embodiment 4
Take by weighing Li
2CO
3, NiO, Mn
3O
4, mol ratio is Li:Ni:Mn=1.20:0.50:0.50, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.21 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 950 ℃, calcine 12 hours (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 4.6 * 10
4Ω cm, to contain concentration of carbon be 0.050 weight %, consists of Li
1.133(Ni
0.501Mn
0.499) O
2Lithium nickel manganese composite oxide (x=0, y=0, z=0.133).Its average primary particle diameter is 0.6 μ m, and median particle diameter is 3.8 μ m, D
90Be 6.1 μ m, volume density is 1.0g/cc, and the BET specific area is 1.9m
2/ g.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Li:Ni:Mn:Co=1.143:0.278:0.463:0.167, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.18 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 950 ℃, calcine 12 hours (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 5.0 * 10
5Ω cm, to contain concentration of carbon be 0.052 weight %, consists of Li
0.986(Li
0.093Ni
0.281Mn
0.458Co
0.168) O
2Lithium nickel manganese cobalt composite oxide (x=0.112, y=0.168, z=-0.014).Its average primary particle diameter is 0.3 μ m, and median particle diameter is 3.0 μ m, 90%, D
90Be 5.1 μ m, volume density is 1.0g/cc, and the BET specific area is 2.6m
2/ g.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Li:Ni:Mn:Co=1.10:0.45:0.45:0.10, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 925 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 1.9 * 10
4Ω cm, to contain concentration of carbon be 0.043 weight %, consists of Li
1.125(Ni
0.455Mn
0.445Co
0.100) O
2Lithium nickel manganese cobalt composite oxide (x=0, y=0.100, z=0.125).Its average primary particle diameter is 0.2 μ m, and median particle diameter is 1.1 μ m, D
90Be 1.6 μ m, volume density is 0.9g/cc, and the BET specific area is 3.3m
2/ g.
Embodiment 7
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, mol ratio is Li:Ni:Mn=1.15:0.50:0.50, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.14 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 2.1 * 10
4Ω cm, to contain concentration of carbon be 0.045 weight %, consists of Li
1.166(Ni
0.504Mn
0.496) O
2Lithium nickel manganese composite oxide (x=0, y=0, z=0.166).Its average primary particle diameter is 0.5 μ m, and median particle diameter is 3.3 μ m, D
90Be 5.6 μ m, volume density is 1.2g/cc, and the BET specific area is 1.9m
2/ g.
Comparative example 1
Take by weighing Ni (OH)
2, Mn
3O
4, mol ratio is Ni:Mn=0.250:0.583, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Add in slip being carried out the particulate powder that spray drying obtains by spray dryer that to mix median particle diameter be the Li of 9 μ m
2CO
3Powder.This powder of about 100g is divided into 6 parts equably puts in 6 aluminium oxide earthenware Crucible, under air atmosphere, under 950 ℃, (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 1.4 * 10 to calcine 12 hours
6Ω cm, to contain concentration of carbon be 0.034 weight %, consists of Li
1.035(Li
0.167Ni
0.252Mn
0.581) O
2Lithium nickel manganese composite oxide (x=0.167, y=0, z=0.035).Its average primary particle diameter is 0.3 μ m, and median particle diameter is 5.7 μ m, 90% accumulation particle diameter (D
90) be 8.6 μ m, volume density is 1.7g/cc, the BET specific area is 2.0m
2/ g.
Comparative example 2
Take by weighing Ni (OH)
2, Mn
3O
4, mol ratio is Ni:Mn=0.333:0.556, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.15 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Add in slip being carried out the particulate powder that spray drying obtains by spray dryer that to mix median particle diameter be the Li of 9 μ m
2CO
3Powder.This mixed-powder of about 15.9g is put in the aluminium oxide earthenware Crucible, and under circulation of air, under 1000 ℃, (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 9.4 * 10 to calcine 12 hours
4Ω cm, to contain concentration of carbon be 0.045 weight %, consists of Li
1.082(Li
0.111Ni
0.335Mn
0.554) O
2Lithium nickel manganese composite oxide (x=0.111, y=0, z=0.082).Confirm that its crystalline texture constitutes by containing stratiform R (3) m structure again.Its average primary particle diameter is 0.4 μ m, and median particle diameter is 5.9 μ m, D
90Be 8.8 μ m, volume density is 1.5g/cc, and the BET specific area is 1.1m
2/ g.
Comparative example 3
Take by weighing Ni (OH)
2, Mn
3O
4, mol ratio is Ni:Mn=0.50:0.50, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Add in slip being carried out the particulate powder that spray drying obtains by spray dryer that to mix median particle diameter be the Li of 9 μ m
2CO
3Powder.This mixed-powder of about 87.8g is divided into 6 parts equably to be put in 6 aluminium oxide earthenware Crucible, under circulation of air, under 1000 ℃, calcine 12 hours (5 ℃ of warming and cooling rates/min) afterwards, pulverize, to obtain specific insulation be 3.9 * 104 Ω cm, contain concentration of carbon is 0.031 weight %, consists of Li
1.084(Ni
0.505Mn
0.495) O
2Lithium nickel manganese composite oxide (x=0, y=0, z=0.084).Its average primary particle diameter is 0.5 μ m, and median particle diameter is 4.7 μ m, D
90Be 6.9 μ m, volume density is 1.6g/cc, and the BET specific area is 1.2m
2/ g.
Comparative example 4
Take by weighing Ni (OH)
2, Mn
3O
4, mol ratio is Ni:Mn=0.50:0.50, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Add in slip being carried out the particulate powder that spray drying obtains by spray dryer that to mix median particle diameter be the Li of 9 μ m
2CO
3Powder.This mixed-powder of about 15g is put in the aluminium oxide earthenware Crucible, and under circulation of air, under 1000 ℃, (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 1.2 * 10 to calcine 12 hours
4Ω cm, to contain concentration of carbon be 0.035 weight %, consists of Li
1.152(Ni
0.505Mn
0.496) O
2Lithium nickel manganese composite oxide (x=0, y=0, z=0.152).Its average primary particle diameter is 0.6 μ m, and median particle diameter is 6.1 μ m, and D90 is 9.1 μ m, and volume density is 1.5g/cc, and the BET specific area is 0.7m
2/ g.
Comparative example 5
Take by weighing Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Ni:Mn:Co=0.278:0.463:0.167, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Add in slip being carried out the particulate powder that spray drying obtains by spray dryer that to mix median particle diameter be the Li2CO3 powder of 9 μ m.This mixed-powder of about 15.4g is put in the aluminium oxide earthenware Crucible, and under circulation of air, under 900 ℃, (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 1.1 * 10 to calcine 12 hours
6Ω cm, to contain concentration of carbon be 0.046 weight %, consists of Li
0.960(Ni
0.280Mn
0.459Co
0.168) O
2Lithium nickel manganese cobalt composite oxide (x=0.112, y=0.168, z=-0.040).Its average primary particle diameter is 0.2 μ m, and median particle diameter is 5.2 μ m, D
90Be 7.7 μ m, volume density is 1.8g/cc, and the BET specific area is 2.2m
2/ g.
Comparative example 6
Take by weighing Ni (OH)
2, Mn
3O
4, Co (OH)
2, mol ratio is Ni:Mn:Co=0.45:0.45:0.10, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.15 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
In slip being carried out the particulate powder that spray drying obtains by spray dryer, add mixed powder and be broken to the LiOH powder of median particle diameter below 20 μ m.This mixed-powder of about 13.1g is put in the aluminium oxide earthenware Crucible, and under circulation of air, under 950 ℃, (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 1.7 * 10 to calcine 10 hours
4Ω cm, to contain concentration of carbon be 0.031 weight %, consists of Li
1.130(Ni
0.443Mn
0.453Co
0.105) O
2Lithium nickel manganese cobalt composite oxide (x=0, y=0.105, z=0.130).Its average primary particle diameter is 0.5 μ m, and median particle diameter is 11.1 μ m, D
90Be 18.4 μ m, volume density is 1.8g/cc, and the BET specific area is 1.3m
2/ g.
The composition transitivity value representation of the lithium transition-metal based compound powder of making in the foregoing description 1～7 and the comparative example 1～6 (positive electrode) is in table 1 and table 2.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Li:Ni:Mn:Co=1.10:0.45:0.45:0.10, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 13 weight % Gu form, viscosity 1350cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 2.7 * 10
4Ω cm, to contain concentration of carbon be 0.023 weight %, consists of Li
1.096(Ni
0.458Mn
0.444Co
0.098) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x '=0.098, y '=0.016, z '=0.096).The average primary particle diameter of this lithium-nickel-manganese-cobalt system complex oxide powder is 0.6 μ m, and median particle diameter is 3.0 μ m, and D90 is 5.1 μ m, and volume density is 1.2g/cc, and the BET specific area is 1.7m
2/ g.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Li:Ni:Mn:Co=1.10:0.45:0.45:0.10, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 13 weight % Gu form, viscosity 1350cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3L/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 975 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 2.2 * 10
4Ω cm, to contain concentration of carbon be 0.030 weight %, consists of Li
1.118(Ni
0.456Mn
0.445Co
0.099) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x '=0.099, y '=0.012, z=0.118).The average primary particle diameter of this lithium-nickel-manganese-cobalt system complex oxide powder is 0.5 μ m, and median particle diameter is 3.1 μ m, D
90Be 5.5 μ m, volume density is 1.1g/cc, and the BET specific area is 2.2m
2/ g.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Li:Ni:Mn:Co=1.05:0.45:0.45:0.10, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 13 weight % Gu form, viscosity 1310cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3L/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is that 9.3 * 104 Ω cm, carbon containing concentration C are 0.030 weight %, consists of Li
1.064(Ni
0.457Mn
0.445Co
0.098) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x '=0.098, y '=0.013, z '=0.064).The average primary particle diameter of this lithium-nickel-manganese-cobalt system complex oxide powder is 0.5 μ m, and median particle diameter is 2.1 μ m, D
90Be 3.8 μ m, volume density is 1.2g/cc, and the BET specific area is 1.9m
2/ g.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Li:Ni:Mn:Co=1.10:0.475:0.475:0.05, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.13 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 14 weight % Gu form, viscosity 1960cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3L/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 2.6 * 10
4Ω cm, carbon containing concentration C are 0.031 weight %, consist of Li
1.115(Ni
0.481Mn
0.470Co
0.049) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x '=0.049, y '=0.012, z '=0.115).The average primary particle diameter of this lithium-nickel-manganese-cobalt system complex oxide powder is 0.4 μ m, and median particle diameter is 3.7 μ, D
90Be 6.1 μ m, volume density is 1.1g/cc, and the BET specific area is 1.9m
2/ g.
Comparative example 7
Take by weighing Ni (OH)
2, Mn
3O
4, Co (OH)
2, mol ratio is Ni:Mn:Co=0.45:0.45:0.10, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.15 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 12 weight % Gu form, viscosity 700cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 30L/min, and slip import volume S is 38 * 10
-3L/min (gas liquid ratio G/S=789).Again, dry inlet temperature is 150 ℃.
In the aforesaid particulate powder of carrying out spray drying and obtaining, add mixed powder and be broken to the LiOH powder of median particle diameter below 20 μ m.This mixed-powder of about 13.1g is put in the aluminium oxide earthenware Crucible, and under circulation of air, under 950 ℃, (5 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 1.7 * 10 to calcine 10 hours
4Ω cm, carbon containing concentration C are 0.031 weight %, consist of Li
1.130(Ni
0.443Mn
0.453Co
0.105) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x '=0.105, y '=0.012, z '=0.130).The average primary particle diameter of this lithium-nickel-manganese-cobalt system complex oxide powder is 0.5 μ m, and median particle diameter is 11.1 μ m, D
90Be 18.4 μ m, volume density is 1.8g/cc, and the BET specific area is 1.3m
2/ g.
Comparative example 8
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, mol ratio is Li:Ni:Mn=1.10:0.50:0.50, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.14 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 13 weight % Gu form, viscosity 1270cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3L/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 2.4 * 10
4Ω cm, carbon containing concentration C are 0.044 weight %, consist of Li
1.081(Ni
0.505Mn
0.495) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x '=0, y '=0.010, z '=0.081).The average primary particle diameter of this lithium nickel manganese composite oxide powder body is 0.4 μ m, and median particle diameter is 1.4 μ m, D
90Be 2.1 μ m, volume density is 1.0g/cc, and the BET specific area is 2.7m
2/ g.
Comparative example 9
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, mol ratio is Li:Ni:Mn=1.15:0.50:0.50, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.14 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 13 weight % Gu form, viscosity 1020cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3L/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains to slip and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is that 2.1 * 104 Ω cm, carbon containing concentration C are 0.045 weight %, consists of Li
1.166(Ni
0.505Mn
0.495) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x '=0, y '=0.008, z '=0.166).The average primary particle diameter of this lithium nickel manganese composite oxide powder body is 0.5 μ m, and median particle diameter is 3.3 μ m, D
90Be 5.6 μ m, volume density is 1.2g/cc, and the BET specific area is 1.9m
2/ g.
The lithium-nickel-manganese-cobalt system complex oxide powder of making in the foregoing description 8～11 and the comparative example 7～9 or the composition transitivity value representation of lithium nickel manganese composite oxide powder body are in table 3-and table 6.To be illustrated in table 4 as the powder properties of the spray drying powder of calcining presoma again, ' in.
Table 6
The powder properties of dry body
6) US represents to utilize ultrasonic wave to disperse the processing of " Ultra Sonic dispersion ", numeric representation processing time (branch) thereafter.
Again, the lithium nickel manganese cobalt composite oxide powder that embodiment 8～11 and comparative example 7～9 are made or the pore distribution curve of lithium nickel manganese composite oxide powder body are illustrated respectively in Figure 40～46, SEM image (photo) (multiplying power * 10,000) be illustrated in Figure 47～53, x-ray diffractogram of powder looks like to be illustrated in Figure 54～60.
Embodiment 12
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, Li
2WO
4, mol ratio is Li:Ni:Mn:Co:W=1.10:0.45:0.45:0.10:0.005, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 15 weight % Gu form, viscosity 1720cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 5.4 * 10
4Ω cm, carbon containing concentration C are 0.042 weight %, consist of Li
1.114(Ni
0453Mn
0.450Co
0.097) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x ＂=0.097, y ＂=0.003, z ＂=0.114).Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of W is 0.62 mole of %.Its average primary particle diameter is 0.4 μ m, and median particle diameter is 1.4 μ m, D
90Be 2.1 μ m, volume density is 1.1g/cc, and the BET specific area is 2.1m
2/ g.Further, the atomic ratio of the W on primary particle surface is 9.8 times of atomic ratio (W/ (Ni+Mn+Co)) of the W (tungsten) of whole particle.
Embodiment 13
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, Li
2WO
4, mol ratio is Li:Ni:Mn:Co:W=1.10:0.45:0.45:0.10:0.01, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.17 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 15 weight % Gu form, viscosity 1890cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 4.7 * 10
4Ω cm, carbon containing concentration C are 0.030 weight %, consist of Li
1.139(Ni
0.450Mn
0.452Co
0.098) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x ＂=0.098, y ＂=-0.002, z ＂=0.139).Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of W is 1.03 moles of %.Its average primary particle diameter is 0.3 μ m, and median particle diameter is 2.2 μ m, D
90Be 3.9 μ m, volume density is 1.0g/cc, and the BET specific area is 2.9m
2/ g.Further, the atomic ratio of the W on primary particle surface is 9.4 times of atomic ratio (W/ (Ni+Mn+Co)) of the W (tungsten) of whole particle.
Embodiment 14
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, Li
2MoO
4, mol ratio is Li:Ni:Mn:Co:Mo=1.10:0.45:0.45:0.10:0.005, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 15 weight % Gu form, viscosity 1710cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 3.6 * 10
4Ω cm, carbon containing concentration C are 0.027 weight %, consist of Li
1.124(Ni
0.452Mn
0.450Co
0.098) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x ＂=0.098, y ＂=0.002, z ＂=0.124).Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of Mo is 0.48 mole of %.Its average primary particle diameter is 0.7 μ m, and median particle diameter is 2.0 μ m, D
90Be 3.2 μ m, volume density is 1.3g/cc, and the BET specific area is 1.6m
2/ g.Further, the atomic ratio of the Mo on primary particle surface is 21 times of atomic ratio (Mo/ (Ni+Mn+Co)) of the Mo (molybdenum) of whole particle.Embodiment 15
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, WO
3, mol ratio is Li:Ni:Mn:Co:W=1.10:0.45:0.45:0.10:0.005, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.17 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 14 weight % Gu form, viscosity 1670cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 5.8 * 10
4Ω cm, carbon containing concentration C are 0.033 weight %, consist of Li
1.094(Ni
0.453Mn
0.450Co
0.097) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x ＂=0.097, y ＂=-0.003, z ＂=0.094).Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of W is 0.51 mole of %.Its average primary particle diameter is 0.5 μ m, and median particle diameter is 1.6 μ m, D
90Be 2.4 μ m, volume density is 1.0g/cc, and the BET specific area is 2.2m
2/ g.Further, the atomic ratio of the W on primary particle surface is 12 times of atomic ratio (W/ (Ni+Mn+Co)) of the W (tungsten) of whole particle.
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, Nb
2O
5, mol ratio is Li:Ni:Mn:Co:Nb=1.10:0.45:0.45:0.10:0.005, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.17 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 14 weight % Gu form, viscosity 1660cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 4.4 * 10
4Ω cm, carbon containing concentration C are 0.027 weight %, consist of Li
1.118(Ni
0.448Mn
0.450Co
0.1102) O
2The lithium nickel manganese cobalt composite oxide with layer structure (x ＂=0.102, y ＂=-0.002, z ＂=0.118).Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of Nb is 0.48 mole of %.Its average primary particle diameter is 0.6 μ m, and median particle diameter is 2.0 μ m, D
90Be 3.3 μ m, volume density is 1.2g/cc, and the BET specific area is 1.9m
2/ g.Further, the atomic ratio of the Nb on primary particle surface is 8.8 times of atomic ratio (Nb/ (Ni+Mn+Co)) of the Nb (niobium) of whole particle.Comparative example 10
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, mol ratio is Li:Ni:Mn:Co=1.10:0.45:0.45:0.10, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 13 weight % Gu form, viscosity 1350cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 2.7 * 10
4Ω cm, carbon containing concentration C are 0.023 weight %, consist of Li
1.096(Ni
0.458Mn
0.444Co
0.098) O
2Lithium nickel manganese cobalt composite oxide (x ＂=0.098, y ＂=0.016, z ＂=0.096).Its average primary particle diameter is 0.6 μ m, and median particle diameter is 3.0 μ m, D
90Be 5.1 μ m, volume density is 1.2g/cc, and the BET specific area is 1.7m
2/ g.
Comparative example 11
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, Li
2WO
4, mol ratio is Li:Ni:Mn:Co:W=1.10:0.45:0.45:0.10:0.02, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.13 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 15 weight % Gu form, viscosity 1910cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 1.1 * 10
4Ω cm, carbon containing concentration C are 0.050 weight %, consist of the lithium nickel manganese cobalt composite oxide (x ＂=0.097, y ＂=0.012, z ＂=0.124) of Li1.124 (Ni0.457Mn0.446Co0.097) O2.Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of W is 2.06 moles of %.Its average primary particle diameter is 0.2 μ m, and median particle diameter is 0.8 μ m, D
90Be 1.3 μ m, volume density is 0.9g/cc, and the BET specific area is 3.8m
2/ g.Further, the atomic ratio of the W on primary particle surface is 6.0 times of atomic ratio (W/ (Ni+Mn+Co)) of the W (tungsten) of whole particle.
Comparative example 12
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, Li
2B
4O
7, mol ratio is Li:Ni:Mn:Co:B=1.10:0.45:0.45:0.10:0.005, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.16 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 15 weight % Gu form, viscosity 1460cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 5.3 * 10
4Ω cm, carbon containing concentration C are 0.047 weight %, consist of Li
1.096(Ni
0.450Mn
0.451Co
0.099) O
2Lithium nickel manganese cobalt composite oxide (x ＂=0.099, y ＂=-0.001, z ＂=0.096).Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of B is 0.24 mole of %.Its average primary particle diameter is 1.0 μ m, and median particle diameter is 5.9 μ m, D
90Be 8.9 μ m, volume density is 1.8g/cc, and the BET specific area is 0.8m
2/ g.Further, the atomic ratio of the B on primary particle surface is 213 times of atomic ratio (B/ (Ni+Mn+Co)) of the B (boron) of whole particle.
Comparative example 13
Take by weighing Li
2CO
3, Ni (OH)
2, Mn
3O
4, CoOOH, SnO
2, mol ratio is Li:Ni:Mn:Co:Sn=1.10:0.45:0.45:0.10:0.005, after the mixing, adds pure water inward, the preparation slip.This slip is stirred on the limit, and the limit is crushed to median particle diameter 0.17 μ m with circulating medium-stirring wet-type pulverizer with the solid formation branch in the slip.
Then, (the former chemical industry machine in great river (strain) is made: the LT-8 type) this slip (dividing content 14 weight % Gu form, granularity 1580cp) is carried out spray drying with second fluid nozzle type spray dryer.As dry gas use air at this moment, dry gas import volume G is 45L/min, and slip import volume S is 11 * 10
-3ML/min (gas liquid ratio G/S=4091).Again, dry inlet temperature is 150 ℃.The spray dryer that passes through of about 15g is carried out the particulate powder that spray drying obtains and puts in the aluminium oxide earthenware Crucible, under air atmosphere, under 1000 ℃, calcine 6 hours (3.33 ℃ of warming and cooling rates/min) afterwards, pulverize, obtaining specific insulation is 3.1 * 10
4Ω cm, carbon containing concentration C are 0.028 weight %, consist of Li
1.083(Ni
0.448Mn
0.456Co
0.096) O
2Lithium nickel manganese cobalt composite oxide (x ＂=0.096, y ＂=-0.009, z ＂=0.083).Again, (Ni, Mn, Co) total mol ratio was made as 1 o'clock, the molar ratio that contains of Sn is 0.49 mole of %.Its average primary particle diameter is 0.5 μ m, and median particle diameter is 3.8 μ m, D
90Be 6.2 μ m, volume density is 1.1g/cc, and the BET specific area is 1.7m
2/ g.Further, the atomic ratio of the Sn on primary particle surface is 3.5 times of atomic ratio (Sn/ (Ni+Mn+Co)) of the Sn (tin) of whole particle.
The composition transitivity value representation of the lithium transition-metal based compound powder of making in the foregoing description 12～16 and the comparative example 10～13 is in table 7-10 and table 11.To be illustrated among table 5 ＂ as the powder properties of the spray drying body of calcining presoma again.
Again, the pore distribution curve of the lithium nickel manganese cobalt composite oxide powder of making in embodiment 12～16 and the comparative example 10～13 is illustrated respectively in Figure 61～69, SEM image (photo) (multiplying power * 10,000) is illustrated in Figure 70～78, and x-ray diffractogram of powder looks like to be illustrated respectively in Figure 79～87.
Table 7
※ 1) summation of the interpolation metallic element of the surface portion of particle with remove lithium, add atomic ratio (add element/(Ni+Mn+Co)), and the ratio of this atomic ratio of whole primary particle of the summation of the metallic element the metallic element.
Table 9
※5)：(1-x)(0.05-0.98y)
※6)：(1-x)(0.20-0.88y)
Table 11
The powder properties of spray drying body
※ 7) US represents to utilize ultrasonic wave to disperse the processing of " Ultra Sonic dispersion ", numeric representation processing time (branch) thereafter.
[making of battery and evaluation 1-1]
The lithium nickel manganese cobalt composite oxide powder of the foregoing description 1～5 and comparative example 1～5 manufacturing is used as positive electrode (positive active material) respectively, make lithium secondary battery, estimate according to following method.
The speed experiment
Take by weighing the following mixture of mixed proportion, be lithium nickel manganese cobalt composite oxide powder each 75 weight %, acetylene carbon black 20 weight %, the polytetrafluorethylepowder powder 5 weight % that embodiment 1～5 and comparative example 1～5 are made, this mixture is fully mixed in mortar, the fry batter in a thin layer material of shape punches to it with 9mm Φ puncher.At this moment, whole weight is adjusted into about 8mg.Its pressure is bonded at the aluminium expanding metal, as the positive pole of 9mm Φ.
With the positive pole of this 9mm Φ as the test utmost point, with the lithium metallic plate as to the utmost point, in the solvent of EC (ethyl carbonate): EMC (carbonic acid ethyl methyl esters)=3:7 (Capacity Ratio), be dissolved with the LiPF6 of 1mol/L, with it as electrolyte, with thickness be the porous polyethylene film of 25 μ m as barrier film, be assembled into the coin shape battery.
About the coin shape battery that obtains, initial stages two circulation is that the charging upper voltage limit is set to 4.8V, carries out constant current constant voltage and (uses current density: 0.137mA/cm
2(0.1C) constant current charge is after 4.8V, and constant voltage charge is to 0.01C again) charging after, the lower voltage limit that will discharge is arranged on 3.0V, carries out constant-current discharge (current density: 0.137mA/cm
2(0.1C)).Then carry out the 3rd circulation, with the constant current of 0.1C, the constant-current constant-voltage charging that is set to 4.4V by the charging upper voltage limit (is used current density 0.137mA/cm
2(0.1C) constant current charge is behind 4.4V, constant voltage charge is to 0.01C again), the discharge lower voltage limit is set to the constant-current discharge of 3.0V, discharge and recharge the test of 1 circulation, further carry out 4～11 circulations, carry out the test of each constant current charge of constant-current constant-voltage charging (behind 4.4V, constant voltage charge is to 0.01C again with the 0.2C constant current charge), 0.1C, 0.2C, 0.5C, 1C, 3C, 5C, 7C and the 9C of 0.2C.Just, being assumed to the every 1g active material of the suitable electric current of 1C is 150mA.The 0.1C discharge capacity (mAh/g) (first discharge capacity) of investigation the 1st circulation at this moment, the 0.1C discharge capacity (mAh/g) (the 4th cyclic discharge capacity [a]) of the 4th circulation, the 1C discharge capacity (mAh/g) (the 7th cyclic discharge capacity [b]) of the 7th circulation, the percentage (%) that the 7th cyclic discharge capacity [b] accounts for the 4th cyclic discharge capacity [a], the 9C discharge capacity (mAh/g) of the 11st circulation, the result is shown in the table 12.
In addition, qualification determination benchmark as embodiment, the initial stage discharge capacity of above-mentioned the 1st circulation is set in more than the 200mAh/g, the 1C discharge capacity of above-mentioned the 7th circulation is set in more than the 150mAh/g, the percentage (%) that the 1C discharge capacity accounts for above-mentioned 0.1C discharge capacity is set in more than 82%, and the 9C discharge capacity of above-mentioned the 11st circulation is set in more than the 60mAh/g.
Can know following thing according to table 12.
Because in comparative example 1～4, the mercury amount of being pressed into is very few, then the discharge capacity of battery is at low speed, all lower at a high speed.
In comparative example 5, because the mercury amount of being pressed into is very few and Li measures z less than lower limit, so the discharge capacity of battery is at low speed, all lower at a high speed.
[making of battery and evaluation 1-2]
The lithium-nickel-manganese-cobalt system complex oxide powder of the foregoing description 6,7 and comparative example 6 manufacturings is used as positive electrode (positive active material) respectively, make lithium secondary battery, estimate according to following method.
The speed experiment
Take by weighing the following mixture of mixed proportion, be lithium-nickel-manganese-cobalt system complex oxide powder each 75 weight %, acetylene carbon black 20 weight %, the polytetrafluorethylepowder powder 5 weight % that embodiment 6,7 and comparative example 4,6 are made, this mixture is fully mixed in mortar, the fry batter in a thin layer material of shape punches to it with 9mm Φ puncher.At this moment, whole weight is adjusted into about 8mg.Its pressure is bonded at the aluminium expanding metal, as the positive pole of 9mm Φ.
With the positive pole of this 9mm Φ as the test utmost point, with the lithium metallic plate as to the utmost point, in the solvent of EC (ethyl carbonate): DMC (dimethyl carbonate): EMC (carbonic acid ethyl methyl esters)=3:3:4 (Capacity Ratio), be dissolved with the LiPF6 of 1mol/L, with it as electrolyte, with thickness be the porous polyethylene film of 25 μ m as barrier film, be assembled into the coin shape battery.
About the coin shape battery that obtains, initial stages two circulation is that the charging upper voltage limit is set to 4.4V, carries out constant current constant voltage and (uses current density: 0.137mA/cm
2(0.1C) constant current charge is after 4.4V, and constant voltage charge is to 0.01C again) charging after, the lower voltage limit that will discharge is arranged on 3.0V, carries out constant-current discharge (current density: 0.137mA/cm
2(0.1C)).Then carry out 3～10 circulations, carry out the test of each constant current charge of constant-current constant-voltage charging (behind 4.4V, constant voltage charge is to 0.01C again with the 0.2C constant current charge), 0.1C, 0.2C, 0.5C, 1C, 3C, 5C, 7C and the 9C of 0.2C.Just, being assumed to the every 1g active material of the suitable electric current of 1C is 150mA.The 0.1C discharge capacity (mAh/g) (first discharge capacity) of investigation the 1st circulation at this moment, the 0.1C discharge capacity (mAh/g) (the 3rd cyclic discharge capacity) [a] of the 3rd circulation, the 1C discharge capacity (mAh/g) (the 6th cyclic discharge capacity) [b] of the 6th circulation, the 9C discharge capacity (mAh/g) (the 10th cyclic discharge capacity) [c] of the 10th circulation, the result is shown in the table 13.
In addition, qualification determination benchmark as embodiment, the initial stage discharge capacity of above-mentioned the 1st circulation is set in more than the 170mAh/g, the 0.1C discharge capacity of the 3rd circulation is set in more than the 175mAh/g, the 1C discharge capacity of the 6th circulation is set in more than the 155mAh/g, and the 9C discharge capacity of the 10th circulation is set in more than the 110mAh/g.
Can know following thing according to table 13.
In comparative example 4,6, because the mercury amount of being pressed into is very few, then to compare with the roughly equal embodiment sample (embodiment 7,6) of Co mol ratio (y), the discharge capacity of battery is at low speed, all lower at a high speed.
Relatively, lithium transition-metal based compound powder of the present invention by having the specific mercury amount of being pressed into is as positive electrode, and a kind of circulation deterioration, capacity height, part throttle characteristics anode materials for lithium secondary cells also good, that performance balance is good when suppressing high pressure and using can be provided.
Again, the powder properties (median particle diameter, volume density, specific area) with the spray drying body (calcining presoma) of embodiment 1～5, comparative example 1～5 is illustrated in the table 14.
The powder properties of table 14 spray drying body
5) US represents to utilize ultrasonic wave to disperse " Ultra Sonic dispersion ".
According to table 14, can know median particle diameter that the ultrasonic wave of embodiment 1～5 disperses (5 minutes) more than the 0.1 μ m, below the 1 μ m, the BET specific area is 10～60m
2/ g, and comparative example 1～5 to 1 μ m big (all more than 5 μ m) compares 60m
2/ g is big.
[making of battery and estimate 2]
The lithium-nickel-manganese-cobalt system complex oxide powder or the lithium nickel manganese composite oxide powder body of the foregoing description 8～11 and comparative example 7～9 manufacturings are used as positive electrode (positive active material) respectively, make lithium secondary battery, estimate.
The making of lithium secondary battery and speed trial are carried out with above-mentioned " battery make and estimate 1-2 " the samely.
In addition, qualification determination benchmark as embodiment, the initial stage discharge capacity of above-mentioned the 1st circulation is set in more than the 175mAh/g, the 0.1C discharge capacity of the 3rd circulation is set in more than the 175mAh/g, the 1C discharge capacity of the 6th circulation is set in more than the 160mAh/g, and the 9C discharge capacity of the 10th circulation is set in more than the 116mAh/g.
The result is shown in the table 15.
Can understand that according to table 15 positive electrode material of lithium secondary cell according to the present invention can be realized the lithium secondary battery that composite attribute is good with lithium-nickel-manganese-cobalt system complex oxide powder.
[making of battery and estimate 3]
(1) speed trial
The lithium-nickel-manganese-cobalt system complex oxide powder or the lithium nickel manganese composite oxide powder body of the foregoing description 12～16 and comparative example 10～13 manufacturings are used as positive electrode (positive active material) respectively, make lithium secondary battery, estimate.
The making of lithium secondary battery and speed trial are carried out with above-mentioned " battery make and estimate 1-2 " the samely.
In addition, qualification determination benchmark as embodiment, the initial stage discharge capacity of above-mentioned the 1st circulation is set in more than the 176mAh/g, the 0.1C discharge capacity of the 3rd circulation is set in more than the 176mAh/g, the 1C discharge capacity of the 6th circulation is set in more than the 160mAh/g, and the 9C discharge capacity of the 10th circulation is set in more than the 116mAh/g.
The result is shown in the table 16.
(2) low temperature load-characteristic test
Take by weighing the following mixture of mixed proportion, be lithium nickel manganese cobalt composite oxide powder each 75 weight %, acetylene carbon black 20 weight %, the polytetrafluorethylepowder powder 5 weight % that embodiment 12～16 and comparative example 10～13 are made, this mixture is fully mixed in mortar, the fry batter in a thin layer material of shape punches to it with 9mm Φ and 12mm Φ puncher.At this moment, whole weight is adjusted into about 8mg, 18mg.Its pressure is bonded at the aluminium expanding metal, as the positive pole of 9mm Φ and 12mm Φ.Being called of 9mm Φ " anodal A ", being called of 12mm Φ " anodal B ".
With the anodal A of 9mm Φ as the test utmost point, with the lithium metallic plate as to the utmost point, in the solvent of EC (ethyl carbonate): DMC (dimethyl carbonate): EMC (carbonic acid ethyl methyl esters)=3:3:4 (Capacity Ratio), be dissolved with the LiPF6 of 1mol/L, with it as electrolyte, with thickness be the porous polyethylene film of 25 μ m as barrier film, be assembled into the coin shape battery.
Coin shape battery about obtaining carries out 0.2mA/cm
2Constant-current constant-voltage charging, promptly under upper limit 4.2V, carry out emitting the reaction of lithium ion from positive pole.Then, with 0.2mA/cm
2, the positive active material per unit weight the initial stage charging capacity be made as Qs (C) [mAh/g], the initial stage discharge capacity is made as Qs (D) [mAh/g].
As negative electrode active material use average grain diameter 8～10 μ m powdered graphite (
), use Kynoar as binding agent, take by weighing these, with the weight ratio ratio of 92.5:7.5, in N-methyl pyrrolidone solution, mix them, make negative pole depolarising mixture slip.This slip is coated on the one side of Copper Foil that thickness is 20 μ m, drying, make solvent evaporation after, beat the hole of 12mm Φ, use 0.5ton/cm
2(49MPa) carry out extrusion process, make negative pole B.At this moment, the amount of the negative electrode active material on the electrode is adjusted to about 5～12mg.
In addition, this negative pole B as the test utmost point, as to the utmost point, is formed battery with this lithium metal, under lower limit 0V, use 0.2mA/cm
2When constant current-constant-voltage method of-3mV (cutting off electric current 0.05mA) made negative pole embed the test of lithium ion, the initial stage embedding capacity of negative electrode active material per unit weight was Qf[mAh/g].
With above-mentioned anodal A and negative pole B combination, use the coin shape battery, be assembled into testing battery, its battery performance is estimated.Promptly, on the anodal cylinder of coin shape battery, place the above-mentioned anodal B that makes, the thickness of placing thereon as barrier film is the porous polyethylene film of 25 μ m, after compressing with the gasket seal of polypropylene system, as nonaqueous electrolytic solution, use is dissolved with the electrolyte of the LiPF6 of 1moll/L in the solvent of EC (ethyl carbonate): DMC (dimethyl carbonate): EMC (carbonic acid ethyl methyl esters)=3:3:4 (Capacity Ratio), in cylinder, add this electrolyte, fully after the osmotic membrane, place above-mentioned negative pole B, put the negative pole cylinder and seal, make the lithium secondary battery of coin shape.In addition, at this moment, the balance of the weight of positive active material and negative electrode active material weight is set at the formula below roughly satisfying.
Positive active material weight [g]/negative electrode active material weight [g]
＝(Qf[mAh/g]/1.2)Qs(C)[mAh/g]
In order to measure the low temperature part throttle characteristics of the battery that obtains like this, according to 1 hour rate current value of following formula setting battery, promptly 1C carries out following test.
1C[mA]=Qs (D) * positive active material weight [g]/h
At first, at room temperature, carry out constant current 0.2C discharge and recharge 2 the circulation and constant current 1C discharge and recharge 1 the circulation.In addition, be limited to 4.1V in the charging, lower voltage limit is 3.0V.Then, after will under-30 ℃ lower-temperature atmosphere, keeping more than 1 hour by the coin shape battery that the 1/3C constant current charge-discharge is adjusted into depth of charge 40%, with constant current 0.5C[mA] down the voltage behind discharge 10 seconds during 10 seconds be V[mV], voltage before the discharge is made as V0[mV] time, Δ V=V-V0 calculates resistance value R[Ω by following formula].
R[Ω]＝ΔV[mV]/0.5C[mA]
The resistance value that the lithium nickel manganese cobalt composite oxide of embodiment 12～16 and comparative example 10～13 is measured as the battery of positive active material is used in expression respectively in table 16.Resistance value is more little, represents that then the low temperature part throttle characteristics is good more.In addition, as the qualification determination benchmark of embodiment, set this resistance value below 480 Ω.
Can understand by table 16,, can realize the lithium secondary battery that part throttle characteristics is good according to positive electrode material of lithium secondary cell according to the present invention lithium-nickel-manganese-cobalt system complex oxide powder etc.
The present invention is had been described in detail, and with reference to specific execution mode, but do not break away from the spirit and scope of the present invention and in addition various changes and correction will be readily apparent to persons skilled in the art.
The application is based on the Japanese patent application (the special 2006-106288 of hope) of application on April 7th, 2006, the Japanese patent application (spy is willing to 2006-266580) of application on September 2nd, 2006, the Japanese patent application (the special 2006-257260 of hope) of application on September 22nd, 2006 and the Japanese patent application of applying on November 10th, 2006 (the special 2006-305015 of hope), and its content is here put into as a reference.
The possibility of utilizing on the industry
The purposes of lithium secondary battery of the present invention is especially restriction not, can be used for known purposes. As concrete example, can So that notebook computer, pen computer, palm PC, e-book, mobile phone, mobile fax, mobile multiple to be arranged for example Seal machine, mobile printer, stereophone, portable type shooting, LCD TV, portable suction fan, portable CD, MD, portable radio transceiver, PDA, calculator, storage card, ghetto blaster, radio, back-up source, Motor, ligthing paraphernalia, toy, game machine, clock and watch, stroboscope, electric tool, automobile are with power source etc.
Claims (63)
1. a positive electrode material of lithium secondary cell is characterized in that with lithium transition-metal based compound powder the mercury that obtains in mercury penetration method is pressed in the curve, and mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.8cm
3/ g is above, 3cm
3Below/the g.
2. lithium transition-metal based compound powder as claimed in claim 1, it is characterized in that, the pore distribution curve that mercury penetration method obtains more than pore radius 300nm, locate to have the main peak that has summit below the 1000nm, and more than pore radius 80nm, less than the 300nm place, do not have the submaximum that has summit.
3. lithium transition-metal based compound powder as claimed in claim 1 is characterized in that, in the pore distribution curve that mercury penetration method obtains, more than pore radius 300nm, locate to exist pore capacity that the main peak of summit relates at 0.5cm below the 1000nm
3/ g is above, 1.5cm
3Below/the g.
4. lithium transition-metal based compound powder as claimed in claim 1, it is characterized in that, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than the 0.6 μ m, below the 5 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
5. lithium transition-metal based compound powder as claimed in claim 1 is characterized in that, is the lithium-nickel-manganese-cobalt system complex oxide by following composition formula (I) expression,
Li[Li
Z/ (2+z){ (Li
xNi
(1-3x)/2Mn
(1+x)/2)
1-yCo}
2/ (2+z)] O
2... composition formula (I)
Wherein, in composition formula (I), 0 ≦ x ≦ 0.33,0 ≦ y ≦ 0.2 ,-0.02 ≦ z ≦ 0.2 (1-y) (1-3x).
6. lithium transition-metal based compound powder as claimed in claim 1 is characterized in that volume density is 0.5～1.5g/cm
3
7. lithium transition-metal based compound powder as claimed in claim 1 is characterized in that the BET specific area is 1.5～5m
2/ g.
8. lithium transition-metal based compound powder as claimed in claim 1 is characterized in that, in the time of will containing concentration of carbon and be made as C (weight %), the C value is more than the 0.005 weight %, below the 0.2 weight %.
9. the manufacture method of the described lithium transition-metal based compound of claim 1 powder, it is characterized in that, in liquid medium with lithium compound and at least a more than transistion metal compound pulverize, to making its homodisperse slip carry out spray drying and obtain the spray drying body, this spray drying body is calcined in oxygen-containing gas atmosphere.
10. manufacture method as claimed in claim 9 is characterized in that, the spray drying body comprises a kind of interior interstitial compound of second particle that makes the spray drying body at least, uses as the calcining presoma.
11. manufacture method as claimed in claim 10 is characterized in that, produces when the compound that the space is formed is calcining or is sublimed into decomposition gas and makes interstitial compound in the second particle.
12. manufacture method as claimed in claim 11 is characterized in that, one of decomposition gas is carbonic acid gas (CO
2).
13. manufacture method as claimed in claim 9 is characterized in that, lithium compound is a lithium carbonate.
14. the spray drying body of a lithium transition-metal based compound, it is characterized in that, described spray drying body by in liquid medium with lithium compound and at least a above transistion metal compound pulverizing, to making its homodisperse slip carry out spray drying and obtaining, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of this spray drying body of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.01 μ m, below the 4 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
15. spray drying body as claimed in claim 14 is characterized in that, the BET specific area is 10～70m
2/ g.
16. the calcining presoma of a lithium transition-metal based compound is characterized in that, at least also contains the interstitial compound in the second particle that makes more than a kind in the described spray drying body of claim 14.
17. a secondary lithium batteries positive pole is characterized in that, has the positive electrode active material layer that contains claim 1 described lithium transition-metal based compound powder and binding agent on the collector.
18. a lithium secondary battery is characterized in that, described lithium secondary battery possesses negative pole, nonaqueous electrolyte that contains lithium salts that can embed removal lithium embedded and the positive pole that can embed removal lithium embedded, uses the described secondary lithium batteries of claim 17 anodal as anodal.
19. positive electrode material of lithium secondary cell lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, contain compound by following composition formula (I ') expression, contain the crystalline texture that belongs to layer structure and constitute, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is made as FWHM (110), then use 0.01 ≦ FWHM (110) ≦ 0.2 expression
Li[Li
z′/(2+z′){(Ni
(1+y′)/2Mn
(1-y′)/2)
1-x′Co
x’}
2/(2+z′)]O
2 ......(I′)
Wherein, in composition formula (I '), 0 ≦ x ′ ≦ 0.1 ,-0.1 ≦ y ′ ≦ 0.1, (1-x ') (0.05-0.98y ') ≦ z ′ ≦ (1-x ') (0.15-0.88y ').
20. positive electrode material of lithium secondary cell as claimed in claim 19 lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, in composition formula (I '), 0.04 ≦ x ′ ≦ 0.099,-0.03 ≦ y ′ ≦ 0.03, (1-x ') (0.08-0.98y ') ≦ z ′ ≦ (1-x ') (0.13-0.88y ').
21. lithium transition metal-based compound powder for positive electrode material in lithium rechargeable battery as claimed in claim 19; It is characterized in that; In the powder x-ray diffraction that uses Cuk α line is measured; The angle of diffraction 2 θ are near (018) diffraction maximum 64 °, near (110) diffraction maximum 64.5 ° and near (113) diffraction maximum 68 °; High corner side at separately summit does not have the heterogeneous diffraction maximum that causes; When perhaps having the heterogeneous diffraction maximum that causes; The integrated intensity of heterogeneous peak and the diffraction maximum of original crystalline phase is than respectively in following scope
0≦I
018*/I
018≦0.20
0≦I
110*/I
110≦0.25
0≦I
113*/I
113≦0.30
Here, I
018, I
110, I
113The integrated intensity of representing (018), (110), (113) diffraction maximum respectively, I
018*, I
110*, I
113*Express the integrated intensity of the heterogeneous diffraction maximum that causes of the high corner side of the summit of (018), (110), (113) diffraction maximum now respectively.
22. positive electrode material of lithium secondary cell as claimed in claim 19 is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder the mercury that obtains in mercury penetration method is pressed in the curve, mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.7cm
3/ g is above, 1.5cm
3Below/the g.
23. positive electrode material of lithium secondary cell as claimed in claim 19 lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, the pore distribution curve that mercury penetration method obtains more than pore radius 300nm, locate to have the main peak that has summit below the 1000nm, and more than pore radius 80nm, less than the 300nm place, do not have the submaximum that has summit.
24. positive electrode material of lithium secondary cell as claimed in claim 19 lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, in the pore distribution curve that mercury penetration method obtains, more than pore radius 300nm, locate to exist pore capacity that the main peak of summit relates to below the 1000nm at 0.3cm
3/ g is above, 1.0cm
3Below/the g.
25. positive electrode material of lithium secondary cell as claimed in claim 19 lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than the 1 μ m, below the 5 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
26. positive electrode material of lithium secondary cell as claimed in claim 19 is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder volume density is 0.5～1.7g/cm
3
27. positive electrode material of lithium secondary cell as claimed in claim 19 is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder the BET specific area is 1.4～3m
2/ g.
28. positive electrode material of lithium secondary cell as claimed in claim 19 is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder, in the time of will containing concentration of carbon and be made as C (weight %), the C value is more than the 0.005 weight %, below the 0.05 weight %.
29. positive electrode material of lithium secondary cell as claimed in claim 19 is characterized in that with lithium-nickel-manganese-cobalt system complex oxide powder the specific insulation when compressing with 40MPa pressure is 1 * 10
3Ω cm is above, 1 * 10
6Below the Ω cm.
30. the described positive electrode material of lithium secondary cell of claim 19 manufacture method of lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, comprise: the slip preparation section, in liquid medium, lithium compound, nickel compound, manganese compound and cobalt compound are pulverized, obtained making its homodisperse slip; The spray drying operation is carried out spray drying to the slip that obtains; Calcination process, in oxygen-containing gas atmosphere, the temperature T of 940 ℃ ≦ T ≦ 1200 ℃ (℃) under, the spray drying body that obtains is calcined.
31. positive electrode material of lithium secondary cell as claimed in claim 30 is characterized in that with the manufacture method of lithium-nickel-manganese-cobalt system complex oxide powder lithium compound is a lithium carbonate.
32. the positive electrode material of lithium secondary cell as claimed in claim 30 manufacture method of lithium-nickel-manganese-cobalt system complex oxide powder, it is characterized in that, in the slip preparation section, in liquid medium with lithium compound, nickel compound, manganese compound and cobalt compound are pulverized, be crushed to median particle diameter below 0.3 μ m, this median particle diameter is to disperse (power output 30W at the ultrasonic wave that carried out 5 minutes, frequency 22.5kHz) afterwards, measure by laser diffraction/diffuse transmission type particle size distribution device and to obtain, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference, in the spray drying operation, slip viscosity during with spray drying is made as V (cp), the slip quantity delivered is made as S (L/min), when gas delivery volume is made as G (L/min), then at 50cp ≦ V ≦ 4000cp, carry out spray drying under the condition of 1500 ≦ G/S ≦ 5000.
33. the spray drying powder of a lithium-nickel-manganese-cobalt system complex oxide, it is characterized in that, pass through in liquid medium lithium compound as the spray drying powder of positive electrode material of lithium secondary cell with the presoma of lithium-nickel-manganese-cobalt system complex oxide powder, nickel compound, manganese compound and cobalt compound are pulverized, to making its homodisperse slip carry out spray drying and obtaining, the ultrasonic wave that described spray drying powder was carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of this spray drying powder of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.01 μ m, below the 4 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
34. spray drying powder as claimed in claim 33 is characterized in that, the BET specific area is 10～100m
2/ g.
35. a secondary lithium batteries positive pole is characterized in that, has on the collector to contain the positive electrode active material layer of the described positive electrode material of lithium secondary cell of claim 19 with lithium-nickel-manganese-cobalt system complex oxide powder and binding agent.
36. a lithium secondary battery is characterized in that, described lithium secondary battery possesses negative pole, nonaqueous electrolyte that contains lithium salts that can embed removal lithium embedded and the positive pole that can embed removal lithium embedded, uses the described secondary lithium batteries of claim 35 anodal as anodal.
37. lithium secondary battery as claimed in claim 36 is characterized in that, the charging potential that is designed to the positive pole in the fully charged state is more than 4.35V (vs.Li/Li+).
38. positive electrode material of lithium secondary cell lithium transition-metal based compound powder, it is characterized in that, with the lithium transition-metal based compound with the function that can embed the removal lithium embedded ion is main component, the grain growth when in this main component raw material, adding the inhibition calcining more than at least a kind and the additive of sintering, the ratio of the integral molar quantity of the transition metal in the addition of this additive and the main component raw material is at 0.01 mole more than the % and less than 2 moles of %, calcines then and obtains.
39. positive electrode material of lithium secondary cell as claimed in claim 38 lithium transition-metal based compound powder, it is characterized in that, described additive is the oxide that contains at least a above element that is selected from Mo, W, Nb, Ta and Re (below, be called " interpolation element ").
40. positive electrode material of lithium secondary cell as claimed in claim 38 lithium transition-metal based compound powder, it is characterized in that the atomic ratio of the summation of the summation of this interpolation element of the surface portion of primary particle and the metallic element except that Li and described interpolation element is more than 5 times of this atomic ratio of whole particle.
41. positive electrode material of lithium secondary cell as claimed in claim 38 lithium transition-metal based compound powder, it is characterized in that, the ultrasonic wave that carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.1 μ m, less than 3 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
42. positive electrode material of lithium secondary cell as claimed in claim 38 is characterized in that with lithium transition-metal based compound powder the average grain diameter of primary particle is more than the 0.1 μ m, below the 0.9 μ m.
43. positive electrode material of lithium secondary cell as claimed in claim 38 is characterized in that with lithium transition-metal based compound powder the BET specific area is at 1.5m
2/ g is above, 5m
2Below/the g.
44. positive electrode material of lithium secondary cell as claimed in claim 38 is characterized in that with lithium transition-metal based compound powder the mercury that obtains in mercury penetration method is pressed in the curve, mercury the be pressed into amount of pressure when 3.86kPa rises to 413MPa is at 0.7cm
3/ g is above, 1.5cm
3Below/the g.
45. positive electrode material of lithium secondary cell as claimed in claim 38 lithium transition-metal based compound powder, it is characterized in that, the pore distribution curve that mercury penetration method obtains more than pore radius 300nm, locate to have at least the main peak that has summit more than 1 below the 1000nm, and more than pore radius 80nm, less than the 300nm place, do not have the submaximum that has summit.
46. positive electrode material of lithium secondary cell as claimed in claim 38 lithium transition-metal based compound powder, it is characterized in that, in the pore distribution curve that mercury penetration method obtains, more than pore radius 300nm, locate to exist pore capacity that the peak of summit relates to below the 1000nm at 0.4cm
3/ g is above, 1cm
3Below/the g.
47. it is characterized in that with lithium transition-metal based compound powder volume density is at 0.5g/cm as any described positive electrode material of lithium secondary cell in the claim 38～46
3More than, 1.7g/cm
3Below.
48. positive electrode material of lithium secondary cell as claimed in claim 38 is characterized in that with lithium transition-metal based compound powder the specific insulation when compressing with 40MPa pressure is 1 * 10
3Ω cm is above, 1 * 10
6Below the Ω cm.
49. positive electrode material of lithium secondary cell as claimed in claim 38 is characterized in that with lithium transition-metal based compound powder the lithium-nickel-manganese-cobalt system complex oxide that constitutes is main component to contain the crystalline texture that belongs to layer structure.
50. positive electrode material of lithium secondary cell as claimed in claim 49 lithium transition-metal based compound powder is characterized in that, its row composition formula composed as follows (I ") shown in,
LiMO
2 (I”)
Wherein, in the above-mentioned formula (I "), M is the element that is made of Li, Ni and Mn or Li, Ni, Mn and Co, and the Mn/Ni mol ratio is more than 0.8, below 5; Co/ (Mn+Ni+Co) mol ratio is more than 0, below 0.30, and the Li mol ratio is more than 0.001, below 0.2 among the M.
51. positive electrode material of lithium secondary cell as claimed in claim 49 is characterized in that with lithium transition-metal based compound powder, is under oxygen-containing gas atmosphere, is that calcining obtains more than 970 ℃ in calcining heat.
52. positive electrode material of lithium secondary cell as claimed in claim 49 is characterized in that with lithium transition-metal based compound powder, in the time of will containing concentration of carbon and be made as C (weight %), the C value is more than the 0.005 weight %, below the 0.05 weight %.
53. positive electrode material of lithium secondary cell as claimed in claim 50 is characterized in that with lithium transition-metal based compound powder, the M in the described composition formula (I ") is by following formula (II ") expression,
M＝Li
z′’/(2+z′’){(Ni
(1+y′’)/2Mn
(1-y’′)/2)
1-x’′Co
x”}
2/(2+z’′)... ...(II”)
Wherein, in above-mentioned formula (II "), 0 ≦ x ′ ’ ≦ 0.1 ,-0.1 ≦ y ’ ′ ≦ 0.1, (1-x ' ') (0.05-0.98y ' ') ≦ z ′ ’ ≦ (1-x ' ') (0.20-0.88y ' ').
54. positive electrode material of lithium secondary cell as claimed in claim 53 lithium transition-metal based compound powder, it is characterized in that, in the powder x-ray diffraction that uses CuK α line is measured, when near the half width of the angle of diffraction 2 θ (110) diffraction maximum 64.5 ° is made as FWHM (110), then use 0.01 ≦ FWHM (110) ≦ 0.2 expression.
55. such as claim 53 or 54 described lithium transition metal-based compound powder for positive electrode material in lithium rechargeable batteries; It is characterized in that; In the powder x-ray diffraction that uses CuK α line is measured; The angle of diffraction 2 θ are near (018) diffraction maximum 64 °, near (110) diffraction maximum 64.5 ° and near (113) diffraction maximum 68 °; High corner side at separately summit does not have the heterogeneous diffraction maximum that causes; When perhaps having the heterogeneous diffraction maximum that causes; The integrated intensity of heterogeneous peak and the diffraction maximum of original crystalline phase is than respectively in following scope
0≦I
018*/I
018≦0.20
0≦I
110*/I
110≦0.25
0≦I
113*/I
113≦0.30
Here, I
018, I
110, I
113The integrated intensity of representing (018), (110), (113) diffraction maximum respectively, I
018*, I
110*, I
113*Express the integrated intensity of the heterogeneous diffraction maximum that causes of the high corner side of the summit of (018), (110), (113) diffraction maximum now respectively.
56. the described positive electrode material of lithium secondary cell of claim 38 manufacture method of lithium transition-metal based compound powder, it is characterized in that, comprise: the slip preparation section, in liquid medium with lithium compound, be selected from the transistion metal compound more than a kind among V, Cr, Mn, Fe, Co, Ni and the Cu, particle when suppressing calcining is grown up and the additive of sintering is pulverized, and obtains making its homodisperse slip; The spray drying operation is carried out spray drying to the slip that obtains; Calcination process is calcined the spray drying powder that obtains.
57. the positive electrode material of lithium secondary cell as claimed in claim 56 manufacture method of lithium transition-metal based compound powder, it is characterized in that, in the slip preparation section, in liquid medium with lithium compound, transistion metal compound and additive are pulverized, be crushed to median particle diameter below 0.4 μ m, this median particle diameter is to disperse (power output 30W at the ultrasonic wave that carried out 5 minutes, frequency 22.5kHz) afterwards, measure by laser diffraction/diffuse transmission type particle size distribution device and to obtain, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference, in the spray drying operation, slip viscosity during with spray drying is made as V (cp), the slip quantity delivered is made as S (L/min), when gas delivery volume is made as G (L/min), then at 50cp ≦ V ≦ 4000cp, carry out spray drying under the condition of 1500 ≦ G/S ≦ 5000.
58. the positive electrode material of lithium secondary cell as claimed in claim 56 manufacture method of lithium transition-metal based compound powder, it is characterized in that, at least comprise nickel compound, manganese compound and cobalt compound as transistion metal compound, in calcination process, under oxygen-containing gas atmosphere, more than 970 ℃ the spray drying powder is being calcined.
59. positive electrode material of lithium secondary cell as claimed in claim 56 is characterized in that with the manufacture method of lithium transition-metal based compound powder lithium compound is a lithium carbonate.
60. spray drying body, it is characterized in that, described spray drying body is as the spray drying body of positive electrode material of lithium secondary cell with the presoma of lithium transition-metal based compound powder, by in liquid medium with lithium compound, be selected from V, Cr, Mn, Fe, Co, the transistion metal compound more than at least a kind among Ni and the Cu, particle when suppressing calcining is grown up and the additive of sintering is pulverized, to making its homodisperse slip carry out spray drying and obtaining, the ultrasonic wave that described spray drying body was carried out 5 minutes disperses (power output 30W, frequency 22.5kHz) afterwards, the median particle diameter of this spray drying powder of measuring by laser diffraction/diffuse transmission type particle size distribution device is more than 0.01 μ m, below the 4 μ m, wherein refractive index is set to 1.24, with the particle diameter benchmark as volume reference.
61. spray drying body as claimed in claim 60 is characterized in that, the BET specific area is 10m
2/ g is above, 100m
2Below/the g.
62. a secondary lithium batteries positive pole is characterized in that, has on the collector to contain the positive electrode active material layer of the described positive electrode material of lithium secondary cell of claim 38 with lithium transition-metal based compound powder and binding agent.
63. a lithium secondary battery is characterized in that, described lithium secondary battery possesses negative pole, nonaqueous electrolyte that contains lithium salts that can embed removal lithium embedded and the positive pole that can embed removal lithium embedded, uses described 62 described secondary lithium batteries anodal as anodal.
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| JP106288/2006 | 2006-04-07 | ||
| JP2006106288 | 2006-04-07 | ||
| JP257260/2006 | 2006-09-22 | ||
| JP266580/2006 | 2006-09-29 | ||
| JP305015/2006 | 2006-11-10 |
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| CN2010105659638A Division CN102044673B (en) | 2006-04-07 | 2007-04-06 | Lithium nickel manganese cobalt series compound oxide powder for positive electrode material in lithium rechargeable battery |
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