CN103280561A - Transition metal compound hydroxide and lithium compound metal oxide - Google Patents
Transition metal compound hydroxide and lithium compound metal oxide Download PDFInfo
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- CN103280561A CN103280561A CN2013102229523A CN201310222952A CN103280561A CN 103280561 A CN103280561 A CN 103280561A CN 2013102229523 A CN2013102229523 A CN 2013102229523A CN 201310222952 A CN201310222952 A CN 201310222952A CN 103280561 A CN103280561 A CN 103280561A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a compound hydroxide containing an alkaline earth metal and a transition metal element, and a lithium compound metal oxide obtained by sintering a mixture of the transition metal compound hydroxide and a lithium compound at a temperature of 650-1,000 DEG C. Compared with a conventional lithium secondary battery, a non-aqueous electrolyte secondary battery by using the lithium compound metal oxide as a positive electrode active substance has better capacity and output characteristics, and in particular, is extremely useful in applications demanding high capacity and high output during a high current rate, especially for power tools such as automobiles, power tools, etc.
Description
Technical field
Invention relates to transition metal complex hydroxide and lithium complex metal oxide, is specifically related to as the lithium complex metal oxide of the positive active material in rechargeable nonaqueous electrolytic battery and the transition metal complex hydroxide that is used as the raw material of described oxide.
Background technology
The transition metal complex hydroxide is used as the raw material of the positive active material in the rechargeable nonaqueous electrolytic batteries such as lithium secondary battery at present.Lithium secondary battery has been used as the Miniature Power Unit of mobile phone or notebook computer purposes etc. and practical application, and then, in the large-scale power supply of automobile purposes or electric power storage applications etc., also attempting application.
As existing transition metal complex hydroxide, patent documentation 1(TOHKEMY 2008-84871 communique) specifically put down in writing following transition metal complex hydroxide in, wherein, principal component consists of Ni and Mn, S0
4content be 730 ppm by weight, alkali-metal content is 1700 ppm by weight.
Summary of the invention
Goal of the invention: still, with regard to using, using lithium complex metal oxide that above-mentioned transition metal complex hydroxide makes as raw material as for the rechargeable nonaqueous electrolytic battery of positive active material, its capacity and output characteristic can be said and be insufficient.The object of the present invention is to provide a kind of lithium complex metal oxide for positive active material, described positive active material is for better rechargeable nonaqueous electrolytic battery aspect capacity and output characteristic.
Technical scheme: a kind of transition metal complex hydroxide of the present invention, it contains alkali metal and S0 beyond Li
4and transition metal, described alkali-metal molar content is with respect to described S0
4the mol ratio of molar content more than 0.06 and be less than 2.2.
As optimization, described mol ratio is more than 1 and is less than 2.
As optimization, described transition metal means Ni, Mn and Zn.
As optimization, the mol ratio of Ni: Mn: Zn is 1-x-y: x:y, and wherein, x is more than 0. 3 and below 0. 7, and y is for being greater than 0 and be less than 0. 2.
As optimization, described alkali-metal molar content is 0.001 0.03 with respect to the mol ratio of the molar content of transition metal complex hydroxide.
As optimization, described alkali metal is Mg.
The invention also discloses a kind of manufacture method of lithium complex metal oxide: the mixture of above-mentioned transition metal complex hydroxide and lithium compound is remained at the temperature of 650 1000 ℃ and burnt till.
As optimization, the method for the operation of described transition metal complex hydroxide following by comprising (1) and (2) obtains:
(1) make to contain transition metal and alkali earth metal and S0
4the aqueous solution with alkali-metal alkali, contact, obtain the operation of coprecipitate slurry;
(2) obtained the operation of transition metal complex hydroxide by described coprecipitate slurry.
As preferably, the aqueous solution that the sulfate of the sulfate that the described aqueous solution is the sulfate by Ni, Mn, the sulfate of Mg and Zn is dissolved in the water and obtains, the sulfate that the sulfate of described Zn is divalent Zn.
A kind of lithium complex metal oxide, its mixture by above-mentioned transition metal complex hydroxide and lithium compound remains at the temperature of 650 1000 ℃ and is burnt till and obtain.
Beneficial effect: lithium complex metal oxide of the present invention is compared with lithium secondary battery in the past for the rechargeable nonaqueous electrolytic battery of positive active material, capacity and output characteristic are more excellent, especially in the purposes of the output of the height under needing high power capacity and high current rate, that is exceedingly useful in the rechargeable nonaqueous electrolytic battery that, the power tools such as automobile use or electric tool are used.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
A kind of transition metal complex hydroxide, it contains alkali metal and S0 beyond Li
4and transition metal, alkali-metal molar content is with respect to described S0
4the mol ratio of molar content more than 0.06 and be less than 2.2, wherein further take, optimize mol ratio as more than 1 and be less than 2, transition metal means Ni, Mn and Zn, the mol ratio of Ni: Mn: Zn is 1-x-y: x:y, wherein, x is more than 0. 3 and below 0. 7, and y is for being greater than 0 and be less than 0. 2, alkali-metal molar content is 0.001 0.03 with respect to the mol ratio of the molar content of transition metal complex hydroxide, and alkali metal is Mg.
Transition metal complex hydroxide of the present invention can be the raw material of lithium complex metal oxide, lithium complex metal oxide can be the positive active material of rechargeable nonaqueous electrolytic battery, in order further to improve the output characteristic of resulting rechargeable nonaqueous electrolytic battery, the aforementioned bases earth metal is preferably Mg.
In order further to improve capacity and the output characteristic of resulting rechargeable nonaqueous electrolytic battery, the transition metal that formed metal composite hydroxide is preferably Ni, Mn and Zn.The mol ratio of Ni in the transition metal complex hydroxide: Mn: Zn is set as to 1-x-y: x: during y, preferably x be 0. 3 or more and 0. 7 below and y be greater than 0 and be less than 0.2, more preferably x is more than 0.4 and below 0.5, and y is greater than 0 and be less than 0.1.
In the scope of not damaging effect of the present invention, also a part that forms the transition metal of transition metal complex hydroxide can be replaced with other element.As other element, can enumerate the elements such as B, Al, Ga, In, Si, Ge, Sn, P, Ca, Sr, Ba and Ti.
<manufacture method of lithium complex metal oxide>
Remain on by the mixture by transition metal complex hydroxide and lithium compound at the temperature of 650 1000 ℃ and burnt till, can manufacture lithium complex metal oxide.This lithium complex metal oxide is suitable as positive electrode active material for nonaqueous electrolyte secondary battery.
As the method for manufacturing transition metal complex hydroxide of the present invention and lithium complex metal oxide, particularly, can enumerate the method for the operation that comprises successively following (1), (2) and (3):
(1) make to contain transition metal and S0
4the aqueous solution with containing that alkali-metal alkali beyond Li contacts the operation that obtains the coprecipitate slurry;
(2) obtained the operation of transition metal complex hydroxide by this coprecipitate slurry;
(3) mix this transition metal complex hydroxide and lithium compound, resulting mixture is remained at the temperature of 650 1000 ℃ and burnt till, obtain the operation of lithium complex metal oxide.
The transition metal complex hydroxide especially can above-mentioned by comprising (1) and the method for the operation of (2) obtain.In operation (1), for containing transition metal and S0
4the aqueous solution, can use the sulfate of the transition metal more than a kind as the raw material that contains transition metal, also can use the water soluble salt of the transition metal more than a kind beyond the sulfate of the transition metal more than a kind and sulfate as the raw material that contains transition metal.Can use the following aqueous solution, that is, the water soluble salt of the transition metal more than a kind beyond sulfate is used as to the raw material that contains transition metal and this water-soluble salt dissolves is being added to so such as containing sulfuric acid in water and in the aqueous solution formed
4solution and the aqueous solution that obtains; Also can use the aqueous solution formed after sulfuric acid dissolution for raw metal that will contain transition metal.
Contain transition metal and S0
4the aqueous solution for containing Ni, Mn, Zn, Mg and S0
4the aqueous solution time, use the mol ratio with Ni: Mn: Zn to become example (l-x-y) described above: the sulfate of the mode weighing Ni of x: y, the sulfate of Mn and the sulfate of Zn, and it is dissolved in the water and the aqueous solution that obtains gets final product.As the sulfate of Zn, be preferably the sulfate of divalent Fe.
In operation (1), as containing Li alkali-metal alkali in addition, can enumerate from NaOH (NaOH), K0H (potassium hydroxide), Na
2c0
3(sodium carbonate) and K
2c0
3the compound more than a kind of selecting in (potash), this compound can be anhydride, can be also hydrate.Also can in aforementioned bases, add LiOH (lithium hydroxide), Li
2c0
3(lithium carbonate), and (NH
4)
2c0
3the compound more than a kind of selecting in (ammonium carbonate).Operation (1) in, preferably use the aqueous solution of above-mentioned alkali.Also can add ammoniacal liquor in the aqueous solution of alkali.The concentration of the alkali in the aqueous solution of alkali is generally 0. 5 10M (mol/ L) left and right, is preferably 1 8M left and right.From the aspect of manufacturing cost, consider, alkali is preferably NaOH, and Na0H can be anhydride, can be also hydrate.Can use two or more above-mentioned alkali.
As the method for the contact in operation (1), can enumerate and contain transition metal and S0
4the aqueous solution in add the aqueous solution of alkali and the method for being mixed; Add and contain transition metal so in the aqueous solution of alkali
4the aqueous solution and the method for being mixed; And add and contain transition metal so in water
4the aqueous solution and the aqueous solution of alkali and the method for being mixed.Preferably follow stirring while carrying out above-mentioned mixing.In the method for above-mentioned contact, the aspect changed from easy maintenance pH is considered, in the aqueous solution of alkali, adds and contains transition metal and S0
4the aqueous solution and the method for being mixed is preferred.Now, along with in the aqueous solution of alkali, adding and contain transition metal and S0
4the aqueous solution and mixed, the pH of mixed liquid exists and is tending towards the tendency reduced, but preferably in the situation that this pH is adjusted become 9 or more, preferably become interpolation more than 10 and contain transition metal and S0
4the aqueous solution.Containing transition metal and S0
4the aqueous solution and the aqueous solution of alkali in, if in the situation that wherein any one party or both sides' the aqueous solution remain on the temperature of 40 80 ℃ and contacted, can obtain the coprecipitate formed relatively uniformly.
In operation (1), can generate by the way coprecipitate, obtain the coprecipitate slurry.
In operation (2), by above-mentioned coprecipitate slurry, obtain the transition metal complex hydroxide.As long as can access the transition metal complex hydroxide, operation (2) can be utilized method arbitrarily, but, from the viewpoint of operability, is preferably based on the method for the Separation of Solid and Liquid such as filtration.By using the coprecipitate slurry and utilizing the heating such as spray drying to make the method evaporated, also can obtain the transition metal complex hydroxide.
In operation (2), while by Separation of Solid and Liquid, obtaining the transition metal complex hydroxide, the operation of described (2) is preferably the operation of following (2 '):
After (2 ') carry out Separation of Solid and Liquid by this coprecipitate slurry, cleaned, drying, obtain the operation of transition metal complex hydroxide.
In operation (2 '), there are alkali and S0 in resulting solid constituent after Separation of Solid and Liquid superfluously
4the time, can remove excessive composition by cleaning.
In order effectively to clean solid constituent, preferably make water as cleaning fluid.As required, also can in cleaning fluid, add the water-miscible organic solvents such as alcohol, acetone.Cleaning can be carried out more than 2 times, and for example, after carrying out the water cleaning, also the available water solubleness organic solvent cleans once again.
In operation (2 '), the alkali contained in resulting solid constituent after Separation of Solid and Liquid and S0
4amount can control by cleaning method.As concrete method, can control alkali and so contained in aforementioned solid constituent by the amount of cleaning fluid
4amount, also can will contain a certain amount of alkali and S0
4solution as cleaning fluid.In operation (1), as alkali, when not using the alkali-metal alkali contained beyond Li, for example only use and be selected from LiOH (lithium hydroxide), Li
2c0
3(lithium carbonate) and (NH
4)
2c0
3the compound more than a kind in (ammonium carbonate) (wherein, this compound can be anhydride, can be also hydrate) time, while for example perhaps only using ammoniacal liquor, in operation (2) or in (2 '), contain Li alkali-metal cleaning fluid in addition by use and cleaned, thereby can control alkali contained in solid constituent and S0
4amount.
In operation (2 '), after solid constituent is cleaned, carry out drying, can obtain the transition metal complex hydroxide.Drying can be undertaken by heating usually, also can be undertaken by the drying of blowing, vacuumize etc.While by heating, carrying out drying, baking temperature is generally 50 300 ℃, is preferably 100 200 ℃ of left and right.
In operation (3), by mixing transition metal complex hydroxide and the lithium compound obtained by aforesaid way, and resulting mixture is burnt till, thereby obtained the lithium complex metal compound.As lithium compound, can enumerate the compound more than a kind of selecting from lithium hydroxide, lithium chloride, lithium nitrate and lithium carbonate, this compound can be anhydride, can be also hydrate.
Mixing can mix by dry type, any method in wet mixed is carried out, but, from the viewpoint of simplicity, preferred dry is mixed.As mixing arrangement, can enumerate stirring mixer, V-Mixer, Wtypeofblender, ribbon stirrer, barrel mixer and ball mill.
Aspect the particle diameter and BET specific area of the particle diameter of the primary particle for adjusting lithium complex metal oxide, offspring, the maintenance temperature in aforementioned burning till is important factor.Usually, keep temperature higher, have the tendency that particle diameter is larger, the BET specific area is less of particle diameter and the offspring of primary particle.As keeping temperature, be preferably 650 1000 ℃.While keeping temperature lower than 650 ℃, the life characteristic of resulting battery descends, thereby not preferred, and while keeping temperature higher than 1000 ℃, the output characteristic of the high rate discharge of resulting battery descends, thereby not preferred.The time kept at aforementioned maintenance temperature is generally 0.1 20 hours, is preferably 0.5 8 hours.Reach aforementioned maintenance temperature programming rate before and be generally 50 400 ℃/hs, the cooling rate from aforementioned maintenance greenhouse cooling to room temperature is generally 10 400 ℃/hs.As the atmosphere of burning till, can use atmosphere, oxygen, nitrogen, argon gas or their mist, be preferably atmosphere.
After carrying out aforementioned burning till, the lithium complex metal oxide obtained can be used ball mill or injector-type mill etc. are pulverized.By pulverizing, the BET specific area of capable of regulating lithium complex metal oxide sometimes.Also can repeat 2 times by pulverizing and burning till.Lithium complex metal oxide can be cleaned or classification as required.
<lithium complex metal oxide >
With regard to the lithium complex metal oxide obtained by aforesaid way, for the high output characteristic under capacity and high rate discharge, good rechargeable nonaqueous electrolytic battery is useful.
In the scope of not damaging effect of the present invention, on the surface that can form at the particle by lithium complex metal oxide, adhere to the compound different from this lithium complex metal oxide.As this compound, can enumerate and contain the compound that is selected from the element more than a kind in B, C, Al, Ga, In, Si, Ge, Sn, Mg and transition metal, preferably contain the compound that is selected from the element more than a kind in B, C, A1, Mg, Ga, In and Sn, more preferably contain the compound of A1; As compound, particularly, can enumerate oxide, hydroxide, alkali formula hydroxide, carbonate, nitrate and the acylate of aforementioned elements, be preferably oxide, hydroxide, alkali formula hydroxide.Also can mix these compounds uses.In these compounds, particularly preferred compound is aluminium oxide.Can after adhering to, be heated.
In order to obtain high power capacity and to have the rechargeable nonaqueous electrolytic battery of high output characteristic, the mean value of particle diameter that forms the primary particle of lithium complex metal oxide is preferably 0. 01 0. 5 μ m.Lithium complex metal oxide consists of primary particle and the offspring formed by the primary particle cohesion usually.The particle diameter of offspring is preferably 0. 13 μ m.The particle diameter of primary particle, offspring can be observed to measure by scanning electron microscope (below be sometimes referred to as SEM).The mean value of the particle diameter of primary particle is 0.05 0.3 μ m more preferably, and the mean value of the particle diameter of offspring is 0.15 2 μ m more preferably.The BET specific area of lithium complex metal oxide is preferably 3 20m
2/ g.
In order further to improve effect of the present invention, lithium complex metal oxide preferably has a-NaFe0
2type crystal structure, belong to the crystal structure of the space group of R3m.Crystal structure can carry out usining CuK α for lithium complex metal oxide to be measured as radiogenic powder x-ray diffraction, according to resulting x-ray diffractogram of powder shape, is identified.
Anodal
?
Above-mentioned lithium complex metal oxide can be used as positive active material.The positive active material that contains lithium complex metal oxide can be used for positive pole.Positive pole is suitable for rechargeable nonaqueous electrolytic battery.
As using above-mentioned lithium complex metal oxide (positive active material) to manufacture the method for aforementioned positive pole, can take the situation of manufacturing positive electrode for nonaqueous electrolyte secondary battery to illustrate as follows as example.
Aforementioned positive pole supports in positive electrode collector and manufactures by the anode mixture that will contain positive active material, electric conducting material and binding agent.As aforementioned electric conducting material, can use Carbon Materials, as Carbon Materials, can enumerate powdered graphite, carbon black (such as acetylene black), fibrous carbon material etc.The surface area of the particulate of carbon black is large, therefore, by a small amount of interpolation the in anode mixture, can improve anodal inner conductivity, can improve efficiency for charge-discharge and the output characteristic of the rechargeable nonaqueous electrolytic battery obtained thus.On the other hand, if more add carbon black in anode mixture, can become anode mixture and the caking property between positive electrode collector reduced based on binding agent, the reason that increases internal resistance.Usually, the ratio of the electric conducting material in anode mixture, with respect to positive active material 100 weight portions, is 5 20 weight portions.As electric conducting material, when the fibrous carbon materials such as use graphitized carbon fiber, CNT (carbon nano-tube), also can reduce aforementioned proportion.
As conductive agent, so long as do not cause the electric conducting material of chemical change in the battery formed, be not particularly limited.Such as listing: the carbon black class such as the graphite such as native graphite and electrographite, carbon black, acetylene black, Ketjen black, channel black, furnace black, dim, thermal black, the conducting fibre such as carbon fiber, metallic fiber class, the metal dust classes such as fluorocarbons, aluminium, nickel powder, the conductivity such as zinc oxide, potassium titanate whisker class, the conductive materials such as the conductive metal oxides such as titanium oxide or polyphenyl derivative, as native graphite, such as listing: blocky graphite, flaky graphite and amorphous graphite etc.They can use a kind or be used in combination two or more.The compounding ratio of conductive agent, for being 1 50 % by weight in anode mixture, is preferably 2 30 % by weight.
As binding agent, for example can list: starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, PVP, tetrafluoroethene, polyethylene, polypropylene, sulfonated epdm, styrene butadiene rubbers, fluorubber, tetrafluoroethene-hexafluoroethylene copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, polytrifluorochloroethylene, vinylidene fluoride pentafluor propylene copolymer, propylene-TFE copolymer, ethylene-chlorotrifluoro-ethylene copolymer, biasfluoroethylene-hexafluoropropylene-TFE copolymer, vinylidene-perfluoro methyl vinyl ether-TFE copolymer, ethylene-acrylic acid copolymer or its (Na
+) ionomer body, ethylene-methacrylic acid copolymer or its (Na
+) ionomer body, ethylene-methyl acrylate copolymer or its (Na
+) ionomer body, ethylene-methyl methacrylate methyl terpolymer or its (Na
+) polysaccharide, the thermoplastic resin such as ionomer body, polyethylene glycol oxide, thering is the polymer of caoutchouc elasticity etc., they can use a kind or be used in combination two or more.Using while containing the compound of the functional group of reacting such with lithium as polysaccharide, for example preferably adding the such compound of NCO and make this functional group's inactivation.The compounding ratio of binding agent is 1 50 % by weight in anode mixture, is preferably 5 15 % by weight.
Negative pole is by coating negative material on negative electrode collector and carry out drying etc. and form.As negative electrode collector, so long as do not cause that the electric conductor of chemical change just is not particularly limited in the battery formed, such as listing: stainless steel, nickel, copper, titanium, aluminium, calcining carbon, on copper or stainless surface, carbon, nickel, titanium, silver surface are processed to the collector body that forms and aluminium cadmium alloy etc.In addition, also the surface oxidation of these materials can be used, can also form concavo-convex the use on the collector body surface by surface treatment.In addition, as the form of collector body, such as listing: the formed body of the collector body that paper tinsel, film, sheet, net, punching form, lath body, porous plastid, foaming body, fiber group, nonwoven fabrics etc.Thickness to collector body is not particularly limited, and is preferably 1 500 μ m.
As negative material, be not particularly limited, such as listing: carbonaceous material, composite oxide of metal, lithium metal, lithium alloy, baby are associated gold, tin is associated gold, metal oxide, electroconductive polymer, chalcogenide, Li-Co-Ni based material etc.As carbonaceous material, such as listing: difficult graphitized carbon material, graphite are material with carbon element etc.
As barrier film, used the film of the insulating properties of the mechanical strength that there is the heavy ion transmitance and possess regulation.From organic solvent resistance and hydrophobic viewpoint, can use sheet, the nonwoven fabrics made by the olefin polymers such as polypropylene or glass fibre or polyethylene etc.As the aperture of barrier film, so long as useful scope gets final product usually used as battery use, 0.01 10 μ m for example.As the thickness of barrier film, so long as the scope that common battery is used gets final product, be for example 5 300 μ m.Wherein, when using the solid electrolyte such as polymer as electrolyte described later, solid electrolyte can also be for doubling as the such material of barrier film.
The nonaqueous electrolyte that contains lithium salts is the electrolyte formed by nonaqueous electrolyte and lithium salts.As nonaqueous electrolyte, can use nonaqueous electrolytic solution, organic solid electrolyte based, inorganic solid electrolyte.As nonaqueous electrolytic solution, for example can list: by METHYLPYRROLIDONE, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, the tetrahydroxy furans, the 2-methyltetrahydrofuran, methyl-sulfoxide, formamide, dimethyl formamide, dioxolanes, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, dioxolane derivatives, sulfolane, methyl sulfolane, 3-methyl-2-oxazolidone, the polypropylene carbonate ester derivant, tetrahydrofuran derivatives, methyl propionate, 1 kind or the solvent that two or more mixes in the non-proton organic solvents such as ethyl propionate.
(4) evaluation of transition metal complex hydroxide
The composition analysis of transition metal complex hydroxide
The aqueous solution formed in hydrochloric acid for the powder dissolution by the transition metal complex hydroxide, carry out composition analysis with inductively coupled plasma luminescence analysis (SII SPS3000 processed).
Embodiment 1
1. the manufacture of transition metal complex hydroxide and lithium complex metal oxide
In polypropylene beaker processed, add NaOH 30.32g in distilled water 200ml, by stirring, dissolved, NaOH is dissolved fully, prepare sodium hydrate aqueous solution (alkaline aqueous solution).In glass beaker processed, add nickelous sulfate (II) hexahydrate 18. 53g, manganese sulfate (II) monohydrate 12. 17g and zinc sulfate (II) heptahydrate 2. 85g (mol ratio of Ni: Mn: Zn is 0.47: 0. 48: 0. 05) in distilled water 200ml, dissolved by stirring, obtained nickel-manganese-zinc mixed aqueous solution.Drip wherein aforementioned nickel-manganese-zinc mixed aqueous solution when stirring aforementioned sodium hydrate aqueous solution, generate thus the coprecipitate as the transition metal complex hydroxide, obtain the coprecipitate slurry, the pH of reaction end is 13.
Then, the coprecipitate slurry is filtered, use the Hang Cheongju of distilled water Jin of 500ml to wash, made its drying under 100 ℃, obtained the coprecipitate as the transition metal complex hydroxide.Use agate mortar to carry out the dry type mixing to this coprecipitate 6.0g with as lithium carbonate 2. 14g of lithium compound, obtain mixture.Then, this mixture oxidation aluminum of packing into is burnt till in container, use electric furnace to keep 6 hours in air atmosphere, under 850 ℃, this mixture is burnt till, be cooled to room temperature, obtain burning till product, it is pulverized, carry out the cleaning based on decant with distilled water, then filtered, under 300 ℃, drying is 6 hours, obtains the powder as lithium complex metal oxide.
The mol ratio that the result of the composition analysis of coprecipitate is Ni: Mn: Zn is 0.47: 0. 48: 0.05.The molar content of Mg is 0. 01 with respect to the mol ratio of the molar content of transition metal complex hydroxide.S0
4molar content with respect to the mol ratio of the molar content of transition metal complex hydroxide, be 0.000189.
The discharge rate test of rechargeable nonaqueous electrolytic battery
Manually make Coin-shaped battery with powder, carried out the discharge rate test, the discharge capacity (mAh/g) of result under 0. 2C, 5C is respectively 160,144 high like this values.
Utilizability on industry
According to the present invention, can obtain comparing with existing lithium secondary battery, can provide better rechargeable nonaqueous electrolytic battery aspect capacity and output characteristic, particularly in the purposes that needs high power capacity and the output of the height under high current rate, exceedingly useful in the rechargeable nonaqueous electrolytic battery that power tools such as automobile use or electric tool are used.
Claims (10)
1. a transition metal complex hydroxide is characterized in that: it contains alkali metal and S0 beyond Li
4and transition metal, described alkali-metal molar content is with respect to described S0
4the mol ratio of molar content more than 0.06 and be less than 2.2.
2. transition metal complex hydroxide according to claim 1, it is characterized in that: described mol ratio is more than 1 and is less than 2.
3. transition metal complex hydroxide according to claim 1 and 2, it is characterized in that: described transition metal means Ni, Mn and Zn.
4. transition metal complex hydroxide according to claim 3, it is characterized in that: Ni: Mn: the mol ratio of Zn is 1-x-y: x:y, and wherein, x is more than 0.3 and below 0.7, and y is for being greater than 0 and be less than 0.2.
5. according to the described transition metal complex hydroxide of any one in claim 14, it is characterized in that: described alkali-metal molar content is 0.001 0.03 with respect to the mol ratio of the molar content of transition metal complex hydroxide.
6. according to the described transition metal complex hydroxide of any one in claim 15, it is characterized in that: described alkali metal is Mg.
7. the manufacture method of a lithium complex metal oxide is characterized in that:
The mixture of the described transition metal complex hydroxide of any one in claim 16 and lithium compound is remained at the temperature of 650 1000 ℃ and burnt till.
8. method according to claim 7 is characterized in that:
The method of the operation of described transition metal complex hydroxide following by comprising (1) and (2) obtains:
(1) make to contain transition metal and alkali earth metal and S0
4the aqueous solution with alkali-metal alkali, contact, obtain the operation of coprecipitate slurry;
(2) obtained the operation of transition metal complex hydroxide by described coprecipitate slurry.
9. method according to claim 8 is characterized in that:
The aqueous solution that the sulfate of the sulfate that the described aqueous solution is the sulfate by Ni, Mn, the sulfate of Mg and Zn is dissolved in the water and obtains, the sulfate that the sulfate of described Zn is divalent Zn.
10. a lithium complex metal oxide is characterized in that: its mixture by the described transition metal complex hydroxide of any one in claim 16 and lithium compound remains at the temperature of 650 1000 ℃ and is burnt till and obtain.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626635A (en) * | 1994-12-16 | 1997-05-06 | Matsushita Electric Industrial Co., Ltd. | Processes for making positive active material for lithium secondary batteries and secondary batteries therefor |
| CN101874320A (en) * | 2007-09-28 | 2010-10-27 | 住友化学株式会社 | Lithium complex metal oxide and nonaqueous electrolyte secondary battery |
| CN102947226A (en) * | 2010-06-17 | 2013-02-27 | 住友化学株式会社 | Transition metal composite hydroxide and lithium composite metal oxide |
-
2013
- 2013-06-06 CN CN2013102229523A patent/CN103280561A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626635A (en) * | 1994-12-16 | 1997-05-06 | Matsushita Electric Industrial Co., Ltd. | Processes for making positive active material for lithium secondary batteries and secondary batteries therefor |
| CN101874320A (en) * | 2007-09-28 | 2010-10-27 | 住友化学株式会社 | Lithium complex metal oxide and nonaqueous electrolyte secondary battery |
| CN102947226A (en) * | 2010-06-17 | 2013-02-27 | 住友化学株式会社 | Transition metal composite hydroxide and lithium composite metal oxide |
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Application publication date: 20130904 |