CN105428637A - Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material - Google Patents
Lithium ion battery, positive electrode material of lithium ion battery and preparation method for positive electrode material Download PDFInfo
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- CN105428637A CN105428637A CN201410479797.8A CN201410479797A CN105428637A CN 105428637 A CN105428637 A CN 105428637A CN 201410479797 A CN201410479797 A CN 201410479797A CN 105428637 A CN105428637 A CN 105428637A
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Abstract
The invention discloses a lithium ion battery, a positive electrode material of the lithium ion battery and a preparation method for the positive electrode material. The positive electrode material is a lithium-rich manganese-base positive electrode material with the surface coated with a fast ion conductor material, and is prepared with a liquid phase method; and the lithium ion battery is a battery taking the positive electrode material as a positive active substance. Compared with the prior art, the positive electrode material of the lithium ion battery adopts a fast ion conductor as a surface coating material, so that the rate performance and the cycle stability under high voltage are greatly improved, and the battery taking the positive electrode material as the positive active substance has the advantages of high rate performance, high specific capacity, high cycle stability, high first efficiency and the like.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly, the present invention relates to a kind of positive electrode and preparation method thereof.
Background technology
The key factor of current limiting lithium ion cell energy density lifting and price, mainly in positive electrode.On market, existing positive electrode is mainly with stratiform LiCoO
2be main, spinel lithium manganate, layered lithium manganate, stratiform nickle cobalt lithium manganate, olivine lithium iron phosphate etc. also respectively occupy certain market share.In these materials, LiCoO
2be one of the most ripe material of commercialization, particularly in consumption electronic product, occupy the very large market share; But weak point is Co belongs to scarce resource, expensive, also can to environment, and structure becomes unstable after voltage is higher than 4.3V, cause secure context to be also a very large challenge.Manganese system LiMnO
2there is cheap, theoretical capacity advantages of higher, but this material is in a kind of thermodynamic instability state, not only prepare very difficult, and the transformation of layer structure to spinel structure also can be there is in charge and discharge process, cause capacity attenuation ratio in cyclic process very fast, chemical property is unstable; Manganese system LiMn
2o
4liMnO can be made up to a certain extent
2deficiency, but the easy dissolving occurring manganese ion in cyclic process, particularly at high temperature, the dissolving of manganese can be exacerbated, and LiMn
2o
4in manganese ion easily there is Jahn-Teller effect, cause loop attenuation than very fast and high-temperature behavior is undesirable.And LiFePO
4although raw material is extensive, low price, also have the plurality of advantages such as excellent cycle performance, security performance and thermal stability, working voltage platform is lower, thus can not meet the requirement of battery to high-energy-density.By contrast, the stratiform ternary material Li-Ni-Co-Mn with three metal ion species cooperative effects compensate for the deficiency of above-mentioned stratified material, there is the advantages such as specific capacity is high, good cycle, security performance stable, synthesis and preparation process is simple, mournfully be, the specific capacity of this type of material still within 200mAh/g, to such an extent as to has certain restriction to the lifting of battery energy density.
Research finds, in above-mentioned stratiform ternary material, add excessive lithium can obtain a kind of new rich lithium manganese base solid solution positive electrode, this material can be considered Li
2mnO
3with LiMO
2(M is Co, Fe, Ni, Ni
xco
y, Ni
xco
ymn
z) solid solution, its specific capacity is higher than 250mAh/g (being more than 2 times of the actual gram volume of positive electrode current material), and there is the cyclical stability of stable structure, cheap price, wider charging/discharging voltage scope, good security performance and excellence, this makes this material receive to pay close attention to widely, and is considered as the first-selected positive electrode of lithium ion battery of future generation by numerous scholar and industrial circle.But although this material has higher actual specific capacity, charge-discharge magnification is very low, after charge-discharge magnification increases, its specific capacity declines very fast, shows very poor high rate performance; In addition, this material is only charged on 4.5V, by Li
2mnO
3after activation, just there is very high specific capacity, material structure under high voltage, also can be made to be damaged.Visible, the actual performance of this material does not reach the requirement of high-energy-density, therefore in the urgent need to carrying out modification to it, to make it can be greatly improved in structural stability under high rate performance, first efficiency, high voltage etc., thus industrial applications is realized as early as possible.
At present, industry has done a lot of work in the cyclical stability improving above-mentioned stratiform ternary material, also achieves certain effect, such as: utilize Al
2o
3to Li
1.2ni
0.13co
0.13mn
0.54carry out coated after, its cycle performance and high rate performance obtain very large improvement, and circulate after 50 times, capability retention also brings up to 94% from 90%; Utilize TiO
2and AlF
3coated Li
1.2ni
0.13co
0.13mn
0.54, first charge-discharge efficiency is improved while, the cycle performance at 55 DEG C have also been obtained and improves significantly.Visible, above-mentioned method for coating has very great help to the efficiency first and cyclical stability aspect of improving Li-Ni-Co-Mn ternary material really, but because these clad materials itself have poor ionic conductivity, so method for coating is caused not have too large help improving in multiplying power.In addition, someone proposes to adopt fast-ionic conductor to modify mutually with rare earth doped lithium-rich manganese-based anode material for lithium-ion batteries, and this method achieves certain effect equally in cycle performance and high rate performance, and extends the discharge and recharge temperature range of battery; But, due to Li in lithium-rich manganese base material
2mnO
3structure itself do not activated, and adopt Solid phase synthesis, be difficult between different materials particle obtain nanoscale Homogeneous phase mixing, therefore certain restriction received to the improvement effect of high rate performance.
In view of this, necessaryly a kind of surface modifying method preparing high power capacity lithium-rich manganese-based anode material is provided, to improve the deficiency of existing lithium-rich manganese-based anode material.
Summary of the invention
The object of the invention is to: a kind of surface coated lithium-rich manganese-based anode material and preparation method thereof is provided, to improve the deficiency of existing lithium-rich manganese-based anode material.
In order to realize foregoing invention object, the invention provides a kind of positive electrode, it comprises bulk material Li [Li
(1-2x)/3M
xmn
(2-x)/3] O
2with the fast ion conducting material being coated on bulk material surface; In described bulk material, M is selected from least one in Ni, Co, Cr, and x is 0 ~ 0.33; Lithium ion in fast ion conducting material be positioned at four sides position, and can participate in lithium ion deintercalation and make up bulk material consume lithium ion; The percentage that fast ion conducting material accounts for bulk material and fast ion conducting material gross mass is 0.5% ~ 12%.
Compared with prior art, positive electrode of the present invention have employed tetrahedral fast-ionic conductor as surface cover, therefore under high rate performance and high voltage, cyclical stability obtains and effectively improves, thus the battery using it as positive active material is had good rate capability, specific capacity are high, cyclical stability by force, efficiency advantages of higher first.
One as positive electrode of the present invention is improved, and described fast-ionic conductor is Li
3v
2(PO
4)
3, Li
2zrS
3, Li
2o-AlO-SiO
2, Li
2o-mB
2o
3in one or more.
In order to realize foregoing invention object, present invention also offers a kind of method for preparing anode material, it comprises the following steps:
1) raw material preparing fast-ionic conductor are dissolved in solvent, add 5 ~ 50ml acid, and stir with the rotating speed of 70 ~ 240r/min under 60 ~ 120 DEG C of water bath condition;
2) according to fast-ionic conductor account for fast-ionic conductor and bulk material gross mass mark be 0.5% ~ 12% amount take Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2powder suspension is in step 1) in the solution made, continue under 60 ~ 120 DEG C of water bath condition, first ultrasonic 1h ~ 6h, then stir and make Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2powder is in the solution dispersed, and the most at last in solution all solvents evaporate, obtain the composite material mixed; Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2m in powder is selected from least one in Ni, Co, Cr, and x is 0 ~ 0.33;
3) by step 2) composite material that obtains calcines 3 ~ 20h at 300 ~ 600 DEG C, can obtain the positive electrode that Surface coating has fast-ionic conductor.
Compared with prior art, the present invention adopts the surface coated lithium-rich manganese-based anode material of Liquid preparation methods fast-ionic conductor, at least has the following advantages:
1) wet chemical methods can realize the mixing of ion nanoscale, makes modified ion more uniformly be coated on bulk material surface and improves its performance;
2) employing has lithium at the next coated bulk material lithium-rich manganese-based anode material of the fast ion conducting material of four sides position, pass through Liquid preparation methods, fast-ionic conductor can be evenly distributed on the surface of bulk material, suppress the dissolving of transition metal and the generation of side reaction in bulk material, can effectively prevent this positive electrode to react with electrolyte under high cut-ff voltage destruction material structure, and then improve its cycle performance in operating voltage range, greatly improve the high rate performance of this material, and after suppression circulation, also there is effect significantly in voltage platform,
3) in addition, the introducing of acid in step 1 can make bulk material Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2middle Li
2mnO
3first construction unit is activated, and while increase ionic conduction, the capacity of bulk material is farthest played, reaches the requirement of high-energy-density;
4) there is the advantages such as process route is simple, technological parameter easily controls, flow process is short, environmentally safe, be applicable to large-scale production, therefore there is wide large-scale production prospect.
One as the preparation method of positive electrode of the present invention is improved, described step 1) and 2) in fast-ionic conductor refer to Li
3v
2(PO
4)
3, Li
2zrS
3, Li
2o-AlO-SiO
2, Li
2o-mB
2o
3in one or more.
One as the preparation method of positive electrode of the present invention is improved, described step 1) in prepare fast-ionic conductor raw material be select by the fast-ionic conductor of required preparation, each element in fast-ionic conductor is respectively from following raw material:
Li element, from Li compound, specifically comprises one or more in lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate;
B element is from one or more in boric acid, carbonic acid boron and diboron trioxide;
V element carrys out one or more in self-bias alum acid ammonium, vanadic oxide, vanadium trioxide;
Al element is from one or more in aluminium acetate, aluminum nitrate, aluminium chloride, aluminum sulfate;
Si element is from one or more in silicon dioxide, silicic acid, sodium metasilicate;
Zr element is from one or more in zirconium dioxide, chlorine monoxid zirconium, zirconium sulfate, zirconium nitrate;
S element is from one or more in sodium sulphate, vulcanized sodium;
P element is from one or more in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate.
One as the preparation method of positive electrode of the present invention is improved, described step 2) in Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2powder adopts existing method to be prepared, and the new method of subsequent development also can be adopted to be prepared, include but not limited to solid phase method, hydroxide or carbonate or oxalate precipitation process, combustion method or sol-gal process etc.
One as the preparation method of positive electrode of the present invention is improved, described step 1) in acid optional from sulfuric acid, hydrochloric acid, nitric acid.
One as the preparation method of positive electrode of the present invention is improved, described step 1) in solvent can be selected from deionized water, absolute ethyl alcohol.
In order to realize foregoing invention object, invention further provides a kind of lithium ion battery, comprise positive plate, negative plate, be interval in barrier film between positive/negative plate, and electrolyte, positive plate comprises plus plate current-collecting body and is distributed in the positive active material on plus plate current-collecting body, negative plate comprises negative current collector and is distributed in the negative electrode active material on negative current collector, and wherein, positive active material is the surface coated lithium-rich manganese-based anode material described in above-mentioned any one.
Compared with prior art, lithium ion battery of the present invention adopts the surface coated lithium-rich manganese-based anode material of above-mentioned fast-ionic conductor as positive active material, therefore has very high discharge capacity, excellent high rate performance, stable cycle performance.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, to anode material for lithium-ion batteries of the present invention, preparation method, the obtained lithium ion battery of this positive electrode and beneficial effect thereof is used to be described in detail.
Fig. 1 is the Li that the embodiment of the present invention 1 obtains
2o-mB
2o
3the SEM figure of coated lithium-rich manganese-based anode material.
Fig. 2 is the Li that the embodiment of the present invention 1 obtains
2o-mB
2o
3the XRD figure of coated lithium-rich manganese-based anode material.
Fig. 3 adopts the obtained positive electrode of the embodiment of the present invention 1 to be the first charge-discharge curve chart of button cell under 30mA current density of positive active material.
Fig. 4 adopts the obtained positive electrode of the embodiment of the present invention 1 to be the cyclic curve figure of button cell under different current density of positive active material.
Fig. 5 adopts the obtained positive electrode of the embodiment of the present invention 2 to be the cyclic curve figure of button cell under 30mA current density of positive active material.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and Advantageous Effects more clear, below in conjunction with embodiment, the present invention is further elaborated.Should be understood that, the embodiment described in this specification is only used to explain the present invention, and be not intended to limit the present invention, the formula, ratio etc. of embodiment can suit measures to local conditions make a choice and there is no substantial effect to result.
Embodiment 1
Prepare positive electrode:
A) in molar ratio for the ratio of 1:0.5 takes lithium hydroxide and boric acid, it is dissolved into respectively after in deionized water, adds 10ml nitric acid, and at the temperature of 80 DEG C, stir with the rotating speed of 70r/min and make it dissolve;
B) according to Li
2o-mB
2o
3the mass fraction accounting for bulk material and fast ion conducting material is 0.5% take Li [Li
0.22ni
0.17mn
0.61] O
2dusty material, makes it be suspended to a) in solution, to continue under the condition of 80 DEG C of water-baths, first after ultrasonic 1h, then to stir and make Li [Li
0.22ni
0.17mn
0.61] O
2powder is dispersed in a solution, is evaporated by solvents all in solution, obtain the composite material mixed after being uniformly dispersed;
C) composite material obtained by step b is heat treatment 3h at 350 DEG C, namely obtains fast-ionic conductor Li
2o-mB
2o
3coated lithium-rich manganese-based anode material.
Fig. 1 and Fig. 2 is respectively Li
2o-mB
2o
3sEM figure and the XRD figure of coated lithium-rich manganese-based anode material, as can be seen from Fig. 1 and Fig. 2, employing liquid phase method, can coating be made evenly the surface being distributed in bulk material, and there is no impurity phase.
Prepare battery and test:
With Li
2o-mB
2o
3li [the Li that fast-ionic conductor is coated
0.22ni
0.17mn
0.61] O
2for positive active material, itself and conductive agent, binding agent are pressed the mass ratio of 85:10:5, Homogeneous phase mixing in nitrogen methyl pyrrolidone (NMP), is then coated in aluminum foil current collector, obtains positive plate under being placed in vacuum environment at 120 DEG C after drying; Be negative pole with metal lithium sheet, be conventionally assembled into button cell.At room temperature carry out constant current charge-discharge test to assembled button cell, wherein test voltage scope is 2.0 ~ 4.8V.Result shows, and use the present embodiment through the obtained battery of the positive electrode of coated process, its discharge capacity reaches 297mAh/g, and efficiency, up to 89%, circulate 50 times later 98.8% first.
Embodiment 2
Prepare positive electrode:
A) ratio being 1.5:1:1.5 according to mol ratio takes Li
2cO
3, V
2o
5and NH
4h
2pO
4, be dissolved in absolute ethyl alcohol, added 50ml hydrochloric acid, and at the temperature of 80 DEG C, stir with the rotating speed of 150r/min and make it dissolve;
B) according to Li
3v
2(PO
4)
3the mass fraction 5% accounting for bulk material and fast ion conducting material takes Li [Li
0.14ni
0.15co
0.14mn
0.57] O
2dusty material, makes it be suspended in a solution, continues, under the condition of 80 DEG C of water-baths after first ultrasonic 1h, then to stir and make its Li [Li
0.14ni
0.15co
0.14mn
0.57] O
2powder is dispersed in a) in solution, is evaporated by solvents all in solution, obtain the composite material mixed after being uniformly dispersed;
C) composite material obtained by step b is heat treatment 10h at 500 DEG C, namely obtains fast-ionic conductor Li
3v
2(PO
4)
3coated lithium-rich manganese-based anode material.
Prepare battery and test:
According to the method for embodiment 1, adopt Li
3v
2(PO
4)
3li [the Li that fast-ionic conductor is coated
0.14ni
0.15co
0.14mn
0.57] O
2material is positive active material, is assembled into button cell, in 2.0 ~ 4.8V voltage range, carry out charge-discharge test with 0.1C electric current.Result shows, and the discharge capacity of battery is 298mAh/g, and efficiency is 91% first; Meanwhile, by regulating charging/discharging voltage scope, also obtain very high capacity, as discharge and recharge between 2.0 ~ 4.6V, battery capacity reaches 275mAh/g, and efficiency is up to 88% first, and circulate 50 times is 98.3% later.
Embodiment 3
Prepare positive electrode:
A) ratio being 1:1:1 according to mol ratio takes Li
2cO
3, Al (NO
3)
3and SiO
2, be dissolved in absolute ethyl alcohol, added 15ml sulfuric acid, and at the temperature of 80 DEG C, stir with the rotating speed of 240r/min and make it dissolve;
B) according to Li
2o-AlO-SiO
2the mass fraction 12% accounting for bulk material and fast ion conducting material takes Li [Li
0.3cr
0.05mn
0.65] O
2dusty material, makes it be suspended to a) in solution, to continue under the condition of 80 DEG C of water-baths, first after ultrasonic 1h, then to stir and make its Li [Li
0.3cr
0.05mn
0.65] O
2powder is dispersed in a solution, is evaporated by solvents all in solution, obtain the composite material mixed after being uniformly dispersed;
C) composite material obtained by step b is heat treatment 20h at 600 DEG C, namely obtains fast-ionic conductor Li
2o-AlO-SiO
2coated lithium-rich manganese-based anode material.
Prepare battery and test:
According to the method for embodiment 1, adopt Li
2o-AlO-SiO
2li [the Li that fast-ionic conductor is coated
0.3cr
0.05mn
0.65] O
2for positive active material, be assembled into button cell, in 2.0 ~ 4.8V voltage range, carry out charge-discharge test with 0.1C electric current, the discharge capacity obtaining battery is 290mAh/g, and efficiency is 89% first, and circulate 50 times is 97.2% later; Meanwhile, adopt different current densities to carry out cycle charge-discharge, find have excellent high rate performance and stable cycle performance by the lithium-rich manganese-based anode material that fast-ionic conductor is coated.
Embodiment 4
Prepare positive electrode:
A) ratio being 1.5:1:1.5 according to mol ratio takes Li
2cO
3, V
2o
5and NH
4h
2pO
4, be dissolved in absolute ethyl alcohol, added 5ml nitric acid, and at the temperature of 80 DEG C, stir with the rotating speed of 80r/min and make it dissolve;
B) according to Li
3v
2(PO
4)
3the mass fraction 7% accounting for bulk material and fast ion conducting material takes Li [Li
0.16cr
0.15ni
0.18mn
0.51] O
2dusty material, makes it be suspended to a) in solution, to continue under the condition of 80 DEG C of water-baths, first after ultrasonic 1h, then to stir and make its Li [Li
0.16cr
0.15ni
0.18mn
0.51] O
2powder is dispersed in a solution, is evaporated by solvents all in solution, obtain the composite material mixed after being uniformly dispersed;
C) composite material obtained by step b is heat treatment 12h at 550 DEG C, namely obtains fast-ionic conductor Li
3v
2(PO
4)
3coated lithium-rich manganese-based anode material.
Prepare battery and test:
According to the method for embodiment 1, adopt Li
3v
2(PO
4)
3li [the Li that fast-ionic conductor is coated
0.16cr
0.15ni
0.18mn
0.51] O
2material is positive active material, is assembled into button cell, in 2.0 ~ 4.8V voltage range, carry out charge-discharge test with 0.1C electric current, and the discharge capacity obtaining battery is 295mAh/g, and efficiency is 90% first, and circulate 50 times is 98.1% later.
Comparative example 1
With used not through the coated Li [Li processed in embodiment 1
0.22ni
0.17mn
0.61] O
2as positive active material, itself and conductive agent, binding agent are pressed the mass ratio of 85:10:5, Homogeneous phase mixing in nitrogen methyl pyrrolidone (NMP), is then coated in aluminum foil current collector, obtains positive plate under being placed in vacuum environment at 120 DEG C after drying; Take metal lithium sheet as negative pole, conventionally be assembled into button cell, at room temperature constant current charge-discharge test is carried out to assembled button cell, be carry out discharge and recharge with 0.1C electric current in 2.0 ~ 4.8V in voltage range, the discharge capacity obtaining battery is 241mAh/g, efficiency is 78% first, and circulate 50 times is 85% later.
Comparative example 2
According to Li
3v
2(PO
4)
3mass fraction 7% take Li [Li
0.16cr
0.15ni
0.18mn
0.51] O
2dusty material, and be medium with ethanol, mechanical activation 2h in fixed star ball mill, by gained presoma after 80 DEG C of dryings, high-temperature heat treatment 12h at the mixture material of gained and 550 DEG C, namely obtains fast-ionic conductor Li
3v
2(PO
4)
3coated lithium-rich manganese-based anode material.
The assembling of button cell
Respectively with 1 ~ 2 obtained positive electrode in embodiment 1 ~ 4 and comparative example for positive active material, itself and conductive agent, binding agent are pressed the mass ratio of 85:10:5, Homogeneous phase mixing in nitrogen methyl pyrrolidone (NMP), then be coated in aluminum foil current collector, at 120 DEG C, obtain positive plate after drying under being placed in vacuum environment, be then washed into the sequin that diameter is 2mm; And be negative pole with metal lithium sheet, with LiPF
6/ EC+DMC is electrolyte, with PP or PE for barrier film, is assembled into 2032 type button cells in the glove box being full of inert gas.
Battery performance test
At room temperature, the button cell that embodiment 1 ~ 4 and comparative example 1 ~ 2 are assembled first with 0.1C constant current charge to 4.8V, after leaving standstill 3min, again with 0.1C constant-current discharge to 3.0V, record the initial charge capacity that current charging capacity is this material, discharge capacity is the discharge capacity first of this material, and the ratio of discharge capacity and initial charge capacity is the efficiency first of this material first.Cycle performance test adopts the identical multiplying power of charging and discharging to test, and test result is as shown in Fig. 3-5 and table 1.
The battery performance test result of table 1, embodiment 1 ~ 4 and comparative example 1 ~ 2
As can be seen from Fig. 3-5 and table 1:
1) as can be seen from the test result of embodiment 1 and comparative example 1, the coated lithium-rich manganese-based anode material for lithium-ion batteries processed of fast-ionic conductor being positioned at four sides position through Li not only has clear improvement in discharge capacity, high rate performance and cyclicity first, and have also been obtained in efficiency first and improve greatly, this mainly improves cycle performance because the dissolving of the manganese under high voltages of the lithium-rich manganese-based anode material after fast-ionic conductor is coated is suppressed; In addition, fast-ionic conductor has ionic conduction ability faster, and Li is positioned at four sides position and can identifies oneself with the deintercalation of lithium ion, therefore improves efficiency and improve high rate performance first;
2) as can be seen from the test result of embodiment 1 and comparative example 2, through Li
3v
2(PO
4)
3the coated lithium-rich manganese-based anode material processed is improved in cycle performance, and this is consistent with the result of the coated process of fast-ionic conductor, can suppress the stripping of manganese and the structure of stable bulk material under high voltage; But discharge capacity and efficiency difference is comparatively obvious first first, adopts liquid phase method mainly due to embodiment 1, is conducive to nanoscale Homogeneous phase mixing between different materials particle, moreover the adding of acid in liquid phase, Li in lithium-rich manganese base material can be made
2mnO
3structure activated, capacity in its bulk material is not fully exerted, and it is discharge capacity and efficiency is higher first first;
3) as can be seen from contrast with embodiment 1,3 of embodiment 2, the treatment effect of embodiment 2 to lithium-rich manganese-based anode material for lithium-ion batteries is better, this may be more appraise at the current rate because V ion in the fast-ionic conductor in embodiment 2 has, when the Li being positioned at four sides position participates in the deintercalation reaction of lithium, V ion can carry out the adjustment of valence state, but overall structure can not be subject to micro-destruction, thus improve the performance of bulk material better.
In sum, at lithium-rich manganese base material Surface coating one deck, there is the fast-ionic conductor that Li is positioned at four sides position, especially Li
3v
2(PO
4)
3fast-ionic conductor, lithium-rich manganese base material can be made not only to get a promotion in discharge capacity first, doubly forthright and cyclicity, and the more important thing is the efficiency first can improving this material significantly, inhibit the decline of voltage platform in cyclic process simultaneously.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and amendment to above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (9)
1. a positive electrode, is characterized in that: described positive electrode comprises bulk material Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2with the fast ion conducting material being coated on bulk material surface; In described bulk material, M is selected from least one in Ni, Co, Cr, and x is 0 ~ 0.33; Lithium ion in fast ion conducting material be positioned at four sides position, and can participate in lithium ion deintercalation and make up bulk material consume lithium ion; The percentage that fast ion conducting material accounts for bulk material and fast ion conducting material gross mass is 0.5% ~ 12%.
2. positive electrode according to claim 1, is characterized in that: described fast-ionic conductor is Li
3v
2(PO
4)
3, Li
2zrS
3, Li
2o-AlO-SiO
2, Li
2o-mB
2o
3in one or more.
3. a preparation method for positive electrode, is characterized in that, comprises the following steps:
1) raw material preparing fast-ionic conductor are dissolved in solvent, add 5 ~ 50ml acid, and stir with the rotating speed of 70 ~ 240r/min under 60 ~ 120 DEG C of water bath condition;
2) according to fast-ionic conductor account for fast-ionic conductor and bulk material gross mass mark be 0.5% ~ 12% amount take Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2powder suspension is in step 1) in the solution made, continue under 60 ~ 120 DEG C of water bath condition, first ultrasonic 1h ~ 6h, then stir and make Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2powder is in the solution dispersed, and the most at last in solution all solvents evaporate, obtain the composite material mixed; Li [Li
(1-2x)/3M
xmn
(2-x)/3] O
2m in powder is selected from least one in Ni, Co, Cr, and x is 0 ~ 0.33;
3) by step 2) composite material that obtains calcines 3 ~ 20h at 300 ~ 600 DEG C, can obtain the positive electrode that Surface coating has fast-ionic conductor.
4. the preparation method of positive electrode according to claim 3, is characterized in that: described step 1) and 2) in fast-ionic conductor refer to Li
3v
2(PO
4)
3, Li
2zrS
3, Li
2o-AlO-SiO
2, Li
2o-mB
2o
3in one or more.
5. the preparation method of positive electrode according to claim 4, it is characterized in that: described step 1) in prepare fast-ionic conductor raw material be select by the fast-ionic conductor of required preparation, each element in fast-ionic conductor is respectively from following raw material: Li element is from one or more in lithium hydroxide, lithium carbonate, lithium acetate, lithium chloride, lithium sulfate; B element is from one or more in boric acid, carbonic acid boron and diboron trioxide; V element carrys out one or more in self-bias alum acid ammonium, vanadic oxide, vanadium trioxide; Al element is from one or more in aluminium acetate, aluminum nitrate, aluminium chloride, aluminum sulfate; Si element is from one or more in silicon dioxide, silicic acid, sodium metasilicate; Zr element is from one or more in zirconium dioxide, chlorine monoxid zirconium, zirconium sulfate, zirconium nitrate; S element is from one or more in sodium sulphate, vulcanized sodium; P element is from one or more in ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate.
6. the preparation method of positive electrode according to claim 3, is characterized in that: described step 2) in Li [Li
(1-2x)/3m
xmn
(2-x)/3] O
2powder adopts solid phase method, hydroxide or carbonate or the preparation of oxalate precipitation process, combustion method or sol-gal process.
7. the preparation method of positive electrode according to claim 3, is characterized in that: described step 1) in acid be selected from sulfuric acid, hydrochloric acid, nitric acid.
8. the preparation method of positive electrode according to claim 3, is characterized in that: described step 1) in solvent be selected from deionized water, absolute ethyl alcohol.
9. a lithium ion battery, comprise positive plate, negative plate, be interval in barrier film between positive/negative plate, and electrolyte, positive plate comprises plus plate current-collecting body and is distributed in the positive active material on plus plate current-collecting body, negative plate comprises negative current collector and is distributed in the negative electrode active material on negative current collector, it is characterized in that: described positive active material is the positive electrode in claim 1 to 2 described in any one, or the positive electrode that in claim 3 to 8, any one method is prepared.
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