CN106654224B - A kind of cobalt acid lithium composite material and preparation method, positive electrode - Google Patents

A kind of cobalt acid lithium composite material and preparation method, positive electrode Download PDF

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CN106654224B
CN106654224B CN201710032201.3A CN201710032201A CN106654224B CN 106654224 B CN106654224 B CN 106654224B CN 201710032201 A CN201710032201 A CN 201710032201A CN 106654224 B CN106654224 B CN 106654224B
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cobalt
lithium
acid lithium
cobalt acid
composite material
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刘小雨
公伟伟
周贵海
王剑锋
黄海翔
宋振伟
马群
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Hunan Ruixiang New Materials Co Ltd
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/362—Composites
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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Abstract

The present invention provides a kind of cobalt acid lithium composite material and preparation methods, positive electrode.A kind of cobalt acid lithium composite material is to coat cobalt phosphate lithium LiCoPO on the surface of cobalt acid lithium oxide particle4Made of material；The molecular formula of the cobalt acid lithium oxide particle is Li1+xCo1‑yMyO2, M be selected from magnesium, aluminium, zirconium, titanium, lanthanum, zinc, vanadium it is one or more, the quality of the cobalt phosphate lithium is the 0.25%~10% of the cobalt acid lithium oxide particle.The present invention solves poor circulation under cobalt acid lithium high temperature or high pressure and the low problem of capacitance.

Description

A kind of cobalt acid lithium composite material and preparation method, positive electrode
Technical field
The present invention relates to chemical fields, more particularly, to a kind of cobalt acid lithium composite material and preparation method, positive electrode.
Background technique
In recent years, with the extensive use of portable electronic device, people are higher and higher to the requirement of battery, especially It is to capacity, requirement resistant to high temperature.And lithium ion battery due to high, small in size with operating voltage, specific energy is high, pollution less, The excellent comprehensive performance such as memory-less effect, so always in occupation of the leading position of portable electronic device.
At present in anode material for lithium-ion batteries, for cobalt acid lithium due to simple production process, discharge capacity is big, good cycle Etc. advantages, a large amount of market is occupied, but there is also certain problems as positive electrode for cobalt acid lithium simultaneously, such as the theory of cobalt acid lithium Capacity is 274mAh/g, and when in the range of universal operating voltage 4.2V~2.5V, actual capacity is only 140mAh/g or so, limit The power of battery has been made, theoretically can utilize residual capacity by improving charging voltage.However, when improving charging voltage extremely 4.5V or it is higher when, electrolyte is easy unstable decomposition, and the cobalt of cobalt acid lithium easily dissolves out, and causes cycle performance of battery to reduce, sternly It can set off an explosion when weight, great hidden danger is generated to personal safety, therefore be difficult to improve practical appearance by improving charging voltage Amount.Therefore the high voltage of cobalt acid lithium can be improved, improve the method for capacity and cycle performance to lithium ion battery industry by searching out Development has great significance.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of cobalt acid lithium composite material, and the composite material solves cobalt acid lithium Poor circulation and the low problem of capacitance under high temperature or high pressure.
The second object of the present invention is to provide the preparation method of above-mentioned cobalt acid lithium composite material, the method flow letter It is single, it is easy to promote.
The third object of the present invention is to provide a kind of positive electrode, the positive electrode high, high temperature with capacitance The advantages that cycle of higher pressure performance is good.
In order to achieve the goal above, the present invention provides following technical schemes:
A kind of cobalt acid lithium composite material coats cobalt phosphate lithium LiCoPO on the surface of cobalt acid lithium oxide particle4Made of Material；
The molecular formula of the cobalt acid lithium oxide particle is Li1+xCo1-y MyO2, M is selected from magnesium, aluminium, zirconium, titanium, lanthanum, zinc, vanadium It is one or more, the quality of the cobalt phosphate lithium is the 0.25%~10% of the cobalt acid lithium oxide particle.
The present invention is with existing common cobalt acid lithium or doped with the difference of the cobalt acid lithium of miscellaneous element: by cobalt acid lithium matrix And it is coated on the LiCoPO on its surface4Composition, is a kind of composite structure, and belong to chemically active cladding, LiCoPO4 It can be reduced LiOH and Li2CO3Generation, improve the high-temperature behavior of material indirectly, and the dissolution of cobalt can be prevented, significantly improve cobalt The cycle of higher pressure stability of sour lithium.
Y of the present invention can use zero, i.e. cobalt acid lithium of the present invention suitable for the element that undopes, but remain to reach raising The circulative effect of high temperature and pressure, i.e., under 4.5V high voltage after 100 charge and discharge capacity retention ratio 85% or more.
It is mixed with arbitrary proportion that M of the present invention can be single magnesium, aluminium, zirconium, titanium, lanthanum, zinc or vanadium or magnesium, aluminium Perhaps magnesium, aluminium, zirconium, titanium are mixed with arbitrary proportion or aluminium, zirconium, titanium, lanthanum are mixed with arbitrary proportion for conjunction, and Huo Zhexin, vanadium are to appoint The mixing of meaning ratio.
Cobalt acid lithium oxide particle of the present invention can be LiCoO2, Li1Co0.99Zn0.01O2, Li1.1Co0.8Al0.05 Mg0.05Ti0.05La0.05O2, Li1Co0.9Al0.05Zr0.05O2, Li1.2Co0.9Ti0.05La0.05O2, Li1Co0.9Al0.03Zr0.05V0.02O2 Deng.
The covering amount of cobalt phosphate lithium of the present invention can be 0.25%, 0.5%, 0.7%, 0.9%, 1%, 3%, 4%, 5%, 7%, 9%, 10%.
In order to improve the synergy between doped chemical and coating, capacitance and the high temperature for more significantly improving material are high Press characteristic, it is preferable that -0.1≤X≤0.20,0≤Y≤0.2.
Or, it is preferable that 0.1≤X≤0.20,0.1≤Y≤0.2.
Or, it is preferable that M be selected from aluminium, zirconium, titanium, lanthanum it is one or more.
Alternatively, the quality of the cobalt phosphate lithium is the 0.5%~10% of the cobalt acid lithium oxide particle, more preferably 0.5%~5%.The present invention may be incorporated into another coating --- LiwNi1-mMnmO2, LiwNi1-mMnmO2Have in 4.5V or more One high voltage platform has higher energy density, and resourceful, cheap, and lithium cobaltate cathode can be improved The high voltage performance of material, operating voltage are increased to 4.5V or more by universal 4.2V, to further utilize LiCoO2It is surplus Covolume amount improves the capability value of cobalt acid lithium.
It preferably, is the higher capability value of acquisition and high rate performance, 1.00≤W≤1.05,0≤M≤0.75.
Preferably, the LiwNi1-mMnmO2Gross mass with the cobalt phosphate lithium is the cobalt acid lithium oxide particle When 0.5%~10%, two kinds of covering materials can act synergistically, at the same conspicuousness improve capacity and cycle performance.
Or, it is preferable that the LiwNi1-mMnmO2With mass ratio≤1 of the cobalt phosphate lithium.
Above-described two kinds of coating can be coated on cobalt acid lithium oxide particle surface simultaneously, can also wrap step by step It covers, but sequencing is not restricted by, obtained material property does not have marked difference.
If only coat cobalt phosphate lithium, it is preferred to use following preparation method:
According to formula, coated using wet process cladding or dry method by LiCoPO4It is coated on the table of cobalt acid lithium oxide particle Then face is sintered to obtain the final product.
Wherein, the rate of dry method cladding is fast, high-efficient, but uniformity does not have wet process to coat.
In order to improve the crystalline structure of particle from microstructure, obtain that aperture is small but porosity is high, specific surface area is reasonable Characteristic, to constructively improve electric conductivity, it is preferable that the method for the sintering are as follows: be warming up to 700-1000 DEG C of holding 1-4 hours, the speed of the heating was preferably 2-5 DEG C/min；
It is highly preferred that the method for the sintering are as follows: be warming up to 800-1000 DEG C of holding 1-4 hours.
Preferred wet process cladding process are as follows: according to preset proportion, the solution of soluble cobalt, phosphoric acid/phosphate is molten Liquid, lithium source and the cobalt acid lithium oxide particle hybrid reaction, are dried later.Wherein, the addition sequence of the above raw material not by Limitation.
The phosphate is preferably ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or potassium hydrogen phosphate etc., in order to guarantee sufficiently instead It answers, C (Co): C (P) control is within the scope of 1:1 to 3:2.
The source Co is selected from cobaltous sulfate, cobalt chloride, cobalt nitrate.
Dry method is preferred after reaction are as follows: is dried at 70~90 DEG C.
If coating two kinds of materials, prepared using following methods:
According to LiwNi1-mMnmO2Atomic ratio take lithium source, nickel source, manganese source, then with the cobalt acid lithium oxide particle, And meeting the solution, phosphoric acid/phosphate solution, lithium source mixing of the soluble cobalt of the cobalt phosphate lithium proportion, reaction is reburned Knot is to get product.
Preferably, also, the method for the sintering are as follows: be warming up to 700-1000 DEG C of holding 1-4 hours, the speed of the heating Preferably 2-5 DEG C/min of degree.
Preferably, the method for the sintering are as follows: be warming up to 800-1000 DEG C of holding 1-4 hours.
As described above, composite material of the present invention is mainly for the preparation of positive electrode, naturally it is also possible to be used for it Its field.
To sum up, compared with prior art, invention achieves following technical effects:
(1) it significantly improves high temperature and pressure cycle performance and forthright again: LiCoPO is coated by surface4The above effect is reached Fruit.
(2) it significantly improves the capacitance that material is used as anode: passing through LiCoPO4And LiwNi1-mMnmO2Two kinds of coatings Synergistic effect reached the effect.
(3) improve the microstructure of material: the bonding that the process conditions such as optimization sintering, cladding improve material is stablized The performances such as property, porosity, aperture, specific surface area, density, to improve the synthesis electric conductivity of material.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments, It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Hereafter in addition to embodiment 6 and 7, the cobalt acid lithium matrix of remaining all embodiment is Li1Co0.8Al0.05Zr0.05 Ti0.05La0.05O2。
Embodiment 1
In comparative example 2, first by cobalt nitrate (Co (NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) dissolve in respectively from In sub- water, it is respectively formed the solution of 0.1mol/L concentration.Then by a certain amount of cobalt acid lithium oxide particle and pure water appropriate Mixing is used as bottom liquid, and above-mentioned configured cobalt nitrate solution and diammonium hydrogen phosphate is slowly added dropwise using peristaltic pump cocurrent while stirring Solution is stirred continuously dispersion 1h, revolving speed 1400r/min, until the CoPO generated4The uniform appendix of nano particle is in matrix table Face carries out drying with water bath later at 90 DEG C.Then, it is warming up at 800 DEG C and is kept for 3 hours with 3 DEG C/min of speed, calcined After the completion, product to be obtained drops at 100 DEG C, then by calcined product by dispersion sieving treatment process obtain it is final The lithium cobaltate cathode material of cobalt phosphate lithium cladding.
Embodiment 2
First by lithium carbonate (Li2CO3) powder, nickel hydroxide (Ni (OH)2) powder and manganese carbonate (MnCO3) powder to be to rub You compare Li2CO3: Ni (OH)2: MnCO3=1:0.5:1.5 mixing obtains LiNi0.25Mn0.75O4Precursor powder, precursor powder is logical Sand milling or ball-milling treatment are crossed until average grain diameter becomes 1 μm or smaller, gained slurry and cobalt acid lithium matrix are mixed, secondly By cobalt nitrate (Co (NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) dissolve in deionized water respectively, it is dense to be respectively formed 0.1mol/L The solution of degree.Above-mentioned configured cobalt nitrate solution is slowly added dropwise using peristaltic pump cocurrent while stirring and diammonium hydrogen phosphate is molten Liquid is stirred continuously dispersion 1h, revolving speed 1400r/min, until the Co generated3(PO4)2Nano particle equably appendix in matrix Surface carries out drying with water bath later at 90 DEG C.Then, it is warming up at 800 DEG C and is kept for 3 hours with the speed of 3 DEG C/min, forged After the completion of burning, product to be obtained is dropped at 100 DEG C, then calcined product is obtained finally by dispersion sieving treatment process MULTILAYER COMPOSITE lithium cobaltate cathode material.
Embodiment 3
Be only that the heat treatment temperature finally calcined is different from the difference of embodiment 2, be 700 DEG C, other experiment parameters and The identical method of embodiment 2, obtains the lithium cobaltate cathode material of MULTILAYER COMPOSITE.
Embodiment 4
First by lithium carbonate (Li2CO3) powder, nickel hydroxide (Ni (OH)2) powder and manganese carbonate (MnCO3) powder to be to rub You compare Li2CO3: Ni (OH)2: MnCO3=1.03:1.6:0.4 mixing obtains Li1.03Ni0.8Mn0.2O2Precursor powder, precursor powder End is mixed gained slurry and cobalt acid lithium matrix by being sanded or ball-milling treatment is until average grain diameter becomes 1 μm or smaller, Secondly by cobalt nitrate (Co (NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) dissolve in deionized water respectively, it is respectively formed The solution of 0.1mol/L concentration.Above-mentioned configured cobalt nitrate solution and phosphoric acid is slowly added dropwise using peristaltic pump cocurrent while stirring Two ammonium salt solution of hydrogen is stirred continuously dispersion 1h, revolving speed 1400r/min, until the CoPO generated4The uniform appendix of nano particle exists Matrix surface, later, heat treatment mode same as Example 2 ultimately forms the lithium cobaltate cathode material of MULTILAYER COMPOSITE.
Embodiment 5
First by lithium carbonate (Li2CO3) powder, nickel hydroxide (Ni (OH)2) powder and manganese carbonate (MnCO3) powder to be to rub You compare Li2CO3: Ni (OH)2: MnCO3=1.03:1.6:0.4 mixing obtains Li1.03Ni0.8Mn0.2O2Precursor powder, precursor powder End passes through sand milling or ball-milling treatment until average grain diameter is as 1 μm or smaller, by gained slurry, cobalt acid lithium matrix, nitric acid Three kinds of material mixings of cobalt, are slowly added dropwise configured ammonium dibasic phosphate solution using peristaltic pump while stirring, are stirred continuously dispersion 1h, revolving speed 1400r/min, later, heat treatment mode same as Example 2 is ultimately forming the cobalt acid lithium of MULTILAYER COMPOSITE just Pole material.
Embodiment 6
It is only that cobalt acid lithium matrix is different from the difference of embodiment 2, is LiCoO2, remaining raw material materials and process conditions phase Together, but effect is not so good as embodiment 2.
Embodiment 7
It is only that cobalt acid lithium matrix is different from the difference of embodiment 2, is Li1.2Co0.9Mg0.1O2, remaining raw material materials and work Skill condition is identical, but effect is better than embodiment 2.
Embodiment 8-10
Difference with embodiment 2 is only that cobalt phosphate lithium LiCoPO4Covering amount it is different, be respectively as follows: 10%, 0.25%, 0.5% (referring both to the quality relative to cobalt acid lithium matrix).
Embodiment 11
Difference with embodiment 2 is only that cobalt phosphate lithium and LiNi0.25Mn0.75O4Ratio it is different, but coat total amount not Become, mass ratio 2:1.It is specific as follows:
First by lithium carbonate (Li2CO3) powder, nickel hydroxide (Ni (OH)2) powder and manganese carbonate (MnCO3) powder to be to rub You compare Li2CO3: Ni (OH)2: MnCO3=1:0.5:1.5 mixing obtains LiNi0.25Mn0.75O4Precursor powder, precursor powder is logical Sand milling or ball-milling treatment are crossed until average grain diameter becomes 1 μm or smaller, gained slurry and cobalt acid lithium matrix are mixed, secondly By cobalt nitrate (Co (NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) dissolve in deionized water respectively, it is dense to be respectively formed 0.1mol/L The solution of degree.Above-mentioned configured cobalt nitrate solution is slowly added dropwise using peristaltic pump cocurrent while stirring and diammonium hydrogen phosphate is molten Liquid is stirred continuously dispersion 1h, revolving speed 1400r/min, until the Co generated3(PO4)2Nano particle equably appendix in matrix Surface carries out drying with water bath later at 90 DEG C.Then, it is warming up at 800 DEG C and is kept for 3 hours with the speed of 3 DEG C/min, forged After the completion of burning, product to be obtained is dropped at 100 DEG C, then calcined product is obtained finally by dispersion sieving treatment process MULTILAYER COMPOSITE lithium cobaltate cathode material.
Embodiment 12
Difference with embodiment 2 is only that heating rate when last sintering is 5 DEG C/min, remaining raw material materials and work Skill condition is identical.
Embodiment 13
Temperature when being only that last sintering from the difference of embodiment 12 is different, is 1000 DEG C, remaining raw material materials and work Skill condition is identical.
Comparative example 1
By by lithium carbonate (Li2CO3) powder, nickel hydroxide (Ni (OH)2) powder and manganese carbonate (MnCO3) powder to be to rub You compare Li2CO3: Ni (OH)2: MnCO3=1:0.5:1.5 mixing obtains LiNi0.25Mn0.75O4Precursor powder, precursor powder is logical Sand milling or ball-milling treatment are crossed until average grain diameter becomes 1 μm or smaller, gains and cobalt acid lithium matrix are mixed, and continues It is dispersed with stirring 1h.Later, drying with water bath is carried out at 90 DEG C.Then, it is warming up at 800 DEG C with 3 DEG C/min of speed and keeps 3 Hour, after the completion of calcining, product to be obtained is dropped at 100 DEG C, then by calcined product by dispersion sieving treatment process Obtain final LiNi0.25Mn0.75O4The lithium cobaltate cathode material of cladding.
The performance of all the above embodiment and comparative example material is detected, the results are shown in Table 1.
Initial capacity: using prepared cobalt acid lithium composite particles as the positive electrode of lithium ion, it is assembled into lithium ion half Battery charges and discharges at 45 DEG C of temperature, 4.5V high voltage, and obtains the discharge capacity recycled for the first time as initial Capacity.
100 capacity retention ratios: the discharge capacity that the 100th circulation is detected under 1C relative to the circulation of first time is kept Rate.
Table 1
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (9)

1. a kind of cobalt acid lithium composite material, which is characterized in that coat cobalt phosphate lithium on the surface of cobalt acid lithium oxide particle LiCoPO4Made of material；
The molecular formula of the cobalt acid lithium oxide particle is Li1+xCo1-y MyO2, M be selected from magnesium, aluminium, zirconium, titanium, lanthanum, zinc, vanadium one Kind is a variety of, and the quality of the cobalt phosphate lithium is the 0.25% ~ 10% of the quality of the cobalt acid lithium oxide particle；
0.1≤X≤0.20,0.1≤Y≤0.2；
The surface of the cobalt acid lithium oxide particle is also wrapped on LiwNi1-mMnmO2, 1.00≤W≤1.05,0≤m≤0.75；
The cobalt acid lithium composite material is obtained through following manner: according to LiwNi1-mMnmO2Atomic ratio take lithium source, nickel source, manganese Source and meets solution, the phosphorus of the soluble cobalt of cobalt phosphate lithium proportion then with the cobalt acid lithium oxide particle Acid/phosphate solution, lithium source mixing, reaction re-sinter to get product；
The method of the sintering are as follows: be warming up to 700-1000 DEG C of holding 1-4 hours, the speed of the heating is 2-5 DEG C/min.
2. cobalt acid lithium composite material according to claim 1, which is characterized in that M is selected from one kind or more of aluminium, zirconium, titanium, lanthanum Kind.
3. cobalt acid lithium composite material according to claim 1, which is characterized in that the quality of the cobalt phosphate lithium is the cobalt The 0.5% ~ 10% of the quality of sour oxidate for lithium particle.
4. cobalt acid lithium composite material according to claim 3, which is characterized in that the quality of the cobalt phosphate lithium is the cobalt The 0.5% ~ 5% of the quality of sour oxidate for lithium particle.
5. cobalt acid lithium composite material according to claim 1, which is characterized in that the LiwNi1-mMnmO2With the phosphoric acid Mass ratio≤1 of cobalt lithium.
6. cobalt acid lithium composite material according to claim 5, which is characterized in that the LiwNi1-mMnmO2With the phosphoric acid The gross mass of cobalt lithium is the 0.5% ~ 10% of the quality of the cobalt acid lithium oxide particle.
7. the preparation method of cobalt acid lithium composite material described in claim 1, which is characterized in that according to LiwNi1-mMnmO2Original Sub- ratio takes lithium source, nickel source, manganese source, then with the cobalt acid lithium oxide particle, and meets cobalt phosphate lithium proportion The solution of soluble cobalt, phosphoric acid/phosphate solution, lithium source mixing, reaction re-sinter to get product；
The method of the sintering are as follows: be warming up to 700-1000 DEG C of holding 1-4 hours, the speed of the heating is 2-5 DEG C/min.
8. the preparation method of cobalt acid lithium composite material as claimed in claim 7, which is characterized in that the method for the sintering are as follows: rise Temperature to 800-1000 DEG C holding 1-4 hours.
9. a kind of positive electrode, which is characterized in that be made using cobalt acid lithium composite material as claimed in any one of claims 1 to 6.
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