CN106654224A - Lithium cobaltate composite material and preparation method thereof as well as positive electrode material - Google Patents

Lithium cobaltate composite material and preparation method thereof as well as positive electrode material Download PDF

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CN106654224A
CN106654224A CN201710032201.3A CN201710032201A CN106654224A CN 106654224 A CN106654224 A CN 106654224A CN 201710032201 A CN201710032201 A CN 201710032201A CN 106654224 A CN106654224 A CN 106654224A
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cobalt
acid lithium
cobalt acid
lithium
oxide particle
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CN106654224B (en
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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 RESHINE NEW MATERIAL CO Ltd
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    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • 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
    • H01M4/485—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
    • 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
    • H01M4/52—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
    • 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
    • H01M4/58—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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

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Abstract

The invention provides a lithium cobaltate composite material and a preparation method thereof as well as a positive electrode material. The lithium cobaltate composite material is a material formed by coating lithium cobalt phosphate LiCoPO4 on surfaces of lithium cobaltate oxide particles; the molecular formula of the lithium cobaltate oxide particles is Li1+xCo1-yMyO2 and M is selected from one or more of magnesium, aluminum, zirconium, titanium, lanthanum, zinc and vanadium; the mass of the lithium cobalt phosphate is 0.25 percent to 10 percent of the mass of the lithium cobaltate oxide particles. By adopting the lithium cobaltate composite material, the problems that lithium cobaltate has poor circulating performance at high temperature or under high pressure and the electric capacity is low are solved.

Description

A kind of cobalt acid lithium composite and preparation method thereof, positive electrode
Technical field
The present invention relates to chemical field, more particularly, to a kind of cobalt acid lithium composite and preparation method thereof, positive electrode.
Background technology
In recent years, with the extensive application of portable electric appts, use requirement more and more higher of the people to battery, especially It is to capacity, resistant to elevated temperatures requirement.And lithium ion battery due to operating voltage height, small volume, specific energy be high, pollution less, The excellent combination property such as memory-less effect, so always in occupation of the leading position of portable electric appts.
At present in anode material for lithium-ion batteries, due to simple production process, discharge capacity is big, good cycle for cobalt acid lithium Etc. advantage, substantial amounts of market is occupied, but while cobalt acid lithium there is also certain problem, the such as theory of cobalt acid lithium as positive electrode 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, residual capacity can have been utilized by improving charging voltage in theory.However, work as improving charging voltage extremely 4.5V or it is higher when, electrolyte easily unstable decomposition, the easy dissolution of cobalt of cobalt acid lithium causes cycle performance of battery to reduce, sternly Can set off an explosion during weight, great hidden danger is produced to personal safety, therefore be difficult to improve actual appearance by improving charging voltage Amount.Therefore searching out can improve the high voltage of cobalt acid lithium, improve the method for capacity and cycle performance to lithium ion battery industry Development has great significance.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of cobalt acid lithium composite, and described composite solves cobalt acid lithium Cycle performance is poor under high temperature or high pressure, and the problem that capacitance is low.
The second object of the present invention is the preparation method for providing above-mentioned cobalt acid lithium composite, described method flow letter It is single, easily promote.
The third object of the present invention is to provide a kind of positive electrode, and described positive electrode has capacitance height, high temperature The advantages of cycle of higher pressure performance is good.
In order to realize object above, the invention provides technical scheme below：
A kind of cobalt acid lithium composite, in the Surface coating cobalt phosphate lithium LiCoPO of cobalt acid lithium oxide particle4 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 One or more, the quality of the cobalt phosphate lithium is the 0.25%～10% of the cobalt acid lithium oxide particle.
Difference with existing common cobalt acid lithium or doped with the cobalt acid lithium of miscellaneous element of the invention is：By cobalt acid lithium matrix And it is coated on the LiCoPO on its surface4Composition, is a kind of composite structure, and belongs to chemically active cladding, LiCoPO4 LiOH and Li can be reduced2CO3Generation, 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 null value, i.e., the present invention is applied to the cobalt acid lithium of the element that undopes, but remains to reach raising The circulative effect of HTHP, i.e., under 4.5V high voltages after 100 discharge and recharges capability retention more than 85%.
M of the present invention can be single magnesium, aluminium, zirconium, titanium, lanthanum, zinc or vanadium, or magnesium, aluminium are mixed with arbitrary proportion Close, or magnesium, aluminium, zirconium, titanium with arbitrary proportion mixing, or aluminium, zirconium, titanium, lanthanum with arbitrary proportion mixing, Huo Zhexin, vanadium with appoint Meaning ratio mixes.
Cobalt acid lithium oxide particle of the present invention can be LiCoO2, Li1Co0.99Zn0.01O2, Li1.1Co0.8Al0.05Mg0.05Ti0.05La0.05O2, Li1Co0.9Al0.05Zr0.05O2, Li1.2Co0.9Ti0.05La0.05O2, Li1Co0.9Al0.03Zr0.05V0.02O2Deng.
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%th, 7%, 9%, 10%.
In order to improve the synergy between doped chemical and coating, the capacitance and high temperature for more significantly improving material is high Pressure 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 selected from aluminium, zirconium, titanium, one or more of lanthanum.
Or, 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 more than 4.5V One high voltage platform, with higher energy density, and aboundresources, low price, lithium cobaltate cathode can be improved The high voltage performance of material, operating voltage brings up to more than 4.5V by universal 4.2V, so as to further with LiCoO2It is surplus Covolume amount, improves the capability value of cobalt acid lithium.
Preferably, it is to obtain higher capability value and high rate performance, 1.00≤W≤1.05,0≤M≤0.75.
Preferably, the LiwNi1-mMnmO2It is the cobalt acid lithium oxide particle with the gross mass of the cobalt phosphate lithium When 0.5%～10%, two kinds of covering materials can act synergistically, while conspicuousness ground improves 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 simultaneously be coated on cobalt acid lithium oxide particle surface, it is also possible to which substep is wrapped Cover, but sequencing is not restricted by, and the material property for obtaining does not have marked difference.
If only coat cobalt phosphate lithium, it is preferred to use following preparation method：
According to formula, coated LiCoPO using wet method cladding or dry method4It is coated on the table of cobalt acid lithium oxide particle Face, then sinters and obtains final product.
Wherein, the speed of dry method cladding is fast, efficiency high, but uniformity does not have wet method to coat.
In order to improve the crystalline structure of particle from microstructure, obtain that aperture is little but porosity is high, specific surface area is reasonable Characteristic, so as to constructively improve electric conductivity, it is preferable that the method for the sintering is：It is warming up to 700-1000 DEG C of holding 1-4 hours, the speed of the intensification is preferably 2-5 DEG C/min；
It is highly preferred that the method for the sintering is：It is warming up to 800-1000 DEG C of holding 1-4 hour.
Preferred wet method cladding process is：It is according to default proportioning, the solution of soluble cobalt, phosphoric acid/phosphate is molten Liquid, lithium source and the cobalt acid lithium oxide particle hybrid reaction, are dried afterwards.Wherein, the addition sequence of above raw material is not received Limit.
The phosphate is preferably ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate or potassium hydrogen phosphate etc., fully anti-in order to ensure Should, C (Co)：C (P) is controlled 1:1 to 3:In the range of 2.
The Co sources are selected from cobaltous sulfate, cobalt chloride, cobalt nitrate.
The method being dried after reaction is preferably：It is dried at 70～90 DEG C.
If cladding bi-material, is 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 of the soluble cobalt of the cobalt phosphate lithium proportioning, phosphoric acid/phosphate solution, lithium source mixing, reaction is reburned Knot, obtains final product product.
Preferably, also, the method for the sintering is：It is warming up to 700-1000 DEG C of holding 1-4 hour, the speed of the intensification Degree is preferably 2-5 DEG C/min.
Preferably, the method for the sintering is：It is warming up to 800-1000 DEG C of holding 1-4 hour.
As described above, composite of the present invention is mainly for the preparation of positive electrode, naturally it is also possible to for it Its field.
To sum up, compared with prior art, invention achieves following technique effect：
(1) HTHP cycle performance and forthright again is significantly improved：By Surface coating LiCoPO4Effect more than having reached Really.
(2) capacitance of the material as positive pole is significantly improved：By LiCoPO4And LiwNi1-mMnmO2Two kinds of coatings Synergy reached the effect.
(3) microstructure of material is improved：The process conditions such as optimization sintering, cladding improve the bonding of material and stablize The performances such as property, porosity, aperture, specific surface area, density, so as to improve the comprehensive electric conductivity of material.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with specific embodiment, but ability Field technique personnel will be understood that, following described embodiment is a part of embodiment of the invention, rather than the embodiment of whole, The present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the common skill in this area The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model of present invention protection Enclose.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument Unreceipted production firm person, being can pass through the conventional products that commercially available purchase is obtained.
Hereafter in addition to embodiment 6 and 7, the cobalt acid lithium matrix of remaining all embodiment is Li1Co0.8Al0.05Zr0.05Ti0.05La0.05O2。
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, the solution of 0.1mol/L concentration is formed respectively.Then by a certain amount of cobalt acid lithium oxide particle and appropriate pure water Mixing is slowly added dropwise the good cobalt nitrate solution of above-mentioned configuration and diammonium hydrogen phosphate using peristaltic pump cocurrent while stirring as bottom liquid Solution, is stirred continuously dispersion 1h, and rotating speed is 1400r/min, until the CoPO for generating4The uniform appendix of nano particle is in matrix table Face, afterwards, carries out drying with water bath at 90 DEG C.Subsequently, kept for 3 hours at being warmed up to 800 DEG C with 3 DEG C/min of speed, calcining After the completion of, product to be obtained is dropped at 100 DEG C, then the product after calcining is obtained into final through dispersion handling process of sieving 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 rubbing You compare Li2CO3：Ni(OH)2：MnCO3=1:0.5:1.5 mixing obtain LiNi0.25Mn0.75O4Precursor powder, precursor powder lead to Either ball-milling treatment, until average grain diameter becomes 1 μm or less, gained slurry and cobalt acid lithium matrix is mixed, secondly to cross sand milling By cobalt nitrate (Co (NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) dissolve in respectively in deionized water, it is dense that 0.1mol/L is formed respectively The solution of degree.It is slowly added dropwise the good cobalt nitrate solution of above-mentioned configuration using peristaltic pump cocurrent while stirring and diammonium hydrogen phosphate is molten Liquid, is stirred continuously dispersion 1h, and rotating speed is 1400r/min, until the Co for generating3(PO4)2Nano particle equably appendix in matrix Surface, afterwards, carries out drying with water bath at 90 DEG C.Subsequently, kept for 3 hours at being warmed up to 800 DEG C 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 the product after calcining is obtained finally through dispersion handling process of sieving MULTILAYER COMPOSITE lithium cobaltate cathode material.
Embodiment 3
It is different from the heat treatment temperature for differing only in last calcining 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 rubbing You compare Li2CO3：Ni(OH)2：MnCO3=1.03:1.6:0.4 mixing obtains Li1.03Ni0.8Mn0.2O2Precursor powder, precursor powder By sand milling, either ball-milling treatment becomes 1 μm or less until average grain diameter at end, by gained slurry and the mixing of cobalt acid lithium matrix, Secondly by cobalt nitrate (Co (NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) dissolve in respectively in deionized water, formed respectively The solution of 0.1mol/L concentration.It is slowly added dropwise the good cobalt nitrate solution of above-mentioned configuration and phosphoric acid using peristaltic pump cocurrent while stirring The ammonium salt solution of hydrogen two, is stirred continuously dispersion 1h, and rotating speed is 1400r/min, until the CoPO for generating4The uniform appendix of nano particle exists Matrix surface, afterwards, 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 rubbing You compare Li2CO3：Ni(OH)2：MnCO3=1.03:1.6:0.4 mixing obtains Li1.03Ni0.8Mn0.2O2Precursor powder, precursor powder By sand milling, either ball-milling treatment becomes 1 μm or less until average grain diameter at end, by gained slurry, cobalt acid lithium matrix, nitric acid Three kinds of material mixings of cobalt, are slowly added dropwise while stirring the ammonium dibasic phosphate solution for having configured using peristaltic pump, are stirred continuously dispersion 1h, rotating speed is 1400r/min, and afterwards, heat treatment mode same as Example 2 is ultimately forming the cobalt acid lithium of MULTILAYER COMPOSITE just Pole material.
Embodiment 6
From embodiment 2 to differ only in cobalt acid lithium matrix different, be LiCoO2, remaining raw material materials and process conditions phase Together, but effect be not so good as embodiment 2.
Embodiment 7
From embodiment 2 to differ only in cobalt acid lithium matrix different, be Li1.2Co0.9Mg0.1O2, remaining raw material materials and work Skill condition is identical, but effect is better than embodiment 2.
Embodiment 8-10
Cobalt phosphate lithium LiCoPO is differed only in embodiment 24Covering amount it is different, respectively：10%th, 0.25%, 0.5% (referring both to the quality relative to cobalt acid lithium matrix).
Embodiment 11
Cobalt phosphate lithium and LiNi are differed only in embodiment 20.25Mn0.75O4Ratio it is different, but coat total amount not Become, mass ratio is 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 rubbing You compare Li2CO3：Ni(OH)2：MnCO3=1:0.5:1.5 mixing obtain LiNi0.25Mn0.75O4Precursor powder, precursor powder lead to Either ball-milling treatment, until average grain diameter becomes 1 μm or less, gained slurry and cobalt acid lithium matrix is mixed, secondly to cross sand milling By cobalt nitrate (Co (NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) dissolve in respectively in deionized water, it is dense that 0.1mol/L is formed respectively The solution of degree.It is slowly added dropwise the good cobalt nitrate solution of above-mentioned configuration using peristaltic pump cocurrent while stirring and diammonium hydrogen phosphate is molten Liquid, is stirred continuously dispersion 1h, and rotating speed is 1400r/min, until the Co for generating3(PO4)2Nano particle equably appendix in matrix Surface, afterwards, carries out drying with water bath at 90 DEG C.Subsequently, kept for 3 hours at being warmed up to 800 DEG C 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 the product after calcining is obtained finally through dispersion handling process of sieving MULTILAYER COMPOSITE lithium cobaltate cathode material.
Embodiment 12
Programming rate when differing only in last sintering with embodiment 2 is 5 DEG C/min, remaining raw material materials and work Skill condition is identical.
Embodiment 13
It is different from temperature when differing only in last sintering of embodiment 12, it 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 rubbing You compare Li2CO3：Ni(OH)2：MnCO3=1:0.5:1.5 mixing obtain LiNi0.25Mn0.75O4Precursor powder, precursor powder lead to Either ball-milling treatment, until average grain diameter becomes 1 μm or less, gains and cobalt acid lithium matrix is mixed to cross sand milling, and is continued Dispersed with stirring 1h.Afterwards, drying with water bath is carried out at 90 DEG C.Subsequently, 3 are kept at being warmed up to 800 DEG C with 3 DEG C/min of speed Hour, after the completion of calcining, product to be obtained is dropped at 100 DEG C, then the product after calcining is sieved handling process through dispersion Obtain final LiNi0.25Mn0.75O4The lithium cobaltate cathode material of cladding.
The performance of all the above embodiment and comparative example material is detected, as a result as shown in table 1.
Initial capacity：Using prepared cobalt acid lithium composite particles as the positive electrode of lithium ion, lithium ion half is assembled into Battery, in 45 DEG C of temperature, charges and discharges under 4.5V high voltages, and obtains the discharge capacity of circulation for the first time as initial Capacity.
100 capability retentions：Detect that the 100th circulation keeps relative to the discharge capacity of primary circulation under 1C Rate.
Table 1
Finally it should be noted that：Various embodiments above only to illustrate technical scheme, rather than a limitation；To the greatest extent Pipe has been described in detail with reference to foregoing embodiments to the present invention, it will be understood by those within the art that：Its according to So the technical scheme described in foregoing embodiments can be modified, either which part or all technical characteristic are entered Row equivalent；And these modifications or replacement, do not make the essence disengaging various embodiments of the present invention technology of appropriate technical solution The scope of scheme.

Claims (10)

1. a kind of cobalt acid lithium composite, it is characterised in that in the Surface coating cobalt phosphate lithium of cobalt acid lithium oxide particle LiCoPO4Material；
The molecular formula of the cobalt acid lithium oxide particle is Li1+xCo1-yMyO2, M is selected from magnesium, aluminium, zirconium, titanium, lanthanum, zinc, one kind of vanadium Or it is various, the quality of the cobalt phosphate lithium is the 0.25%～10% of the cobalt acid lithium oxide particle.
2. cobalt acid lithium composite according to claim 1, it is characterised in that -0.1≤X≤0.20,0≤Y≤0.2；
Preferably, 0.1≤X≤0.20,0.1≤Y≤0.2；
Preferably, M selected from aluminium, zirconium, titanium, one or more of lanthanum.
3. cobalt acid lithium composite according to claim 1, it is characterised in that the quality of the cobalt phosphate lithium is the cobalt The 0.5%～10% of sour oxidate for lithium particle, more preferably 0.5%～5%.
4. cobalt acid lithium composite according to claim 1, it is characterised in that the surface of the cobalt acid lithium oxide particle It is also wrapped on LiwNi1-mMnmO2, 1.00≤W≤1.05,0≤M≤0.75.
5. cobalt acid lithium composite according to claim 4, it is characterised in that the LiwNi1-mMnmO2With the phosphoric acid Mass ratio≤1 of cobalt lithium；
Preferably, the LiwNi1-mMnmO2With 0.5% that the gross mass of the cobalt phosphate lithium is the cobalt acid lithium oxide particle ～10%.
6. the preparation method of the cobalt acid lithium composite described in any one of claim 1-3, it is characterised in that including following step Suddenly：
According to formula, coated LiCoPO using wet method cladding or dry method4The surface of cobalt acid lithium oxide particle is coated on, so Afterwards sintering is obtained final product.
7. the preparation method of cobalt acid lithium composite according to claim 6, it is characterised in that the method for the sintering For：700-1000 DEG C of holding 1-4 hour is warming up to, the speed of the intensification is preferably 2-5 DEG C/min；
Preferably, the method for the sintering is：It is warming up to 800-1000 DEG C of holding 1-4 hour.
8. the preparation method of cobalt acid lithium composite according to claim 6, it is characterised in that the wet method cladding is：
According to default proportioning, by the solution of soluble cobalt, phosphoric acid/phosphate solution, lithium source and the cobalt acid lithium oxide Particle hybrid reaction, is dried afterwards.
9. the preparation method of the cobalt acid lithium composite described in claim 4 or 5, it is characterised in that according to LiwNi1-mMnmO2's Atomic ratio takes lithium source, nickel source, manganese source, then with the cobalt acid lithium oxide particle, and meets the cobalt phosphate lithium proportioning The solution of soluble cobalt, phosphoric acid/phosphate solution, lithium source mixing, reaction re-sinters, and obtains final product product；
Preferably, the method for the sintering is：700-1000 DEG C of holding 1-4 hour is warming up to, the speed of the intensification is preferably 2-5 DEG C/min；
Preferably, the method for the sintering is：It is warming up to 800-1000 DEG C of holding 1-4 hour.
10. a kind of positive electrode, it is characterised in that be obtained using the cobalt acid lithium composite described in any one of claim 1-5.
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