CN108417796A - A kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty and preparation method thereof - Google Patents

A kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty and preparation method thereof Download PDF

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CN108417796A
CN108417796A CN201810126139.9A CN201810126139A CN108417796A CN 108417796 A CN108417796 A CN 108417796A CN 201810126139 A CN201810126139 A CN 201810126139A CN 108417796 A CN108417796 A CN 108417796A
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nickel cobalt
cobalt lithium
lithium aluminate
low surface
cathode material
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瞿美臻
陈滔
闫新秀
汪沣
李想
王昊
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Chengdu Organic Chemicals Co Ltd of CAS
University of Chinese Academy of Sciences
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Chengdu Organic Chemicals Co Ltd of CAS
University of Chinese Academy of Sciences
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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
    • H01M4/52—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 discloses a kind of nickel cobalt lithium aluminate cathode materials of low surface alkalinty and preparation method thereof, and the nickel cobalt lithium aluminate cathode material is calcined in oxygen stream with nickel cobalt lithium aluminate positive active material by metal hydrogen phosphates and obtained.Coking phosphate is decomposed when the present invention is calcined using metal hydrogen phosphates, improves reactant activity, is promoted it to be reacted with the however, residual base of nickel cobalt lithium aluminate positive active material and is generated Li3PO4Clad; compared to phosphate; the structural integrity of hydrophosphate is lower; lattice energy smaller, reaction is easier, can significantly reduce calcination temperature; so that the dry method of nickel cobalt lithium aluminate positive active material is coated is changed into medium temperature solid phase reaction (400~600 DEG C) by high temperature solid state reaction in the prior art (700 DEG C); substantially reduce reaction difficulty, and it is simple for process, at low cost, production efficiency is high, be advantageously implemented scale industrial production.

Description

A kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty and preparation method thereof
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and in particular to a kind of nickel cobalt aluminic acid of low surface alkalinty Lithium anode material and preparation method thereof.
Background technology
The tertiary cathode material of nickelic system such as nickel cobalt lithium aluminate cathode material have energy density it is high, it is at low cost, to environment Friendly advantage, therefore receive the extensive concern of people, it is considered to be before having very much in lithium ion battery for electric vehicle The positive electrode of scape.But as nickel cobalt lithium aluminate (NCA) tertiary cathode material of nickelic system, it is more serious there is also one The easy moisture and carbon dioxide with air of problem, i.e. material surface, which reacts, generates LiOH and Li2CO3Equal by-products, make The surface texture for obtaining material deteriorates, also, on the one hand these surface by-products can hinder Li+Diffusion and interface charge Transfer reaction, and accelerate LiPF6The generation of HF in base electrolyte, eventually leads to the decline of NCA material electrochemical performances.In addition, These however, residual bases make the pH value of NCA powder in aqueous solution can easily exceed 12, and the enhancing of material surface alkalinity can be to pole piece Process for making produce serious influence.In NCA anode sizing agent preparation process, PVDF is dissolved in NMP, material surface Basic group can attack adjacent C-F, c h bond, PVDF is easy to that bimolecular elimination reaction occurs, and can be formed on strand The carbon-carbon double bond of a part, when PVDF internal double bonds increase, cohesive force can also increase, this can cause slurry viscosity to increase, very To formation gel state.These phenomenons are all easy to cause pole piece manufacturing process and occur that quality is unstable, and process consistency difference etc. is asked Topic when forming gel slurry, or even makes coating process that can not carry out.Therefore, the problem of NCA surface residuals alkali, limits the material Production and application on a large scale at home.
In order to solve the problems, such as nickelic system NCA positive electrodes surface residual alkali, washing or surface are carried out to this kind of material Modification is more effective two kinds of approach.Wherein, although can preferably eliminate the residual lithium salt on surface by washing, simultaneously The variation that can cause material surface structure and the Li in body phase+Dissolution so that the chemical property of material declines apparent.And it is right In surface modification, Min-JoonLee et al. (J.Journal of Materials Chemistry A2015,3, (25), 13453-13460) use NH4VO3Modification NCA materials, under the calcination condition of high temperature, NH are removed as cladding presoma4VO3With The Li of NCA material surfaces2CO3It reacts with LiOH and generates LiVOxAnd clad is formed, reduce the pH value of material.In addition, Part V5+Doping enters the agent structure of NCA materials, improves the structural stability of material.Based on above 2 points so that NCA The cycle performance of material significantly improves, but this method is coated using wet method, and for ethyl alcohol as solvent, technique used is multiple Miscellaneous, cost is higher, is unfavorable for the scale industrial production of material.Recently, Junhyeok Kim et al. (Adv.Mater.2017,1704309) Co is selected3(PO4)2Dry method cladding is carried out to NCA materials, in 700 DEG C of high-temperature calcination item Under part, Co3+Doping enters in the lattice body phase of NCA material surfaces, PO4 3-Then react with the however, residual base of surface of active material Generate the Li with higher li ionic conductivity3PO4Clad, to make the chemical property of NCA materials be improved.But it selects Use Co3(PO4)2As modification presoma, on the one hand, precursor material cost is higher, and on the other hand, calcination temperature has to Co at 700 DEG C of even higher temperature3(PO4)2It could react with the surface residual alkali of NCA active materials, preparation condition is severe It carves, production cost is higher, and the excessively high lithium nickel mixing degree for being also easy to cause nickel cobalt lithium aluminate cathode material of calcination temperature increases Add, hinders Li+Diffusion, to reduce the chemical property of the material.
Invention content
It is an object of the invention to：It is coated using dry method for the surface modification of above-mentioned existing nickel cobalt lithium aluminate cathode material There are severe reaction conditions, the present invention provides nickel cobalt lithium aluminate cathode material and its preparation side of a kind of low surface alkalinty Method.
The technical solution adopted by the present invention is as follows：
A kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty, the nickel cobalt lithium aluminate cathode material is by metal tripolyphosphate hydrogen Salt is calcined in oxygen stream with nickel cobalt lithium aluminate positive active material and is obtained.
Reacting between metal hydrogen phosphates of the present invention and nickel cobalt lithium aluminate positive active material is solid phase reaction, and solid phase is anti- Ying Zhong, solid material mixture directly react in solid form, are to prepare the most widely used method of polycrystalline solids.Solid phase is anti- High temperature solid state reaction (being higher than 600 DEG C), medium temperature solid phase reaction (100~600 DEG C) and low-temperature solid phase reaction should be divided into and (be less than 100 ℃).Reactant activity has very big influence to solid phase reaction, and reactant interior surface defect is more, and lattice is more imperfect, It is more in high-energy activation state, the reactivity with bigger can activated reactant using reactant decomposition.Metal of the present invention Hydrophosphate calcining when, resolve into pyrophosphate first, to improve reactant activity, promote its with nickel cobalt lithium aluminate just The however, residual base reaction of pole active material generates Li3PO4Clad, compared to phosphate, the structural integrity of hydrophosphate is lower, Lattice energy smaller, reaction are easier.Therefore, the present invention using metal hydrogen phosphates and nickel cobalt lithium aluminate positive active material compared with It can be carried out under low temperature (400~600 DEG C) so that the dry method of nickel cobalt lithium aluminate positive active material is coated by the prior art High temperature solid state reaction (700 DEG C) be changed into medium temperature solid phase reaction, significantly reduce reaction difficulty.
Further, metal hydrogen phosphates include at least one of magnesium monohydrogen phosphate, phosphoric acid hydrogen zirconium.Magnesium monohydrogen phosphate is heated to 1 molecular crystalline water is sloughed at 205 DEG C, is heated to decomposing coking magnesium phosphate (Mg at 550~650 DEG C2P2O7), magnesium pyrophosphate has α types (low temperature) and two kinds of variants of β types (high temperature), knee pointy temperature are 68 DEG C, and still, the two is often to coexist in extensive temperature 's.When using magnesium monohydrogen phosphate when, in nickel cobalt lithium aluminate positive active material reaction process, α types and β type phase co-conversions, this The transformation of kind crystal structure can further improve the reactivity of magnesium pyrophosphate, and improve solid phase reaction rate.
Phosphoric acid hydrogen zirconium is called basic zirconium phosphate, there is two kinds of structures of α and γ, alpha zirconium phosphate (α-Zr (HPO4)2·H2O) it is a kind of sun Layered compounds have regular veneer structure, and the crystallization water (Zr (HPO can be removed by being heated to 90~200 DEG C4)2), heating Phosphorus hydroxyl condensation, which is carried out, to 200~550 DEG C forms zirconium pyrophosphate (ZrP2O7), veneer structure is destroyed.Phosphoric acid hydrogen zirconium have compared with Big specific surface area and surface charge, has good ion exchange property, when using phosphoric acid hydrogen zirconium, just with nickel cobalt lithium aluminate Reaction interface between the active material of pole increases, while enhancing exchanging between zirconium ion and lithium ion, promotes to generate lithium phosphate, Be conducive to further increase solid phase reaction rate.
Further, the molar ratio of metal hydrogen phosphates and the nickel cobalt lithium aluminate positive active material is (0.1~5): 100。
Further, nickel cobalt lithium aluminate positive active material is LiNixCoyAlzO2, wherein x+y+z=1,0.6≤x< 0.9,0<Y≤0.3,0<z≤0.1.
Further, nickel cobalt lithium aluminate cathode material is spherical or spherical particle, and particle size range is 0.5~20um.
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty, the metal hydrogen phosphates and nickel cobalt aluminium Sour lithium positive active material is calcined at 400~600 DEG C, obtains the nickel cobalt lithium aluminate cathode material of low surface alkalinty.
Further, calcination time is 3~8h.The present invention is using metal hydrogen phosphates and nickel cobalt lithium aluminate positive electrode active material When matter is calcined, since metal hydrogen phosphates resolve into pyrophosphate, cause the transformation of lattice effect, improves reactant activity Meanwhile improving solid phase reaction rate so that reaction can be completed in shorter calcination time, be greatly improved production effect Rate.
Further, metal hydrogen phosphates and nickel cobalt lithium aluminate positive active material are mixed using dry ball milling before calcination It closes.It is smaller to react composition granule, specific surface area increases, and reaction interface increases, and is conducive to intensified response ability and diffusivity, to Improve solid phase reaction rate.
Further, rotational speed of ball-mill is 200~350r/min, and Ball-milling Time is 2~5h.
Further, the preparation method of nickel cobalt lithium aluminate positive active material is：By NixCoyAlz(OH)2Ternary forerunner Body is mixed with lithium salts, and nickel cobalt lithium aluminate positive active material is obtained through calcining, cooling down.
Further, NixCoyAlz(OH)2Ternary precursor and lithium salts calcining include the first constant temperature stage and second Constant temperature stage, the first constant temperature stage keep 0.5~20h, the second constant temperature stage to be protected at 700~800 DEG C at 400~500 DEG C Hold 0.5~20h.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1, the present invention using metal hydrogen phosphates calcining when decompose coking phosphate, improve reactant activity, promote its with The however, residual base reaction of nickel cobalt lithium aluminate positive active material generates Li3PO4Clad, compared to phosphate, the structure of hydrophosphate Fastness is lower, lattice energy smaller, and reaction is easier, can significantly reduce calcination temperature so that nickel cobalt lithium aluminate positive electrode active material The dry method of matter is coated is changed into medium temperature solid phase reaction (400~600 DEG C) by high temperature solid state reaction in the prior art (700 DEG C), Substantially reduce reaction difficulty；
2, when the present invention is calcined using metal hydrogen phosphates and nickel cobalt lithium aluminate positive active material, due to metal tripolyphosphate hydrogen Salt decomposes coking phosphate, causes the transformation of lattice effect, while improving reactant activity, improves solid phase reaction speed Rate so that reaction can be completed in shorter calcination time, be greatly improved production efficiency；
3, when the present invention uses magnesium monohydrogen phosphate, the magnesium pyrophosphate generated is decomposed there are the phase co-conversion of α types and β types, this The transformation of kind crystal structure can further improve the reactivity and solid phase reaction rate of magnesium pyrophosphate, when using phosphoric acid hydrogen zirconium, Its reaction interface between nickel cobalt lithium aluminate positive active material increases, while enhancing the friendship between zirconium ion and lithium ion It changes, promotes to generate lithium phosphate, be conducive to further increase solid phase reaction rate；
4, metal ion of the present invention in calcining to diffuseing to form doping vario-property inside nickel cobalt lithium aluminate positive active material Layer, improves the crystal structural stability of material；
5, present invention reaction difficulty is low, simple for process, at low cost, production efficiency is high, is advantageously implemented large-scale industrial life Production.
Description of the drawings
Fig. 1 is the SEM photograph of nickel cobalt lithium aluminate cathode material in the embodiment of the present invention 1, and amplification factor is 2000 times.
Specific implementation mode
All features disclosed in this specification can be with any other than mutually exclusive feature and/or step Mode combines.
Embodiment 1
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty：By NixCoyAlz(OH)2Ternary forerunner Body and LiOH in molar ratio 1：1.05 weigh, and after being sufficiently mixed uniformly, mixed-powder are transferred in corundum boat, and be pushed into tubular type Stove center is calcined, while being passed through oxygen, and heating rate is 5 DEG C/min, the insulation reaction 4h first at 480 DEG C, then is heated up It is sintered 15h to 750 DEG C, obtains nickel cobalt lithium aluminate positive active material；By obtained nickel cobalt lithium aluminate positive active material with Magnesium monohydrogen phosphate presses 98.5：1.5 are added in ball grinder, and setting rotational speed of ball-mill is 230r/min, after ball milling 2h, in oxygen stream plus Heat keeps the temperature 5h to 550 DEG C, obtain low surface alkalinty nickel cobalt lithium aluminate cathode material (its SEM scheme as shown in Figure 1, particle is equal Present spherical), it is 11.86 to measure pH value through pH value, and obtaining first circle specific discharge capacity through electrochemical property test is 188.9mAh g-1, 200 circles are recycled under room temperature and 2C multiplying powers, capacity retention is 86.3%.
Embodiment 2
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty：By NixCoyAlz(OH)2Ternary forerunner Body and LiOH in molar ratio 1：1.05 weigh, and after being sufficiently mixed uniformly, mixed-powder are transferred in corundum boat, and be pushed into tubular type Stove center is calcined, while being passed through oxygen, and heating rate is 5 DEG C/min, the insulation reaction 5h first at 480 DEG C, then is heated up It is sintered 13h to 750 DEG C, obtains nickel cobalt lithium aluminate positive active material；By obtained nickel cobalt lithium aluminate positive active material with Phosphoric acid hydrogen zirconium presses 99：1 is added in ball grinder, and setting rotational speed of ball-mill is 200r/min, after ball milling 3h, is heated in oxygen stream 450 DEG C, and 5h is kept the temperature, the nickel cobalt lithium aluminate cathode material of low surface alkalinty is obtained, it is 11.89 to measure pH value through pH, warp It is 189.5mAh g that electrochemical property test, which obtains first circle specific discharge capacity,-1, 100 circles, capacity are recycled under 55 DEG C and 2C multiplying powers Retention is 87.4%.
Embodiment 3
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty：By NixCoyAlz(OH)2Ternary forerunner Body and LiOH in molar ratio 1：1.05 weigh, and after being sufficiently mixed uniformly, mixed-powder are transferred in corundum boat, and be pushed into tubular type Stove center is calcined, while being passed through oxygen, and heating rate is 5 DEG C/min, the insulation reaction 4h first at 500 DEG C, then is heated up It is sintered 14h to 750 DEG C, obtains nickel cobalt lithium aluminate positive active material；By obtained nickel cobalt lithium aluminate positive active material with Magnesium monohydrogen phosphate, phosphoric acid hydrogen zirconium press 99：0.5：0.5 is added in ball grinder, and setting rotational speed of ball-mill is 250r/min, after ball milling 3h, It is heated to 600 DEG C in oxygen stream, and keeps the temperature 5h, obtains the nickel cobalt lithium aluminate cathode material of low surface alkalinty, tests and surveys through pH It is 11.81 to obtain pH value, and it is 187.8mAh g to obtain first circle specific discharge capacity through electrochemical property test-1, followed under room temperature 2C multiplying powers Ring 200 encloses, and capacity retention is 84.3%.
Comparative example
The nickel cobalt lithium aluminate positive active material prepared using embodiment 1 measures pH value as blank control through pH It is 12.31, it is 190.6mAh g to obtain first circle specific discharge capacity through electrochemical property test-1, 200 are recycled under room temperature and 2C multiplying powers Circle, capacity retention are only 72.3%, and 100 circle of cycle under 55 DEG C and 2C multiplying powers, capacity retention is 74.8%.
Experimental example 1
In embodiment 1, embodiment 2, embodiment 3 and comparative example, pH value test method is：Weigh 1g raw materials at normal temperatures It is dissolved in 100g distilled water, after stirring 5min, pH value measurement is carried out to supernatant using pH meter.
Experimental example 2
In embodiment 1, embodiment 2, embodiment 3 and comparative example, the preparation of electrode and its electrochemical property test method It is as follows：
With N-Methyl pyrrolidone (NMP) for solvent, Kynoar (PVDF) is binder, and Super P are conductive agent, Wherein PVDF is previously dissolved in before use in NMP.In mass ratio 80：10：10 weigh raw material, PVDF and Super P respectively, go forward side by side Row batch mixing is ground, and the obtained slurry of grinding is coated in 9 microns of thickness and as on the bright aluminium foil of collector, waiting for that NMP volatilizations are complete Afterwards, aluminium foil is rolled with roll squeezer, then is punched into the electrode slice of a diameter of 13mm；Then electrode slice be placed in vacuum drying oven in Drying overnight at 105 DEG C；After weighing pole piece, it is transferred quickly in glove box；It is to electrode with lithium metal, Celgard 2400 is Diaphragm, by 1mol/L LiPF6It is dissolved in EC/DMC/EMC (volume ratios 1:1:1) in the mixed solvent is as electrolyte.To assembling Battery carry out electrochemical property test, test equipment is blue electricity CT2001A constant current test cabinets, test voltage ranging from 2.8- 4.3V。
It is the embodiment of the present invention as described above.The present invention is not limited to the above-described embodiments, anyone should learn that The structure change made under the inspiration of the present invention, the technical schemes that are same or similar to the present invention each fall within this Within the protection domain of invention.

Claims (10)

1. a kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty, which is characterized in that the nickel cobalt lithium aluminate cathode material by Metal hydrogen phosphates are calcined in oxygen stream with nickel cobalt lithium aluminate positive active material and are obtained.
2. a kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 1, which is characterized in that the gold It includes at least one of magnesium monohydrogen phosphate, phosphoric acid hydrogen zirconium to belong to hydrophosphate.
3. a kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 1 or 2, which is characterized in that institute The molar ratio for stating metal hydrogen phosphates and the nickel cobalt lithium aluminate positive active material is (0.1~5):100.
4. a kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 1, which is characterized in that the nickel Cobalt lithium aluminate positive active material is LiNixCoyAlzO2, wherein x+y+z=1,0.6≤x<0.9,0<Y≤0.3,0<z≤ 0.1。
5. a kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 1, which is characterized in that the nickel Cobalt lithium aluminate cathode material is spherical or spherical particle, and particle size range is 0.5~20um.
6. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty, which is characterized in that the metal tripolyphosphate hydrogen Salt is calcined with nickel cobalt lithium aluminate positive active material at 400~600 DEG C, and the nickel cobalt lithium aluminate anode material of low surface alkalinty is obtained Material.
7. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 6, feature It is, the calcination time is 3~8h.
8. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 6, feature It is, the metal hydrogen phosphates are mixed using dry ball milling before calcination with nickel cobalt lithium aluminate positive active material.
9. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 6, feature It is, the preparation method of the nickel cobalt lithium aluminate positive active material is：By NixCoyAlz(OH)2Ternary precursor and lithium salts Mixing, nickel cobalt lithium aluminate positive active material is obtained through calcining, cooling down.
10. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of low surface alkalinty according to claim 9, feature It is, the NixCoyAlz(OH)2Ternary precursor and lithium salts calcining include the first constant temperature stage and the second constant temperature stage, First constant temperature stage kept 0.5~20h at 400~500 DEG C, and the second constant temperature stage kept 0.5 at 700~800 DEG C~ 20h。
CN201810126139.9A 2018-02-08 2018-02-08 A kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty and preparation method thereof Pending CN108417796A (en)

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CN109244428A (en) * 2018-11-05 2019-01-18 桑顿新能源科技有限公司 A kind of coating modification method of nickelic ternary material
CN109713284A (en) * 2018-12-29 2019-05-03 蜂巢能源科技有限公司 Anode material for lithium-ion batteries and preparation method thereof and battery
CN109768254A (en) * 2019-01-15 2019-05-17 合肥国轩高科动力能源有限公司 Modified low nickelic tertiary cathode material of residual alkali type and the preparation method and application thereof
CN109950496A (en) * 2019-03-29 2019-06-28 荆门市格林美新材料有限公司 Nickel cobalt lithium aluminate tertiary cathode material and preparation method are covered in a kind of double-contracting
WO2020248984A1 (en) * 2019-06-12 2020-12-17 中国科学院化学研究所 Method for reducing alkalinity of positive electrode material by using phosphorus-containing organic matter

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109244428A (en) * 2018-11-05 2019-01-18 桑顿新能源科技有限公司 A kind of coating modification method of nickelic ternary material
CN109244428B (en) * 2018-11-05 2022-06-14 桑顿新能源科技(长沙)有限公司 Coating modification method of high-nickel ternary material
CN109713284A (en) * 2018-12-29 2019-05-03 蜂巢能源科技有限公司 Anode material for lithium-ion batteries and preparation method thereof and battery
CN109713284B (en) * 2018-12-29 2020-11-24 蜂巢能源科技有限公司 Lithium ion battery anode material and preparation method thereof and battery
CN109768254A (en) * 2019-01-15 2019-05-17 合肥国轩高科动力能源有限公司 Modified low nickelic tertiary cathode material of residual alkali type and the preparation method and application thereof
CN109950496A (en) * 2019-03-29 2019-06-28 荆门市格林美新材料有限公司 Nickel cobalt lithium aluminate tertiary cathode material and preparation method are covered in a kind of double-contracting
CN109950496B (en) * 2019-03-29 2022-01-04 荆门市格林美新材料有限公司 Double-coated lithium nickel cobalt aluminate ternary positive electrode material and preparation method thereof
WO2020248984A1 (en) * 2019-06-12 2020-12-17 中国科学院化学研究所 Method for reducing alkalinity of positive electrode material by using phosphorus-containing organic matter

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