CN108807949A - A kind of preparation method of high nickel lithium manganate cathode material - Google Patents

A kind of preparation method of high nickel lithium manganate cathode material Download PDF

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CN108807949A
CN108807949A CN201810892544.1A CN201810892544A CN108807949A CN 108807949 A CN108807949 A CN 108807949A CN 201810892544 A CN201810892544 A CN 201810892544A CN 108807949 A CN108807949 A CN 108807949A
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lithium manganate
nickelic
positive electrode
preparation
phosphate
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方明
毛秦钟
钱志挺
徐士民
李伟
张中彩
封日升
吉同棕
王寅峰
吴海军
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Zhejiang Mei Du Hai Chuang Lithium Electric Technology Co Ltd
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Zhejiang Mei Du Hai Chuang Lithium Electric Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/20Batteries in motive systems, e.g. vehicle, ship, plane
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The present invention relates to new-energy automobile lithium ion power battery technology fields, and in particular to a kind of preparation method of high nickel lithium manganate cathode material.The present invention, then by low-temperature sintering doping, wet method cladding, high temperature sintering renovation technique, obtains good cycle, the high nickel lithium manganate cathode material of long storage using the spherical nickelic manganese binary presoma of Co deposited synthesis.

Description

A kind of preparation method of high nickel lithium manganate cathode material
Technical field
The present invention relates to new-energy automobile lithium ion power battery technology fields, and in particular to a kind of high nickel ion doped is just The preparation method of pole material.
Background technology
Lithium-ion-power cell is new-energy automobile development core technology link, and the wherein quality of positive electrode is even more to restrict The most important thing of power battery development.With the increase of electric vehicle course continuation mileage and continuously decreasing for public subsidies, to dynamic The energy density of power battery requires also higher and higher.
In June, 2016, the Department of Science and Technology issues 10 emphasis special projects such as " new-energy automobiles ", right in new-energy automobile special project It is as follows in the performance assessment criteria of dynamic lithium battery:
Energy-density lithium ion battery technology (great Key Common Technologies class):Performance assessment criteria:The year two thousand twenty, battery cell energy Metric density >=300Wh/kg, cycle life >=1500 time, cost≤0.8 yuan/Wh, safety etc. reach national standard;Year production The watt-hour of ability >=200,000,000, when product cumulative sale >=3000 myriawatt or entrucking quantity >=1000 set.
Nowadays, high gram volume, high-voltage anode material are the demands in power battery market.Positive electrode is also from initial NCM111 develops to NCM523, NCM622 and NCM811, the directions NCA.Nickel content in positive electrode is improved, while reducing cobalt Content can reduce the cost of raw material simultaneously improving material gram volume, and therefore, nickelic positive electrode is to promote positive electrode enterprise The key of industry added value and the competition highland of positive electrode enterprise.
Nickelic positive electrode is primarily present the problems such as poor circulation, storage capacity are poor, compacted density is low.Currently, industry Ternary precursor material is generally inside prepared using coprecipitation, then high temperature solid-state doping reduces material cation mixing degree, Improve the stability and first charge-discharge efficiency of crystal structure;And the method for middle low temperature cladding, reduce material and electrolyte it Between interfacial reaction, improve the cycle performance and storage capacity of material.
Patent of the present invention is directed to the poor circulation of " nickelic positive electrode ", the feature that storage capacity is poor, of high cost, probes into A method of efficient, low cost improves the cycle performance and storage capacity of nickelic positive electrode.
Invention content
In view of the above problems, a kind of low cost of present invention exploitation, high power capacity, macrocyclic high nickel lithium manganate cathode material, Using the spherical nickelic manganese binary presoma of Co deposited synthesis, then repaiied by low-temperature sintering doping, wet method cladding, high temperature sintering It returns to work skill, obtains good cycle, the high nickel lithium manganate cathode material of long storage.
The technical solution adopted in the present invention is:
A kind of preparation method of nickelic lithium manganate cell positive electrode material, includes the following steps:
S1. soluble nickel salt, manganese salt, alkali metal hydroxide and ammonium hydroxide are stirred, carry out constant temperature in a kettle Coprecipitation reaction centrifuges, drying obtains spherical nickelic manganese binary presoma then by being separated by solid-liquid separation, being aged;
S2. lithium hydroxide, spherical nickelic manganese binary presoma, oxide addition are mixed, under the conditions of oxygen-enriched atmosphere, High temperature sintering is carried out, spherical high nickel ion doped binary positive material is obtained;
S3. soluble cobalt and phosphate are dissolved in deionized water, carries out mechanical agitation until there is light red precipitation It generates, high nickel ion doped binary positive material is then added and continues stirring, filtering, drying, the high nickel ion doped after as coating Positive electrode;
S4. under the conditions of oxygen atmosphere, the positive electrode after cladding is subjected to low temperature sintering, obtains nickelic lithium manganate cathode Material.
Preferably, the molar ratio of soluble nickel ion and manganese ion described in the step S1 is 1:1~10:1;It is spherical high The average grain diameter D50 of nickel manganese binary presoma:8~12um.
Specifically, ammonia concn in the S1:0.1~0.6mol/L;The nickel ion, manganese ion total concentration be 0.5 ~2.0mol/L;The alkali metal hydroxide is NaOH;Mixing speed:500~2000r/min;Coprecipitation reaction temperature:20 DEG C~60 DEG C, pH value in reaction:10~13;Digestion time:10~48h;Drying temperature:100 DEG C~150 DEG C, drying time:2~ 24h。
Preferably, the volumetric concentration of oxygen-enriched atmosphere described in the step S2:50%~99%;The item of the high temperature sintering Part:500 DEG C~900 DEG C of temperature, 10~30h of soaking time.
Specifically, in step s 2, oxide addition ZrO, MgO, Cr2O3、Al2O3、Fe2O3, ZnO and CuO waited Cross at least one of metal oxide;The heating rate of the high-temperature sintering process:1~10 DEG C/min.
Preferably, soluble cobalt described in the step S3 includes:At least one in cobalt nitrate, cobalt chloride and cobaltous sulfate Kind;The phosphate includes:At least one in ammonium hydrogen phosphate, potassium hydrogen phosphate, dibastic sodium phosphate, ammonium phosphate, sodium phosphate and potassium phosphate Kind.
Specifically, third member Co is coated on substrate surface, clad in the form of wet method, fabricated in situ in the step S3 Uniformly so that cycle, the storage performance of material improve;The capsulation condition:Cobalt ions, phosphate anion molar ratio be 3:2, In the mixed solvent cobalt ions, phosphate anion total concentration be 0.01~0.1mol/L;Mixing speed:500~2000r/min; Mixing time:0.5~10h;Whipping temp:10 DEG C~50 DEG C;Drying temperature:100 DEG C~150 DEG C;Drying time:2~for 24 hours.
Preferably, the volumetric concentration of oxygen atmosphere described in the step S4:20%~99%;The item of the low temperature sintering Part:300 DEG C~900 DEG C of temperature, 10~30h of soaking time.
Specifically, the heating rate of the low temperature sintering process:1~10 DEG C/min.
Preferably, the chemical formula of high nickel lithium manganate cathode material described in the step S4:LiNixMnyO2·CozPO4, In:0.6 < x≤1,0.01 < y≤0.4,0.01 < z≤0.2, x+y+z=1.
Specifically, the positive electrode of acquisition is assembled into button cell, specific method is:Positive electrode, gathers partially at acetylene black Vinyl fluoride (PVDF) is according to 95:2.5:2.5 mass ratio is weighed, is uniformly mixed, NMP stirring 4h are added, and slurry is made, so After be coated uniformly on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm.In addition, being equipped with diameter For the lithium piece of 16mm as negative plate, it is electrolysis that 5 drop 1mol/L LiPFO4+DEC/EC (volume ratio 1) mixed solutions, which are added dropwise, in syringe Liquid, microporous polypropylene membrane are diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.
By the button cell after assembling, carry out volume test (3.0~4.3V, 0.1C/0.1C) and loop test (3.0~ 4.3V, 0.5C/0.5C).
Beneficial effects of the present invention:
Using the spherical nickelic manganese binary presoma of Co deposited synthesis, then coated by low temperature sintering doping, wet method, High temperature sintering renovation technique obtains good cycle, the high nickel lithium manganate cathode material of long storage.Specifically:
(1) the spherical nickelic manganese binary presoma of Co deposited synthesis is used, the cost of raw material of presoma is greatly reduced; To reduce the cost of finished product;
(2) third member Co is coated on substrate surface in the form of wet method, fabricated in situ, and clad is uniform, improves material Cycle, storage performance;
(3) in high-temperature sintering process, the cobalt phosphate of substrate surface is easy to form cobalt phosphate lithium, has fast-ionic conductor Performance improves capacity.In addition, the lithium phosphate generated can effectively prevent erosion of the electrolyte to positive electrode, to reduce height The generation of nickel lithium manganate cathode material particle/electrolyte interface side reaction, greatly improves following for high nickel lithium manganate cathode material Ring stability, and the voltage reduced in cyclic process decline drop.
Description of the drawings
Fig. 1:The preparation process flow of high nickel lithium manganate cathode material;
Fig. 2:The microstructure figure of high nickel lithium manganate cathode material;
Fig. 3:The gram volume of high nickel lithium manganate cathode material;
Fig. 4:The cycle figure of high nickel lithium manganate cathode material.
Specific implementation mode
Embodiment 1
According to nickel ion:Manganese ion molar ratio is 9:1 solution, preparing metal ion concentration summation are 1.5mol/L;Match NaOH solution concentration processed:8mol/L;Prepare ammonia spirit concentration:120g/L;By three kinds of solution respectively with 30ml/min, 10ml/ Min and 8ml/min is passed through in reaction kettle simultaneously, control ph 11.5, and temperature is 45 DEG C, successive reaction 20h, is passed through respectively old Change, wash, drying, obtaining the spherical binary persursor material Ni that D50 is 10um0.9Mn0.1(OH)2
Above-mentioned presoma is mixed with lithium hydroxide, zirconium oxide, wherein lithium:Metal ion molar ratio is 1:1, zirconium oxide The mass fraction that addition accounts for total material is that 5000ppmw is sintered under the conditions of oxygen rich air, and temperature is 750 DEG C, heat preservation 20h, after cooling, Hubei Province is broken, two pairs of rollers, obtains basis material after crushing.
0.03mol/L cobalt nitrates and 0.02mol/L ammonium hydrogen phosphate solution are prepared respectively, and two kinds of solvents are mixed, are stirred 1h is mixed, will produce pink precipitate in whipping process;Then, it is 1 according to solid-liquid mass ratio:10 are added basis material, continue to stir 2h is mixed, is filtered, dries, the basis material after being coated.
By the basis material after above-mentioned cladding, under Oxygen Condition, double sintering is carried out, temperature is 450 DEG C, keeps the temperature 20h, The high nickel lithium manganate cathode material of acquisition high power capacity, long storage.
The positive electrode of acquisition is subjected to battery assembling, specific method is:Positive electrode, acetylene black, Kynoar (PVDF) according to 95:2.5:2.5 mass ratio is weighed, is uniformly mixed, NMP stirring 4h are added, and slurry is made, then uniformly Coated on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm.In addition, being equipped with diameter 16mm's For lithium piece as negative plate, it is electrolyte that 5 drop 1mol/L LiPFO4+DEC/EC (volume ratio 1) mixed solutions, which are added dropwise, in syringe, is gathered Propylene microcellular film is diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.Gained battery is carried out to buckle electrical measurement Examination, by test, the use compacted density of the material:3.57g/cm3;Under the conditions of 3.0~4.3V, 0.1C, discharge capacity for the first time: 212mAh/g;Under the conditions of 3.0~4.3V, 0.5C/0.5C, capacity retention ratio is within 50 weeks:97%.
Embodiment 2
According to nickel ion:Manganese ion molar ratio is 8:2 solution, preparing metal ion concentration summation are 1.5mol/L;Match NaOH solution concentration processed:8mol/L;Prepare ammonia spirit concentration:120g/L;By three kinds of solution respectively with 25ml/min, 8ml/ Min and 8ml/min is passed through in reaction kettle simultaneously, control ph 11.2, and temperature is 50 DEG C, successive reaction 20h, is passed through respectively old Change, wash, drying, obtaining the spherical binary persursor material Ni that D50 is 10.5um0.8Mn0.2(OH)2
Above-mentioned presoma is mixed with lithium hydroxide, zirconium oxide, wherein lithium:Metal ion molar ratio is 1.05, zirconium oxide Addition account for total material mass fraction be 3000ppmw be sintered under the conditions of oxygen rich air, temperature be 800 DEG C, heat preservation 20h, after cooling, Hubei Province is broken, two pairs of rollers, obtains basis material after crushing.
0.45mol/L cobalt nitrates and 0.03mol/L ammonium hydrogen phosphate solution are prepared respectively, and two kinds of solvents are mixed, are stirred 1h is mixed, will produce pink precipitate in whipping process;Then, it is 1 according to solid-liquid mass ratio:10 are added basis material, continue to stir 2h is mixed, is filtered, dries, the basis material after being coated.
By the basis material after above-mentioned cladding, under Oxygen Condition, double sintering is carried out, temperature is 550 DEG C, keeps the temperature 20h, The high nickel lithium manganate cathode material of acquisition high power capacity, long storage.
The positive electrode of acquisition is subjected to battery assembling, specific method is:Positive electrode, acetylene black, Kynoar (PVDF) according to 95:2.5:2.5 mass ratio is weighed, is uniformly mixed, NMP stirring 4h are added, and slurry is made, then uniformly Coated on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm.In addition, being equipped with diameter 16mm's For lithium piece as negative plate, it is electrolyte that 5 drop 1mol/L LiPFO4+DEC/EC (volume ratio 1) mixed solutions, which are added dropwise, in syringe, is gathered Propylene microcellular film is diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.Gained battery is carried out to buckle electrical measurement Examination, by test, the use compacted density of the material:3.53g/cm3;Under the conditions of 3.0~4.3V, 0.1C, discharge capacity for the first time: 203mAh/g;Under the conditions of 3.0~4.3V, 0.5C/0.5C, capacity retention ratio is within 50 weeks:97.5%.
Embodiment 3
According to nickel ion:Manganese ion molar ratio is 7:3 solution, preparing metal ion concentration summation are 1.5mol/L;Match NaOH solution concentration processed:8mol/L;Prepare ammonia spirit concentration:120g/L;By three kinds of solution respectively with 30ml/min, 10ml/ Min and 8ml/min is passed through in reaction kettle simultaneously, and control pH value is 11.7, and temperature is 55 DEG C, successive reaction 20h, is passed through respectively old Change, wash, drying, obtaining the spherical binary persursor material Ni that D50 is 11um0.7Mn0.3(OH)2
Above-mentioned presoma is mixed with lithium hydroxide, zirconium oxide, wherein lithium:Metal ion molar ratio is 1.02, zirconium oxide Addition account for total material mass fraction be 1000ppmw be sintered under the conditions of oxygen rich air, temperature be 850 DEG C, heat preservation 20h, after cooling, Hubei Province is broken, two pairs of rollers, obtains basis material after crushing.
0.06mol/L cobalt nitrates and 0.04mol/L ammonium hydrogen phosphate solution are prepared respectively, and two kinds of solvents are mixed, are stirred 1h is mixed, will produce pink precipitate in whipping process;Then, it is 1 according to solid-liquid mass ratio:10 are added basis material, continue to stir 2h is mixed, is filtered, dries, the basis material after being coated.
By the basis material after above-mentioned cladding, under Oxygen Condition, double sintering is carried out, temperature is 650 DEG C, keeps the temperature 20h, The high nickel lithium manganate cathode material of acquisition high power capacity, long storage.
The positive electrode of acquisition is subjected to battery assembling, specific method is:Positive electrode, acetylene black, Kynoar (PVDF) according to 95:2.5:2.5 mass ratio is weighed, is uniformly mixed, NMP stirring 4h are added, and slurry is made, then uniformly Coated on aluminium foil, then 80 DEG C of vacuum bakeouts, tabletting, the positive plate for being cut into diameter 14mm.In addition, being equipped with diameter 16mm's For lithium piece as negative plate, it is electrolyte that 5 drop 1mol/L LiPFO4+DEC/EC (volume ratio 1) mixed solutions, which are added dropwise, in syringe, is gathered Propylene microcellular film is diaphragm, and the assembling of button cell is carried out in the glove box full of argon gas.Gained battery is carried out to buckle electrical measurement Examination, by test, the use compacted density of the material:3.55g/cm3;Under the conditions of 3.0~4.3V, 0.1C, discharge capacity for the first time: 195mAh/g;Under the conditions of 3.0~4.3V, 0.5C/0.5C, capacity retention ratio is within 50 weeks:98%.
The preparation method of high nickel lithium manganate cathode material of the present invention, using the spherical nickelic manganese of Co deposited synthesis two First presoma greatly reduces the cost of raw material of presoma, to reduce the cost of finished product;Third member Co is with wet method, original The form of position synthesis, is coated on substrate surface, clad is uniform, improves cycle, the storage performance of material;In high-temperature sintering process In, the cobalt phosphate of substrate surface is easy to form cobalt phosphate lithium, has the performance of fast-ionic conductor, improves capacity.In addition, generate Lithium phosphate can effectively prevent erosion of the electrolyte to positive electrode, to reduce high nickel lithium manganate cathode material particle/electrolysis The generation of liquid interface side reaction greatly improves the cyclical stability of high nickel lithium manganate cathode material, and reduces cyclic process In voltage decline drop.
The invention is not limited in specific implementation modes above-mentioned.The present invention, which expands to, any in the present specification to be disclosed New feature or any new combination, and disclose any new method or process the step of or any new combination.

Claims (6)

1. a kind of preparation method of nickelic lithium manganate cell positive electrode material, which is characterized in that include the following steps:
S1. soluble nickel salt, manganese salt, alkali metal hydroxide and ammonium hydroxide are stirred, it is coprecipitated carries out constant temperature in a kettle Reaction of forming sediment centrifuges, drying obtains spherical nickelic manganese binary presoma then by being separated by solid-liquid separation, being aged;
S2. lithium hydroxide, spherical nickelic manganese binary presoma, oxide addition are mixed, under the conditions of oxygen-enriched atmosphere, is carried out High temperature sintering obtains spherical high nickel ion doped binary positive material;
S3. soluble cobalt and phosphate are dissolved in deionized water, carry out mechanical agitation and is generated until there is light red to precipitate, Then high nickel ion doped binary positive material is added and continues stirring, filtering, drying, the nickelic lithium manganate cathode material after as coating Material;
S4. under the conditions of oxygen atmosphere, the positive electrode after cladding is subjected to low temperature sintering, obtains nickelic lithium manganate cathode material Material.
2. a kind of preparation method of nickelic lithium manganate cell positive electrode material according to claim 1, which is characterized in that described The molar ratio of soluble nickel ion and manganese ion described in step S1 is 1:1~10:1;Spherical nickelic manganese binary presoma is put down Equal grain size D50:8~12um.
3. a kind of preparation method of nickelic lithium manganate cell positive electrode material according to claim 1, which is characterized in that described The volumetric concentration of oxygen-enriched atmosphere described in step S2:50%~99%;The condition of the high temperature sintering:Temperature 500 DEG C~900 DEG C, 10~30h of soaking time.
4. according to a kind of preparation method of nickelic lithium manganate cell positive electrode material described in claim 1, which is characterized in that institute Stating soluble cobalt described in step S3 includes:At least one of cobalt nitrate, cobalt chloride and cobaltous sulfate;The phosphate packet It includes:At least one of ammonium hydrogen phosphate, potassium hydrogen phosphate, dibastic sodium phosphate, ammonium phosphate, sodium phosphate and potassium phosphate.
5. according to a kind of preparation method of nickelic lithium manganate cell positive electrode material described in claim 1, which is characterized in that institute State the volumetric concentration of oxygen atmosphere described in step S4:20%~99%;The low sintering condition:Temperature 300 DEG C~900 DEG C, 10~30h of soaking time.
6. according to a kind of preparation method of nickelic lithium manganate cell positive electrode material described in claim 1, which is characterized in that institute State the chemical formula of high nickel lithium manganate cathode material described in step S4:LiNixMnyO2·CozPO4, wherein:0.6 < x≤1,0.01 < y≤0.4,0.01 < z≤0.2, x+y+z=1.
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CN110767899A (en) * 2019-10-24 2020-02-07 厦门厦钨新能源材料有限公司 Preparation method of composite anode material of lithium ion battery
CN111430705A (en) * 2019-10-29 2020-07-17 蜂巢能源科技有限公司 Positive electrode material of lithium ion battery and preparation method thereof
CN111434618A (en) * 2020-01-17 2020-07-21 蜂巢能源科技有限公司 Cobalt-free layered positive electrode material, preparation method and lithium ion battery
CN111628147A (en) * 2020-04-25 2020-09-04 湖南鑫碳新材料有限公司 Composite lithium ion battery positive electrode material and preparation method thereof
CN112002905A (en) * 2020-08-26 2020-11-27 中南大学 Titanium lanthanum lithium phosphate modified cobalt-free cathode material and preparation method thereof
CN112768643A (en) * 2019-11-06 2021-05-07 湖南杉杉能源科技股份有限公司 Lithium ion battery anode composite material and preparation method thereof
CN114014382A (en) * 2021-10-29 2022-02-08 蜂巢能源科技有限公司 Method for preparing anode material by adopting supergravity sintering device, anode material and lithium ion battery
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