CN107658460A - A kind of preparation method of modified nickel-cobalt-manganese multi material - Google Patents

A kind of preparation method of modified nickel-cobalt-manganese multi material Download PDF

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CN107658460A
CN107658460A CN201710978130.6A CN201710978130A CN107658460A CN 107658460 A CN107658460 A CN 107658460A CN 201710978130 A CN201710978130 A CN 201710978130A CN 107658460 A CN107658460 A CN 107658460A
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cobalt
nickel
manganese
preparation
lithium
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高伟
安文雅
程冲
邱晓微
王海静
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Terry Chongqing New Energy Materials Co
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Terry Chongqing New Energy Materials Co
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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
    • H01M4/50—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

A kind of preparation method of modified nickel-cobalt-manganese multi material, its chemical formula are LiNixMnyCozMⅠ αO2（MⅡO）β, wherein x:y:z:α:β=(3~9):(1~3):(1~3):(0.001~0.05):(0.0002~0.001), MⅠFor Mg2+、Al3+、Ti4+、Nb5+The one or more of element compound；MⅡFor Al3+、Ti4+、Li3PO4、AlPO4、LiF、AlF3In one or more elements or compound, the present invention in do not use complexing agent, reduce environmental pollution；Ball milling spray art one, the techniques such as coprecipitation reaction, bulk phase-doped, lithium salts mixing and Surface coating are effectively combined, processing step is shortened, reduces equipment investment and loss of material, improve economic benefit；Bulk phase-doped and surface cladding tech is carried out under liquid-phase condition, and uniformity is higher.

Description

A kind of preparation method of modified nickel-cobalt-manganese multi material
Technical field
The present invention relates to technical field of lithium ion, a kind of preparation side of modified nickel-cobalt-manganese multi material of specific design Method.
Background technology
Lithium ion battery is since nineteen ninety comes out, and because it has, voltage is high, energy density is big, service life is long, nothing The advantages that memory effect and wide operating temperature range, rapid popularization, it is widely used to mobile phone, MP3, UPS, camera, notes In the portable equipments such as this computer.High power capacity, high-power lithium ion battery are on electric tool, electric bicycle, electric automobile Deng application it is at the early-stage, application prospect is good.
Positive electrode is the important component for determining performance of lithium ion battery, and nickel-cobalt lithium manganate cathode material is institute's accounting Example is heavier, and nickel-cobalt lithium manganate cathode material method of modifying is then used to be lifted the structural stability of material and reduces material surface With the side reaction of electrolyte, security performance, storge quality and long circulation life of battery core etc. are lifted.
Nickel-cobalt lithium manganate cathode material method of modifying mainly includes bulk phase-doped and surface compound and coats two kinds.Usual bar Under part, it is bulk phase-doped it is middle synthesis presoma be metallic element is embedded in by way of co-precipitation intracell or presoma with Metallic compound is carried out physical mixed by lithium compound mix stages together, and the former implant uniformity is high, but is co-precipitated control strip Part is harsher, and technical difficulty is high；The latter's mixing is simple, but the uniformity is poor under the conditions of physical mixed.And Surface coating then passes through Chemical deposition reaction occurs in surface of material or physical mixed is attached to material surface, then surface is obtained by double sintering and is modified Positive electrode, the former uniformity is preferable but technique is relative complex, and the latter is simple to operate but mixture homogeneity is poor.
The lithium ion battery that doping as described in number of patent application CN201410038234.5 is modified altogether with Surface coating is just Pole material and its preparation method, it is to first pass through lithium source, cobalt, additive mixed sintering, again in oxide on surface phosphate after crushing Cladding；For another example the alumina-coated described in number of patent application CN201310020961.4 is modified the system of lithium nickel cobalt manganese oxygen positive electrode Preparation Method, it is that first synthesis obtains nickel cobalt manganese hydroxide precursor, adds water-soluble aluminum salt and form hydrogen-oxygen on presoma surface Change al deposition, then dry, low-temperature sintering obtains alumina-coated nickel cobalt manganese presoma, mixed carbonic acid lithium sintering, broken obtain oxygen Change aluminium cladding nickel-cobalt lithium manganate material；The shortcomings that mixture homogeneity difference be present in two methods.
In addition, in whole nickel-cobalt lithium manganate cathode material production process, the complexing agent that uses, alkali lye etc. have corrosion Property, pollution environment also increases production cost.
In summary, existing nickel-cobalt lithium manganate cathode material method of modifying exists because of operating procedure and the reason of method The deficiency that complex process, technical difficulty are high, mixture homogeneity is poor, and the use of complexing agent, alkali lye, adds production cost Also pollute environment simultaneously.
The content of the invention
It is an object of the invention to provide a kind of preparation method of modified nickel-cobalt-manganese multi material, it not only shortens technique Step, and it is uniform to be effectively ensured bulk phase-doped and Surface coating Elemental redistribution, can also can also be saved while environmental protection About cost.
The purpose of the present invention realized by such technical scheme, a kind of preparation side of modified nickel-cobalt-manganese multi material Method, the chemical formula of the modification nickel-cobalt-manganese multi material of preparation is LiNixMnyCozMⅠ αO2（MⅡO）β, wherein x:y:z:α:β=(3~ 9):(1~3):(1~3):(0.001~0.05):(0.0002~0.001), wherein MⅠFor Mg2+、Al3+、Ti4+、Nb5+Deng element The one or more of compound；MⅡFor Al3+、Ti4+、Li3PO4、AlPO4、LiF、AlF3In one or more elements or chemical combination Thing；Comprise the following steps：
S1, by nickel salt, cobalt salt, manganese salt, MⅠ1.5~3.0mol/L metal salt solution A is configured to, separately prepares 2~10mol/L gold Belong to aqueous slkali B or lithium metal compound；
S2, two kinds of solution of A/B are pumped into reactor respectively by peristaltic pump, make A/B molten under 150~400rpm stir speed (S.S.)s Liquid disperses and carries out reaction to form slurry, and control course of reaction pH is 10.0~11.5,45~60 DEG C of temperature；
S3, mashing pump is entered into 2~10h of processing in ball mill；
S4, slurry is subjected to spray drying granulation, obtains spheroidization NixMnyCozMⅠ α(OH)2Presoma；
S5, by MⅡElement compound and lithium source are added in deionized water, and constantly grinding obtains suspended slurry under ball action；
S6, by spheroidization NixMnyCozMⅠ α(OH)2Presoma, which adds, stirs 0.5~2h in suspended slurry, in centrifugal spray condition Under obtain mixed lithium and Surface coating MⅡThe Ni of element compoundxMnyCozMⅠ α(OH)2Dried object；
S7, above-mentioned dried object sinter 8~20h at 700~1000 DEG C, you can LiNixMnyCozM is preparedⅠαO2（MⅡO）β is just Pole material.
Further, S4, S5, S6 and S7 step can be：
S4, by soluble MⅡElement compounds, which are dissolved in deionized water, obtains settled solution；
S5, by MⅡElement Solution adds step（4）In slurry, M is obtainedⅡHydroxide deposition and pulp particle surface；
S6, slurry is subjected to spray drying granulation, obtains MⅡHydroxide cladding spheroidization mixes lithium NixMnyCozMⅠα(OH)2Before Drive body；
S7, above-mentioned presoma sinter 8~20h at 700~1000 DEG C, you can LiNi is preparedxMnyCozMⅠ αO2（MⅡO）βPositive pole Material.
Further, nickel salt is at least one of nickel sulfate, nickel chloride or nickel nitrate in S1；Cobalt salt is cobaltous sulfate, chlorine Change at least one of cobalt or cobalt nitrate；Manganese salt is at least one of manganese sulfate, manganese chloride or manganese nitrate.
Further, lithium metal compound is at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate in S5.
Further, mashing pump is entered in S3 and 4h is handled in ball mill.
Further, 150~400rpm of stir speed (S.S.) of slurry is formed in S2.
Further, pH is 10.6 ± 0.2 in S2,52 DEG C of temperature.
Further, spray drying obtains the mixed polynary presoma of lithium and sinters 12h at 900 DEG C in S7.
Further, 2h can be first sintered in S7 at 600 DEG C, then is warming up to 900 DEG C of sintering 12h.
By adopting the above-described technical solution, the present invention has the advantage that：Not only shorten processing step, Er Qieyou Effect ensures that bulk phase-doped and Surface coating Elemental redistribution is uniform, can also be also cost-saved while environmental protection.
Brief description of the drawings
Fig. 1 prepares a kind of SEM schematic diagrames of precursor of lithium ionic cell positive material.
Fig. 2 prepares a kind of SEM schematic diagrames of anode material for lithium-ion batteries.
Fig. 3 prepares a kind of TEM schematic diagrames of anode material for lithium-ion batteries.
Embodiment
Under the invention will be further described in conjunction with the accompanying drawings and embodiments.
Embodiment 1
S1, nickel sulfate 130.00Kg, cobaltous sulfate 53.65Kg, manganese sulfate 32.50Kg and its magnesium sulfate 1.80Kg are pressed into Ni:Mn: Co:Mg mol ratios are 6.0:2.0:1.9:0.1 is configured to 2mol/L metal salt solution A, another to prepare 2mol/L concentration hydroxides Sodium solution B；
S2, two kinds of solution of A/B are pumped into reactor respectively by peristaltic pump, disperse A/B solution under 200rpm stir speed (S.S.)s And carry out reaction and form slurry, control course of reaction pH is 10.2 ± 0.2, temperature 45 C；
S3, mashing pump is entered 2h is handled in ball mill；
S4, slurry is subjected to spray drying granulation, obtains spheroidization Ni0.6Mn0.2Co0.19Mg0.01(OH)2Presoma；
S5, a nanometer Al will be weighed2O325.0g and lithium carbonate 8.43Kg is added in deionized water, is constantly ground under ball action Obtain suspended slurry；
S6, weigh 20Kg spheroidizations Ni0.6Mn0.19Co0.2Mg0.01(OH)2Presoma adds in suspended slurry and stirs 0.5h, from Mixed lithium carbonate and nanometer Al are obtained under heart spray condition2O3Surface coating Ni0.6Mn0.19Co0.2Mg0.01(OH)2Dried object；
S7, above-mentioned dried object sinter 2h at 600 DEG C, then are warming up to 700 DEG C of sintering 20h, and material is broken to can obtain Al2O3Bag Cover LiNi0.6Mn0.19Co0.2Mg0.01O2Positive electrode.
After testing, the nickel-cobalt lithium manganate material average grain diameter that prepared by the present embodiment is 11.62 μm, tap density 2.57g/ cm³.Battery testing is assembled into, material processing characteristics is excellent, and 4.2-3.0V1C gram volumes are 168mAh/g, 2000 circulation volumes Conservation rate is 86.0%, battery good thermal stability.
Example 2
S1, nickel sulfate 130.00Kg, cobaltous sulfate 53.65Kg, manganese sulfate 32.50Kg and its magnesium sulfate 1.80Kg are pressed into Ni:Mn: Co:Mg mol ratios are 6.0:2.0:1.9:0.1 is configured to 2mol/L metal salt solution A；
S2, lithium carbonate 38.14Kg is slowly added to be reacted in solution A under 200rpm stir speed (S.S.)s, under stirring Disperse A/B solution and carry out reaction to form slurry, control course of reaction pH is 10.6 ± 0.2, temperature 60 C；
S3, mashing pump is entered 10h is handled in ball mill；
S4, weighs 800g solubility aluminum nitrates and is dissolved in deionized water and obtain settled solution；
S5, aluminum nitrate solution is added into step（3）In slurry, continue ball milling 1h and obtain Al (OH)3It is deposited on pulp particle surface；
S6, slurry is subjected to centrifugal spray drying granulation, obtains Al (OH)3Coat spherical Ni0.6Mn0.2Co0.19Mg0.01(OH)2It is mixed Lithium presoma；
S7, above-mentioned presoma sinter 2h at 600 DEG C, then are warming up to 1000 DEG C of sintering 8h, and material is broken to can obtain Al2O3Bag Cover LiNi0.6Mn0.19Co0.2Mg0.01O2Positive electrode.
After testing, the nickel-cobalt lithium manganate material average grain diameter that prepared by the present embodiment is 11.30 μm, tap density 2.45g/ cm³.Battery testing is assembled into, material processing characteristics is excellent, and 4.2-3.0V1C gram volumes are 167mAh/g, 2000 circulation volumes Conservation rate is 86.0%, battery good thermal stability.
Embodiment 3
S1, nickel sulfate 130.00Kg, cobaltous sulfate 53.65Kg, manganese sulfate 32.50Kg and its magnesium sulfate 1.80Kg are pressed into Ni:Mn: Co:Mg mol ratios are 6.0:2.0:1.9:0.1 is configured to 2mol/L metal salt solution A, another to prepare 2mol/L concentration hydroxides Sodium solution B；
S2, two kinds of solution of A/B are pumped into reactor respectively by peristaltic pump, disperse A/B solution under 200rpm stir speed (S.S.)s And carry out reaction and form slurry, control course of reaction pH is 11.3 ± 0.2,52 DEG C of temperature；
S3, mashing pump is entered 4h is handled in ball mill；
S4, slurry is subjected to spray drying granulation, obtains spheroidization Ni0.6Mn0.2Co0.19Mg0.01(OH)2Presoma；
S5, a nanometer Al will be weighed2O325.0g and lithium carbonate 8.43Kg is added in deionized water, is constantly ground under ball action Obtain suspended slurry；
S6, weigh 20Kg spheroidizations Ni0.6Mn0.19Co0.2Mg0.01(OH)2Presoma adds in suspended slurry and stirs 2h, is centrifuging Mixed lithium carbonate and nanometer Al are obtained under spray condition2O3Surface coating Ni0.6Mn0.19Co0.2Mg0.01(OH)2Dried object；
S7, above-mentioned dried object sinter 2h at 600 DEG C, then are warming up to 900 DEG C of sintering 12h, and material is broken to can obtain Al2O3Bag Cover LiNi0.6Mn0.19Co0.2Mg0.01O2Positive electrode.
After testing, the nickel-cobalt lithium manganate material average grain diameter that prepared by the present embodiment is 11.50 μm, tap density 2.50g/ cm³.Battery testing is assembled into, material processing characteristics is excellent, and 4.2-3.0V1C gram volumes are 165mAh/g, 2000 circulation volumes Conservation rate is 85.0%, battery good thermal stability.
Embodiment 4
S1, nickel sulfate 130.00Kg, cobaltous sulfate 53.65Kg, manganese sulfate 32.50Kg and its magnesium sulfate 1.80Kg are pressed into Ni:Mn: Co:Mg mol ratios are 6.0:2.0:1.9:0.1 is configured to 2mol/L metal salt solution A；
S2, lithium carbonate 38.14Kg is slowly added to be reacted in solution A under 200rpm stir speed (S.S.)s, under stirring Disperse A/B solution and carry out reaction to form slurry, control course of reaction pH is 10.2 ± 0.2, temperature 45 C；
S3, mashing pump is entered 6h is handled in ball mill；
S4, weighs 800g solubility aluminum nitrates and is dissolved in deionized water and obtain settled solution；
S5, aluminum nitrate solution is added into step（3）In slurry, continue ball milling 1h and obtain Al (OH)3It is deposited on pulp particle surface；
S6, slurry is subjected to centrifugal spray drying granulation, obtains Al (OH)3Coat spherical Ni0.6Mn0.2Co0.19Mg0.01(OH)2It is mixed Lithium presoma；
S7, above-mentioned presoma sinter 2h at 600 DEG C, then are warming up to 900 DEG C of sintering 10h, and material is broken to can obtain Al2O3Bag Cover LiNi0.6Mn0.19Co0.2Mg0.01O2Positive electrode.
After testing, the nickel-cobalt lithium manganate material average grain diameter that prepared by the present embodiment is 11.30 μm, tap density 2.45g/ cm³.Battery testing is assembled into, material processing characteristics is excellent, and 4.2-3.0V1C gram volumes are 167mAh/g, 2000 circulation volumes Conservation rate is 86.0%, battery good thermal stability.
Course of reaction pH is controlled from above example combination blank example, in S2 10.0~11.5, temperature 45 ~60 DEG C；Slurry is pumped into sand mill in S3 and carries out 2~10h of nanosizing ball-milling treatment；In S7 8 are sintered at 700~1000 DEG C ~20h；These parameters are all parameters and step important in the present invention.
In the present invention, complexing agent is not used as using ammoniacal liquor etc., reduces the pollution to environment；Ball milling-spray art one, The techniques such as coprecipitation reaction, bulk phase-doped, lithium salts mixing and Surface coating are effectively combined, not only shorten processing step, and And the equipment investment and loss of material of middle process section are reduced, improve economic benefit；Bulk phase-doped and surface cladding tech is equal Carried out under liquid-phase condition, ensure that uniformity is higher.

Claims (9)

1. a kind of preparation method of modified nickel-cobalt-manganese multi material, it is characterised in that the modification nickel-cobalt-manganese multi material of preparation Chemical formula is LiNixMnyCozMⅠ αO2（MⅡO）β, wherein x:y:z:α:β=(3~9)：(1~3)：(1~3)：(0.001~ 0.05) ：(0.0002~0.001), wherein MⅠFor Mg2+、Al3+、Ti4+、Nb5+The one or more of element compound；MⅡFor Al3 +、Ti4+、Li3PO4、AlPO4、LiF、AlF3In one or more elements or compound；Comprise the following steps：
S1, by nickel salt, cobalt salt, manganese salt, MⅠ1.5~3.0mol/L metal salt solution A is configured to, separately prepares 2~10mol/L gold Belong to aqueous slkali B or lithium metal compound；
S2, two kinds of solution of A/B are pumped into reactor respectively by peristaltic pump, make A/B molten under 150~400rpm stir speed (S.S.)s Liquid disperses and carries out reaction to form slurry, and control course of reaction pH is 10.0~11.5,45~60 DEG C of temperature；
S3, mashing pump is entered into 2~10h of processing in ball mill；
S4, slurry is subjected to spray drying granulation, obtains spheroidization NixMnyCozMⅠ α(OH)2Presoma；
S5, by MⅡElement compound and lithium source are added in deionized water, and constantly grinding obtains suspended slurry under ball action；
S6, by spheroidization NixMnyCozMⅠ α(OH)2Presoma, which adds, stirs 0.5~2h in suspended slurry, in centrifugal spray condition Under obtain mixed lithium and Surface coating MⅡThe Ni of element compoundxMnyCozMⅠ α(OH)2Dried object；
S7, above-mentioned dried object sinter 8~20h at 700~1000 DEG C, you can LiNi is preparedxMnyCozMⅠ αO2（MⅡO）βPositive pole Material.
2. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that S4, S5, S6 and S7 Step can be：
S4, by soluble MⅡElement compounds, which are dissolved in deionized water, obtains settled solution；
S5, by MⅡElement Solution adds step（4）In slurry, M is obtainedⅡHydroxide deposition and pulp particle surface；
S6, slurry is subjected to spray drying granulation, obtains MⅡHydroxide cladding spheroidization mixes lithium NixMnyCozMⅠ α(OH)2Before Drive body；
S7, above-mentioned presoma sinter 8~20h at 700~1000 DEG C, you can LiNi is preparedxMnyCozMⅠ αO2（MⅡO）βPositive pole Material.
3. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that nickel salt is sulphur in S1 At least one of sour nickel, nickel chloride or nickel nitrate；Cobalt salt is at least one of cobaltous sulfate, cobalt chloride or cobalt nitrate；Manganese salt For at least one of manganese sulfate, manganese chloride or manganese nitrate.
4. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that metal lithiumation in S5 Compound is at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate.
5. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that by mashing pump in S3 Enter processing 4h in ball mill.
6. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that slurry is formed in S2 150~400rpm of stir speed (S.S.).
7. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that pH is 10.6 in S2 ± 0.2,52 DEG C of temperature.
8. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that be spray-dried in S7 Obtain the mixed polynary presoma of lithium and sinter 12h at 900 DEG C.
9. the preparation method of modified nickel-cobalt-manganese multi material according to claim 1, it is characterised in that can first exist in S7 2h is sintered at 600 DEG C, then is warming up to 900 DEG C of sintering 12h.
CN201710978130.6A 2017-10-18 2017-10-18 A kind of preparation method of modified nickel-cobalt-manganese multi material Pending CN107658460A (en)

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CN108529687A (en) * 2018-04-25 2018-09-14 北方奥钛纳米技术有限公司 A kind of preparation method of hydroxide nickel cobalt manganese
CN108545786A (en) * 2018-03-22 2018-09-18 杭州金马新能源科技有限公司 A kind of preparation method of high-energy nickel cobalt manganese compound lithium ion positive electrode
CN109786697A (en) * 2018-12-29 2019-05-21 合肥融捷能源材料有限公司 A kind of high voltage nickel-cobalt lithium manganate cathode material and preparation method thereof
CN109904425A (en) * 2019-02-28 2019-06-18 湖北锂诺新能源科技有限公司 A kind of miscellaneous lithium-rich manganese-based composite material of cation-anion co-doping and preparation method
CN111162271A (en) * 2019-06-12 2020-05-15 北京当升材料科技股份有限公司 Multi-element anode material, preparation method thereof and lithium ion battery
CN111384382A (en) * 2020-03-25 2020-07-07 四川大学 Doping and coating dual-regulation nickel-based multi-element positive electrode material and preparation method thereof
CN112635735A (en) * 2020-12-21 2021-04-09 惠州亿纬锂能股份有限公司 Nickel-cobalt lithium manganate precursor with coating structure, preparation method and application thereof
CN113292112A (en) * 2021-05-21 2021-08-24 上海大学 Preparation method of high-nickel ternary positive electrode precursor

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