CN103633312A - Surface modified anode material for lithium ion battery and method - Google Patents
Surface modified anode material for lithium ion battery and method Download PDFInfo
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- CN103633312A CN103633312A CN201210306244.3A CN201210306244A CN103633312A CN 103633312 A CN103633312 A CN 103633312A CN 201210306244 A CN201210306244 A CN 201210306244A CN 103633312 A CN103633312 A CN 103633312A
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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
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- 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
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- 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 surface modified anode material for a lithium ion battery and a method. The anode material and the method are characterized in that: LiNi[x]Co[y]MzO2 (M = Mn, Al or Mg), LiMn2O4 or a composite anode material thereof, a metal salt and a carbon source material are added into a solvent to form a flowable slurry; and the pH value is adjusted under stirring so that metal compounds and the carbon source material form sol and are adsorbed on the surface of the anode material. After being dried, the mixture is subjected to high-temperature thermal treatment to obtain the anode material compositely coated with the metal compounds and the carbon, wherein the metal compounds are metal oxides, metal fluorides or metal phosphates, and the like. That large-current charge and discharge performances of anode materials are influenced by the low electronic conductivity of metal compound coatings at present can be overcome by the coating method provided by the invention, thus enhancing application performances in electric tools, electric automobiles, and other occasions.
Description
Technical field
The present invention relates to a kind of anode material for lithium ion battery through surface modification and method, relate in particular to a kind of anode material for lithium-ion batteries and the method for metallic compound and the modification of carbon compound coating.
Background technology
Energy density is high, power density is high because having for lithium ion battery, have extended cycle life and pollution-free, the advantage such as self-discharge rate is low, has occupied the market of portable type electronic product, in fields such as electric tool, electric automobiles, has good development potentiality.
The core of lithium ion battery is positive and negative electrode storage lithium active material, and wherein positive electrode active materials is as Li in lithium ion battery
+source, be the basis of energy content of battery density, be also the key factor that restriction battery performance promotes.In lithium ion battery, positive electrode is shelved in process in charging and open circuit, the interface of itself and electrolyte is unsettled on thermodynamics, solvent in electrolyte has the oxidized formation trend of stable material more, the metal ion in positive electrode also can stripping in electrolyte.Therefore, lithium ion battery is in circulation or storage process, and the product that anodal surface constantly accumulates side reaction is as LiF and Li
2cO
3deng, the metal ion transport of stripping is to negative pole and be deposited on surface, promotes the growth of SEI film, and this has not only consumed active lithium, and causes electrode surface impedance to increase, and causes the obvious decay of power characteristic, useful life and security performance.Therefore, when anode material for lithium-ion batteries is applied to electrokinetic cell, also need it to carry out modification, to improve the compatibility of itself and electrolyte.Surface modification is to improve one of effective method of positive electrode performance; can directly intercept contacting of positive electrode and electrolyte; suppress side reaction and the corrosion of electrolyte to material between itself and electrolyte; make the integrality of material crystals structure obtain more lasting protection; thereby effectively improve chemistry and the structural stability of material and electrolyte interface, extend the useful life of battery and strengthen security performance.Existing surface modifying method is normally at the coated layer of metal compound in positive electrode surface, as Al
2o
3, MgO, ZrO
2, Co
3(PO
4)
2, AlPO
4and AlF
3deng, although can effectively improve cycle performance and the thermal stability of positive electrode, due to the low electronic conductivity of coating layer self, can affect the high rate during charging-discharging performance of coated rear positive electrode.Thereby be guided out the application's design, imagine surperficial modification and meet coated by metallic compound and carbon.
Summary of the invention
The object of the present invention is to provide a kind of anode material for lithium-ion batteries through surface modification and method, overcome the deficiencies in the prior art.
The technical scheme that the present invention takes is:
A surface modification for anode material for lithium-ion batteries, is characterized in that described positive electrode is LiNi
xco
ym
zo
2, LiMn
2o
4or compound, x+y+z=1 in formula, 0≤x≤1, y, z≤1, M is Mn, Al or Mg, the surface modification described in it is characterized in that is implemented in lithium ion cell positive by metallic compound and material with carbon element compound coating, the mass percent of metallic compound and positive electrode is 0.1-10%, and the mass ratio of material with carbon element and positive electrode is 0.1-5%.Method of modifying is that anode material for lithium-ion batteries metallizing thing, carbon source material are joined together in solvent and form the slurry that can flow, and under agitation regulates pH value to make metallic compound form colloidal sol together with carbon source and is adsorbed on positive electrode surface.After this mixture is dried, again through high-temperature heat treatment, obtain the positive electrode of the surface modification of metallic compound and carbon compound coating, its concrete steps are as follows:
(1) surface of positive electrode is coated
Anode material for lithium-ion batteries, metallic compound are joined and in solvent, form flowable slurry together with carbon source material.Anode material for lithium-ion batteries is LiNi
xco
ym
zo
2(x+y+z=1,0≤x, y, z≤1, M=Mn, Al or Mg), LiMn
2o
4or its composite positive pole.Metallic compound comprises a kind of in oxide, fluoride, phosphate, nitrate, acetate, organic alkoxide or the organic ester salt of metal, and wherein metal is a kind of in Al, Mg, Zn, Ti, Zr, Bi, La or Ce.Carbon source material is one or more in carbon black, CNT (carbon nano-tube), carbon nano-fiber, Graphene or Organic Compounds.Solvent is one or more in organic alcohols, organic ethers or water.
Slurry under agitation regulates pH value to make metallic compound form colloidal sol together with carbon source and is adsorbed on positive electrode surface.
(2) heat treatment of positive electrode
After said mixture is dried at 50-200 ℃, through the high-temperature heat treatment of 300-600 ℃, the time is 0.5-6 hour, makes at high temperature by mutual ion, to spread between surface coating layer and positive electrode matrix, improve the adhesion between coating layer and matrix, and reduce two-layer between Li
+diffusional resistance.The covering amount of metallic compound is controlled at the 0.1-10wt% of positive electrode, and material with carbon element covering amount is controlled at the 0.1-5wt% of positive electrode.
The present invention compared with the existing methods, has the following advantages:
(1) raw material easily obtain.Coated process simply, is easily controlled, and can obtain more uniform coating layer.
(2) positive electrode that the present invention makes has comparatively excellent cycle performance, fail safe and power-performance, overcome the coated shortcoming that causes that positive electrode high rate during charging-discharging reduces of existing metallic compound, improved it at the application performance of the occasions such as electric tool, electric automobile.(referring to embodiment)
Accompanying drawing explanation
Fig. 1: embodiment of the present invention 1LiNi
1/3co
1/3mn
1/3o
2material SEM photo, wherein left figure (a) is for before coated, and right figure (b) is for after coated;
Fig. 2: embodiment of the present invention 1LiNi
1/3co
1/3mn
1/3o
2the 18650 type batteries that material is made are at 55 ℃, the cyclic curve under 1C;
Fig. 3: embodiment of the present invention 1LiNi
1/3co
1/3mn
1/3o
23C, the 5V overcharge test curve of the 18650 type batteries that material is made;
Fig. 4: the embodiment of the present invention 1 and comparative example LiNi
1/3co
1/3mn
1/3o
2the ac impedance spectroscopy of/Li half-cell, wherein A is for before coated, and B is embodiment 1, and C is comparative example 1.
Embodiment
Below in conjunction with specific embodiment, the surface modifying method of anode material for lithium-ion batteries of the present invention is described further.
Embodiment 1: 4g aluminium isopropoxide is dissolved in 400mL isopropyl alcohol, under agitation adds 2.7g citric acid and 100gLiNi
1/3co
1/3mn
1/3o
2, continue stirring reaction 4h and aluminium isopropoxide be fully hydrolyzed and regulate pH value to form colloidal sol to be adsorbed onto LiNi
1/3co
1/3mn
1/3o
2particle surface.Then be warmed up to 80 ℃, evaporate to dryness under agitation, then material is placed in to sintering furnace at 300 ℃, is incubated 5h, heating rate is 5 ℃/min, with obtaining the LiNi of 1wt% aluminium oxide and 1wt% carbon compound coating after cooling rear mistake 400 mesh sieves of stove
1/3co
1/3mn
1/3o
2material.
Comparative example 1: 4g aluminium isopropoxide is dissolved in 400mL isopropyl alcohol, under agitation adds 100gLiNi
1/3co
1/3mn
1/3o
2, continuation stirring reaction 4h makes aluminium isopropoxide fully be hydrolyzed formation colloidal sol and is adsorbed onto LiNi
1/3co
1/3mn
1/3o
2particle surface.Then be warmed up to 80 ℃, evaporate to dryness under agitation, then material is placed in to sintering furnace at 300 ℃, is incubated 5h, heating rate is 5 ℃/min, with obtaining the LiNi of 1wt% alumina-coated after cooling rear mistake 400 mesh sieves of stove
1/3co
1/3mn
1/3o
2material.
From the contrast SEM photo of Fig. 1, can find out the LiNi after being coated
1/3co
1/3mn
1/3o
2material granule has formed even, fine and close coating layer on original smooth surface.Fig. 2 shows, coated front and back LiNi
1/3co
1/3mn
1/3o
2the 18650 type batteries that material is made are at 55 ℃, and the capability retention that 1C circulates after 400 times is respectively 80% and 92%, and the cycle performance of coated rear material is significantly improved.LiNi
1/3co
1/3mn
1/3o
2after battery 1C circulation that material is made 100 times, in 3C, 5V overcharge test, there is thermal runaway, and LiNi after coated
1/3co
1/3mn
1/3o
2there is not thermal runaway in the battery that material is made, maximum temperature only has 43 ℃, as shown in Figure 3; From Fig. 4, can find out the LiNi of simple alumina-coated
1/3co
1/3mn
1/3o
2the impedance ratio of electrode has increased before being coated, and adopts the LiNi of aluminium oxide and carbon compound coating
1/3co
1/3mn
1/3o
2before the impedance ratio of electrode is coated, reduced, electronic conductivity is low causes impedance to increase due to self to show can to overcome existing metallic compound coating layer by method for coating of the present invention, thereby affects the high rate during charging-discharging of positive electrode.
Embodiment 2: 14.6g magnesium nitrate and 5.0g diammonium hydrogen phosphate are dissolved in 50mL deionized water, under agitation form gradually magnesium phosphate colloidal sol, then add 2g CNT (carbon nano-tube) and regulate pH value to form colloidal sol to be adsorbed on 100gLiMn
2o
4material surface.Continue to stir after 2h and transfer in 150 ℃ of baking ovens and dry, after sieving after then processing 0.5h at 600 ℃, obtain the LiMn that magnesium phosphate and carbon nano-tube covering amount are respectively 5wt% and 2wt%
2o
4material.
Embodiment 3: by LiCoO
2be scattered in ethanol and deionized water mixed solvent, wherein the volume ratio of second alcohol and water is 1:1.Then under agitation add superconduction carbon black and polyvinylpyrrolidone, then drip inward the aqueous solution of ammonium fluoride, reaction 1h by 100 ℃ of oven dry after at 500 ℃ heat treatment 3h, obtain the LiCoO of lanthanum fluoride and carbon compound coating
2material.All the other are with embodiment 1.
Claims (5)
1. through an anode material for lithium-ion batteries for surface modification, described positive electrode is LiNi
xco
ym
zo
2, LiMn
2o
4(or compound, x+y+z=1 in formula, 0≤x≤1, y, z≤1, M is Mn, Al or Mg, the surface modification described in it is characterized in that is implemented in lithium ion cell positive by metallic compound and material with carbon element compound coating, the mass percent of metallic compound and positive electrode is 0.1-10%, and the mass percent of material with carbon element and positive electrode is 0.1-5%.
2. by claimed in claim 1 through surface modification positive electrode, it is characterized in that:
1. described metallic compound is metal oxide, fluoride, phosphate, nitrate, acetate, organic alkoxide or organic ester salt; Wherein metal is a kind of in Al, Mg, Zn, Ti, Zr, Bi, La or Ce;
2. described material with carbon element is one or more in carbon black, carbon nano-tube, carbon nano-fiber, Graphene or organic carbon compound.
3. by the positive electrode through surface modification claimed in claim 1, it is characterized in that:
1. the superpacket coating that the material with carbon element that described surface modification is 1% even, fine and close aluminium oxide and 1% by mass percent forms;
2. the superpacket coating that the carbon nano-tube that described surface modification is 5% magnesium phosphate and 2% by mass percent forms.
4. through a method for the anode material for lithium-ion batteries of surface modification, it is characterized in that concrete steps are:
(1) surface of positive electrode is coated
Anode material for lithium-ion batteries, slaine are joined in solvent and form flowable slurry together with carbon source material, and anode material for lithium-ion batteries is LiNi
xco
ym
zo
2, in formula, x+y+z=1,0≤x, y, z≤1, M=Mn, Al or Mg, LiMn
2o
4or its composite positive pole; Metallic compound comprises a kind of in oxide, fluoride, nitrate, phosphate, acetate, organic alkoxide or the organic ester salt of metal; Wherein metal is a kind of in Al, Mg, Zn, Ti, Zr, Bi, La or Ce; Carbon source material is one or more in carbon black, CNT (carbon nano-tube), carbon nano-fiber, Graphene or Organic Compounds; Solvent is one or more in organic alcohols, organic ethers or water;
Slurry under agitation regulates pH value to make metallic compound form colloidal sol together with carbon source and is adsorbed on positive electrode surface;
(2) heat treatment of positive electrode
After said mixture is dried at 50-200 ℃, through the high-temperature heat treatment of 300-600 ℃, make at high temperature by mutual ion, to spread between surface coating layer and positive electrode matrix, improve the adhesion between coating layer and matrix, and reduce two-layer between Li
+diffusional resistance.
5. by method claimed in claim 4, it is characterized in that after the oven dry described in step 2 that the high-temperature heat treatment time is 0.5-6 hour.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855384A (en) * | 2014-03-25 | 2014-06-11 | 海宁美达瑞新材料科技有限公司 | Rare-earth doping modified lithium ion battery ternary positive electrode material and preparation method thereof |
| CN103972499A (en) * | 2014-05-16 | 2014-08-06 | 海宁美达瑞新材料科技有限公司 | Modified nickel-cobalt lithium aluminate positive electrode material and preparation method thereof |
| CN103996832A (en) * | 2014-05-16 | 2014-08-20 | 合肥工业大学 | Carbon-metal oxide two-component cladding modified high-voltage positive material and cladding method |
| CN104332630A (en) * | 2014-10-22 | 2015-02-04 | 深圳市贝特瑞新能源材料股份有限公司 | Surface coated graphite cathode material, preparation method of surface coated graphite cathode material, as well as lithium ion battery containing surface coated graphite cathode material |
| CN104600290A (en) * | 2014-12-30 | 2015-05-06 | 深圳市贝特瑞新能源材料股份有限公司 | Nickel-cobalt lithium aluminate composite positive electrode material and preparation method thereof |
| CN105226287A (en) * | 2014-06-26 | 2016-01-06 | 中兴通讯股份有限公司 | Anode material for lithium-ion batteries and preparation method thereof |
| WO2016029856A1 (en) * | 2014-08-27 | 2016-03-03 | Nivo Systems, Inc. | Lithium metal oxide composites, and methods for preparing and using thereof |
| CN105958021A (en) * | 2016-05-27 | 2016-09-21 | 天津泰和九思科技有限公司 | Lithium titanate composite material and preparation method thereof and lithium-ion battery |
| CN106058203A (en) * | 2016-07-31 | 2016-10-26 | 湖南桑顿新能源有限公司 | Preparation method of double-covering lithium-enriched manganese-based material using zirconium phosphate as outer covering and calcium fluoride as inner covering |
| CN106450277A (en) * | 2016-11-01 | 2017-02-22 | 江苏海四达电源股份有限公司 | Electrode system used in low-temperature rate type lithium ion battery |
| CN107086295A (en) * | 2016-02-12 | 2017-08-22 | 住友大阪水泥股份有限公司 | Lithium rechargeable battery |
| CN109216680A (en) * | 2018-09-18 | 2019-01-15 | 贵州永合益环保科技有限公司 | A kind of method of lithium manganese phosphate, alumina-coated nickel-cobalt lithium manganate cathode material |
| CN110416525A (en) * | 2019-08-08 | 2019-11-05 | 上海华谊（集团）公司 | The composite material and preparation method of phosphoric acid manganese iron lithium with core-shell structure |
| CN110970610A (en) * | 2016-11-18 | 2020-04-07 | 株式会社半导体能源研究所 | Method for manufacturing positive electrode active material and method for manufacturing portable information terminal |
| CN111276681A (en) * | 2020-02-14 | 2020-06-12 | 桑顿新能源科技有限公司 | Positive electrode material, preparation method and application thereof, positive electrode and battery |
| CN111354926A (en) * | 2018-12-22 | 2020-06-30 | 中天新兴材料有限公司 | Nickel cobalt lithium manganate composite material and preparation method thereof |
| CN111354936A (en) * | 2020-04-10 | 2020-06-30 | 湖北亿纬动力有限公司 | Core-shell structure cathode material and preparation method and application thereof |
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| CN103855384B (en) * | 2014-03-25 | 2016-09-28 | 浙江美达瑞新材料科技有限公司 | A kind of ternary cathode material of lithium ion battery of rare-earth-doped modification and preparation method thereof |
| CN103855384A (en) * | 2014-03-25 | 2014-06-11 | 海宁美达瑞新材料科技有限公司 | Rare-earth doping modified lithium ion battery ternary positive electrode material and preparation method thereof |
| CN103972499A (en) * | 2014-05-16 | 2014-08-06 | 海宁美达瑞新材料科技有限公司 | Modified nickel-cobalt lithium aluminate positive electrode material and preparation method thereof |
| CN103996832A (en) * | 2014-05-16 | 2014-08-20 | 合肥工业大学 | Carbon-metal oxide two-component cladding modified high-voltage positive material and cladding method |
| CN105226287A (en) * | 2014-06-26 | 2016-01-06 | 中兴通讯股份有限公司 | Anode material for lithium-ion batteries and preparation method thereof |
| CN107004918A (en) * | 2014-08-27 | 2017-08-01 | 尼沃系统公司 | Lithium metal oxide composite and its preparation and application |
| WO2016029856A1 (en) * | 2014-08-27 | 2016-03-03 | Nivo Systems, Inc. | Lithium metal oxide composites, and methods for preparing and using thereof |
| CN104332630A (en) * | 2014-10-22 | 2015-02-04 | 深圳市贝特瑞新能源材料股份有限公司 | Surface coated graphite cathode material, preparation method of surface coated graphite cathode material, as well as lithium ion battery containing surface coated graphite cathode material |
| CN104600290A (en) * | 2014-12-30 | 2015-05-06 | 深圳市贝特瑞新能源材料股份有限公司 | Nickel-cobalt lithium aluminate composite positive electrode material and preparation method thereof |
| CN107086295B (en) * | 2016-02-12 | 2021-09-17 | 住友大阪水泥股份有限公司 | Lithium ion secondary battery |
| CN107086295A (en) * | 2016-02-12 | 2017-08-22 | 住友大阪水泥股份有限公司 | Lithium rechargeable battery |
| CN105958021B (en) * | 2016-05-27 | 2019-07-30 | 天津泰和九思科技有限公司 | A kind of lithium titanate composite material and preparation method thereof and lithium ion battery |
| CN105958021A (en) * | 2016-05-27 | 2016-09-21 | 天津泰和九思科技有限公司 | Lithium titanate composite material and preparation method thereof and lithium-ion battery |
| CN106058203B (en) * | 2016-07-31 | 2018-08-03 | 湖南桑顿新能源有限公司 | A kind of preparation method for covering lithium-rich manganese base material using basic zirconium phosphate as the double-contracting that outer cladding, calcirm-fluoride are interior cladding |
| CN106058203A (en) * | 2016-07-31 | 2016-10-26 | 湖南桑顿新能源有限公司 | Preparation method of double-covering lithium-enriched manganese-based material using zirconium phosphate as outer covering and calcium fluoride as inner covering |
| CN106450277A (en) * | 2016-11-01 | 2017-02-22 | 江苏海四达电源股份有限公司 | Electrode system used in low-temperature rate type lithium ion battery |
| CN110970610A (en) * | 2016-11-18 | 2020-04-07 | 株式会社半导体能源研究所 | Method for manufacturing positive electrode active material and method for manufacturing portable information terminal |
| CN110970610B (en) * | 2016-11-18 | 2023-04-07 | 株式会社半导体能源研究所 | Method for manufacturing positive electrode active material and method for manufacturing portable information terminal |
| CN109216680A (en) * | 2018-09-18 | 2019-01-15 | 贵州永合益环保科技有限公司 | A kind of method of lithium manganese phosphate, alumina-coated nickel-cobalt lithium manganate cathode material |
| CN111354926A (en) * | 2018-12-22 | 2020-06-30 | 中天新兴材料有限公司 | Nickel cobalt lithium manganate composite material and preparation method thereof |
| CN110416525A (en) * | 2019-08-08 | 2019-11-05 | 上海华谊（集团）公司 | The composite material and preparation method of phosphoric acid manganese iron lithium with core-shell structure |
| CN111276681A (en) * | 2020-02-14 | 2020-06-12 | 桑顿新能源科技有限公司 | Positive electrode material, preparation method and application thereof, positive electrode and battery |
| CN111354936A (en) * | 2020-04-10 | 2020-06-30 | 湖北亿纬动力有限公司 | Core-shell structure cathode material and preparation method and application thereof |
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