CN105958054A - Method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate - Google Patents

Method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate Download PDF

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CN105958054A
CN105958054A CN201610462297.2A CN201610462297A CN105958054A CN 105958054 A CN105958054 A CN 105958054A CN 201610462297 A CN201610462297 A CN 201610462297A CN 105958054 A CN105958054 A CN 105958054A
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lanthanum
lithium
ion battery
nickel cobalt
lithium ion
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郑俊超
汤林波
张宝
李晖
童汇
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Central South University
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Central South University
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

The invention relates to a method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate. The lanthanum phosphate cladding method comprises the following steps: (1) adding a ternary precursor, a lithium salt, a lanthanum salt and phosphate into a high-speed material mixing machine, and stirring for 1-4 h at the speed of 500-2000 rpm; and (2) heating materials treated in the first step in an oxygen-containing atmosphere of 750-1200 DEG C for 5 to 20 hours, preserving the temperature for 4-10 h, and cooling to obtain the lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate. According to the method, an LaPO4 compound in an amorphous state can be formed on the surface of a nickel cobalt lithium manganate ternary cathode material, and the LaPO4 in the amorphous state is coated on the surface of the nickel cobalt lithium manganate ternary cathode material, so that the content of impurity lithium can be effectively reduced, and the cycle performance and electrochemical performance of a lithium ion battery under high voltage can be effectively improved.

Description

A kind of method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium
Technical field
The present invention relates to technical field of lithium ion, nickle cobalt lithium manganate tertiary cathode material particularly relating to a kind of modification and preparation method thereof.
Background technology
Nickle cobalt lithium manganate tertiary cathode material, owing to possessing the advantages such as high specific discharge capacity, safety is good, cheap, discharge voltage is high, specific energy is high, have extended cycle life, safety is good and environmentally friendly, is a kind of portable chemical power supply the most most with prospects.Its key component is lithium intercalation compound positive electrode, occupies larger proportion, and the quality of positive electrode decides the performance indications of lithium ion battery product, and become the bottleneck of restriction high performance lithium ion battery development in lithium ion battery.Along with quickly popularizing of portable electric appts, the requirement to battery performance is more and more higher.Therefore, high voltage, the anode material for lithium-ion batteries of height ratio capacity and good circulation performance becomes the focus of research.In technology today, along with the increase of Ni constituent content in ternary Ni-Co-Mn, the cycle performance of material and capability retention can reduce, it is documented, uses AlPO4、Co3PO4、SnPO4Improve material circulation performance, the most useful Li3PO4Improve material electrochemical performance, but at present still without passing through LaPO4Cladding ternary material improves the report of lithium ion battery chemical property and cycle performance.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, it is provided that a kind of method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium, is effectively improved cycle performance and the chemical property of lithium ion battery.
The method of the lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium of the present invention, comprises the following steps:
(1) ternary precursor, lithium salts, lanthanum salt, phosphate are joined in high speed mixer, with 500～2000rpm stirrings 1～4h；
(2) 5～20h will be heated in 750～1200 DEG C of oxygen-containing atmospheres through the material that step (1) processes, and it is incubated 4～10h, i.e. obtain lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium (anode material lithium nickle cobalt manganic acid of lithium ion battery elementary composition for LiNi after cooling0.5Co0.2Mn0.3O2, LiNi0.6Co0.2Mn0.2O2Or LiNi0.8Co0.1Mn0.1O2In one).
Further, in step (1), described ternary precursor is Ni0.5Co0.2Mn0.3(0H)2Ternary material precursor, Ni0.6Co0.2Mn0.2(0H)2Ternary material precursor or Ni0.8Co0.1Mn0.1(0H)2At least one in ternary precursor.
Further, in step (1), described lithium salts can be at least one in lithium carbonate, lithium nitrate, Lithium hydrate.
Further, in step (1), described lanthanum salt can be at least one in Lanthanum (III) nitrate, lanthanum oxalate, lanthanum acetate, lanthana, lanthanum orthophosphate.Phosphate used is at least one in ammonium dihydrogen phosphate, diammonium phosphate.
Further, in step (1), described ternary precursor is 1:(0.005～0.05 with the mol ratio of the lanthanum element in lanthanum salt), lanthanum element in described lanthanum salt is 1:1 with the mol ratio of the phosphate anion in phosphate, and described ternary precursor is 1:(1～1.2 with the mol ratio of the elemental lithium in lithium salts).After mixing, lanthanum orthophosphate accounts for the 1%～10% of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium gross mass.
Further, in step (2), described sintering atmosphere oxygen-containing atmosphere can be in pure oxygen or air.
During cladding, LaPO4In P=O key can improve the chemical stability of material, shield electrode material can not be improved heat stability by the combination of the acid corrosion of electrolyte, composite and lanthanum.Additionally, amorphous state LaPO can be formed on nickle cobalt lithium manganate tertiary cathode material surface4Compound, the LaPO of amorphous state4It is coated on nickle cobalt lithium manganate tertiary cathode material surface, can effectively reduce the content of impurity lithium, its cycle performance of lithium ion battery and chemical property under high voltages can be effectively improved.
Accompanying drawing explanation
Fig. 1 is nickel-cobalt lithium manganate cathode material circulation figure under 0.1C multiplying power that in comparative example 1 and embodiment 1, lanthanum orthophosphate is modified；
Fig. 2 is that nickel-cobalt lithium manganate material that in embodiment 1, lanthanum orthophosphate is modified is at 0.1C first charge-discharge curve chart.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Comparative example 1
(1) 0.7388g lithium carbonate (0.01mol) and Ni 1.7427g(0.019mol) are weighed0.5Co0.2Mn0.3(OH)2Ternary material precursor, joins in high speed mixer by ternary precursor, lithium carbonate, stirs 4h and obtain homogeneous sample under 500rpm；
(2) by obtained sample in atmosphere with 750 DEG C of heat-agglomerating 20h, after having sintered, it is incubated 10h, after cooling, i.e. obtains the nickle cobalt lithium manganate tertiary cathode material of modification.
Above-mentioned comparative example material being made button cell and carries out charge-discharge performance test, controlling charging/discharging voltage scope is 4.3～3V, and charging and discharging currents is 0.1C, and wherein, 1C is equal to 150mA/g.
Fig. 1 is nickel-cobalt lithium manganate cathode material circulation figure under 0.1C multiplying power that in comparative example 1 and embodiment 1, lanthanum orthophosphate is modified；
Fig. 2 is that nickel-cobalt lithium manganate material that in embodiment 1, lanthanum orthophosphate is modified is at 0.1C first charge-discharge curve chart.
The first discharge specific capacity recording a CR2025 type button cell is 171.6mAh/g, and circulating the specific discharge capacity after 50 times is 159.5mAh/g, and capability retention is 92.95%.
Embodiment 1
(1) 0.7388g (0.01mol) lithium carbonate, 0.3879g (0.9mmol) lanthanum nitrate hexahydrate, 1.4499g(0.9mmol are weighed) ammonium dihydrogen phosphate and the Ni of 1.7427g (0.019mol)0.5Co0.2Mn0.3(OH)2Ternary material precursor, joins in high speed mixer by ternary precursor, lithium carbonate, lanthanum salt, phosphate, stirs 4h and obtain homogeneous sample under 500rpm；
(2) by obtained sample in atmosphere with 750 DEG C of heat-agglomerating 20h, after having sintered, it is incubated 10h, i.e. obtains the nickle cobalt lithium manganate tertiary cathode material of modification after cooling, i.e. obtain LaPO4Coated lithium ion battery anode material nickel cobalt manganic acid lithium (anode material lithium nickle cobalt manganic acid of lithium ion battery elementary composition for LiNi0.5Co0.2Mn0.3O2).Wherein LaPO4Weight account for lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium gross weight (i.e. LaPO4With LiNi0.5Co0.2Mn0.3O2 The weight sum of tertiary cathode material) 8%.
Above-mentioned comparative example material being made button cell and carries out charge-discharge performance test, controlling charging/discharging voltage scope is 4.3～3V, and charging and discharging currents is 0.1C, and wherein, 1C is equal to 150mA/g.The first discharge specific capacity recording a CR2025 type button cell is 175.2mAh/g, and circulating the specific discharge capacity after 50 times is 170mAh/g, and capability retention is 97.03%.Visible, add the cyclical stability that the battery prepared of lanthanum orthophosphate material has had, and capacity performance is slightly higher.
Embodiment 2
(1) weigh 0.7388g (0.01mol) lithium carbonate, 0.1552g (0.4mmol) four is hydrated lanthanum acetate, 0.4392g(0.04mmol) diammonium phosphate and 1.8398g(0.02mol) Ni0.6Co0.2Mn0.2(OH)2Ternary material precursor, joins in high speed mixer by ternary precursor, lithium carbonate, lanthanum salt, diammonium phosphate, stirs 1h and obtain homogeneous sample under 2000rpm；
(2) by obtained sample in atmosphere with 1200 DEG C of heat-agglomerating 6h, after having sintered, it is incubated 6h, i.e. obtains the nickle cobalt lithium manganate tertiary cathode material of modification after cooling, i.e. obtain LaPO4Cladding coated lithium ion battery anode material nickel cobalt manganic acid lithium, (anode material lithium nickle cobalt manganic acid of lithium ion battery elementary composition for LiNi0.6Co0.2Mn0.2O2) wherein LaPO4Weight account for lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium gross weight (i.e. LaPO4With LiNi0.6Co0.2Mn0.2O2 The weight sum of tertiary cathode material) 4%.
Above-described embodiment material being made button cell and carries out charge-discharge performance test, controlling charging/discharging voltage scope is 4.3～3V, and charging and discharging currents is 0.1C, and wherein, 1C is equal to 150mA/g.The first discharge specific capacity recording CR2025 type button cell is 175.6mAh/g, and circulating the specific discharge capacity after 50 times is 169.4mAh/g, and capability retention is 96.47%.
Embodiment 3
(1) weigh 0.2394g (0.01mol) Lithium hydrate, 0.006g (0.2mmol) lanthanum nitrate hexahydrate, 0.0245g(0.2mmol) ammonium dihydrogen phosphate and 0.869g(0.009mol) Ni0.8Co0.1Mn0.1(OH)2Ternary material precursor, joins in high speed mixer by ternary precursor, Lithium hydrate, lanthanum salt, ammonium dihydrogen phosphate, stirs 3h and obtain homogeneous sample under 1200rpm；
(2) by obtained sample in pure oxygen atmosphere with 1000 DEG C of heat-agglomerating 12h, be incubated 5h after having sintered, i.e. obtain after cooling modification nickle cobalt lithium manganate tertiary cathode material, i.e. obtain LaPO4Cladding coated lithium ion battery anode material nickel cobalt manganic acid lithium, (anode material lithium nickle cobalt manganic acid of lithium ion battery elementary composition for LiNi0.8Co0.1Mn0.1O2) wherein LaPO4Weight account for lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium gross weight (i.e. LaPO4With LiNi0.8Co0.1Mn0.1O2 The weight sum of tertiary cathode material) 1%.
Above-described embodiment material being made button cell and carries out charge-discharge performance test, controlling charging/discharging voltage scope is 4.3～3V, and charging and discharging currents is 0.1C, and wherein, 1C is equal to 150mA/g.The first discharge specific capacity recording CR2025 type button cell is 172.5mAh/g, and circulating the specific discharge capacity after 50 times is 167.8mAh/g, and capability retention is 97.28%.

Claims (9)

1. the method for a lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium, it is characterised in that comprise the following steps:
(1) ternary precursor, lithium salts, lanthanum salt, phosphate are joined in high speed mixer, with 500～2000rpm stirrings 1～4h；
(2) 5～20h will be heated in 750～1200 DEG C of oxygen-containing atmospheres through the material that step (1) processes, and be incubated 4～10h, after cooling, i.e. obtain lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium.
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1, it is characterised in that in step (1), described ternary precursor is Ni0.5Co0.2Mn0.3(0H)2Ternary material precursor, Ni0.6Co0.2Mn0.2(0H)2Ternary material precursor or Ni0.8Co0.1Mn0.1(0H)2At least one in ternary precursor.
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1 and 2, it is characterised in that in step (1), described lithium salts is at least one in lithium carbonate, lithium nitrate, Lithium hydrate.
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1 and 2, it is characterised in that in step (1), described lanthanum salt is at least one in Lanthanum (III) nitrate, lanthanum oxalate, lanthanum acetate, lanthana, lanthanum orthophosphate.
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1 and 2, it is characterised in that in step (1), phosphate used is at least one in ammonium dihydrogen phosphate, diammonium phosphate.
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1 and 2, it is characterised in that in step (1), described ternary precursor is 1:(0.005～0.05 with the mol ratio of the lanthanum element in lanthanum salt).
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1 and 2, it is characterised in that in step (1), the lanthanum element in described lanthanum salt is 1:1 with the mol ratio of the phosphate anion in phosphate.
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1 and 2, it is characterised in that in step (1), described ternary precursor is 1:(1～1.2 with the mol ratio of the elemental lithium in lithium salts).
The method of lanthanum orthophosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium the most according to claim 1 and 2, it is characterised in that in step (2), described sintering atmosphere oxygen-containing atmosphere is in pure oxygen or air.
CN201610462297.2A 2016-06-23 2016-06-23 Method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate Pending CN105958054A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108321363A (en) * 2017-12-22 2018-07-24 合肥国轩高科动力能源有限公司 A kind of dysprosium phosphate cladding lithium-rich anode material and preparation method thereof
CN109616665A (en) * 2018-12-13 2019-04-12 合肥国轩高科动力能源有限公司 A kind of preparation method and its product and application reducing nickle cobalt lithium manganate tertiary cathode material residual alkali
CN110137437A (en) * 2018-02-02 2019-08-16 天津国安盟固利新材料科技股份有限公司 A kind of lithium cobalt oxide cathode material for lithium ion battery and its method for coating
CN110400929A (en) * 2019-09-02 2019-11-01 中南大学 A kind of metal-doped ternary positive electrode active material of Phosphate coating and its preparation and application
CN111682201A (en) * 2019-03-11 2020-09-18 中天新兴材料有限公司 Preparation method of nickel cobalt lithium manganate composite material
CN112164798A (en) * 2020-09-28 2021-01-01 桑顿新能源科技有限公司 Surface stability enhanced positive electrode material and preparation method thereof
CN113307314A (en) * 2021-06-04 2021-08-27 浙江帕瓦新能源股份有限公司 Preparation method of ternary precursor coated and modified by polyvalent metal phosphide
CN113488620A (en) * 2021-06-28 2021-10-08 恒大新能源技术(深圳)有限公司 Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery
CN113697869A (en) * 2021-08-20 2021-11-26 浙江帕瓦新能源股份有限公司 Metal phosphide and metal phosphate composite modified ternary positive electrode material precursor
CN115353155A (en) * 2022-08-22 2022-11-18 长沙理工大学 Preparation method of phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery positive electrode material

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108321363A (en) * 2017-12-22 2018-07-24 合肥国轩高科动力能源有限公司 A kind of dysprosium phosphate cladding lithium-rich anode material and preparation method thereof
CN110137437B (en) * 2018-02-02 2022-04-29 天津国安盟固利新材料科技股份有限公司 Lithium cobaltate positive electrode material of lithium ion battery and coating method thereof
CN110137437A (en) * 2018-02-02 2019-08-16 天津国安盟固利新材料科技股份有限公司 A kind of lithium cobalt oxide cathode material for lithium ion battery and its method for coating
CN109616665A (en) * 2018-12-13 2019-04-12 合肥国轩高科动力能源有限公司 A kind of preparation method and its product and application reducing nickle cobalt lithium manganate tertiary cathode material residual alkali
CN111682201A (en) * 2019-03-11 2020-09-18 中天新兴材料有限公司 Preparation method of nickel cobalt lithium manganate composite material
CN110400929A (en) * 2019-09-02 2019-11-01 中南大学 A kind of metal-doped ternary positive electrode active material of Phosphate coating and its preparation and application
CN112164798A (en) * 2020-09-28 2021-01-01 桑顿新能源科技有限公司 Surface stability enhanced positive electrode material and preparation method thereof
CN113307314A (en) * 2021-06-04 2021-08-27 浙江帕瓦新能源股份有限公司 Preparation method of ternary precursor coated and modified by polyvalent metal phosphide
CN113307314B (en) * 2021-06-04 2022-11-25 浙江帕瓦新能源股份有限公司 Preparation method of ternary precursor coated and modified by polyvalent metal phosphide
CN113488620A (en) * 2021-06-28 2021-10-08 恒大新能源技术(深圳)有限公司 Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery
CN113697869A (en) * 2021-08-20 2021-11-26 浙江帕瓦新能源股份有限公司 Metal phosphide and metal phosphate composite modified ternary positive electrode material precursor
CN115353155A (en) * 2022-08-22 2022-11-18 长沙理工大学 Preparation method of phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery positive electrode material
CN115353155B (en) * 2022-08-22 2023-10-24 长沙理工大学 Preparation method of phosphorus and lanthanum co-modified low-cobalt lithium-rich manganese-based lithium ion battery anode material

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Application publication date: 20160921