CN113346055A - Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof - Google Patents

Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof Download PDF

Info

Publication number
CN113346055A
CN113346055A CN202110509371.2A CN202110509371A CN113346055A CN 113346055 A CN113346055 A CN 113346055A CN 202110509371 A CN202110509371 A CN 202110509371A CN 113346055 A CN113346055 A CN 113346055A
Authority
CN
China
Prior art keywords
ion battery
nickel
lithium ion
lini
composite phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110509371.2A
Other languages
Chinese (zh)
Inventor
刘兴泉
李蕾
程文栋
郝帅
纪煜垚
肖雨
何泽珍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN202110509371.2A priority Critical patent/CN113346055A/en
Publication of CN113346055A publication Critical patent/CN113346055A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/38—Condensed phosphates
    • C01B25/44—Metaphosphates
    • 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
    • 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
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Hair brushThe invention belongs to the technical field of preparation of lithium ion battery anode materials, and provides a composite phosphate coated lithium ion battery high-nickel anode material and a preparation method thereof; the method is used for overcoming the defects of poor processing performance, strict requirements on the use environment, poor cycle stability, low coulomb efficiency of the first circle, rapid reduction of high-temperature performance, and poor safety and cycle life in the prior art. The invention uses yttrium metaphosphate Y (PO)3)3As a coating material, Y (PO) was passed3)3With residual alkali (LiOH, Li) on the surface of the parent material2CO3) The compound multifunctional phosphate coating layer is generated by the in-situ reaction, so that the lithium salt residue on the surface of the parent material is greatly reduced, the processing performance is improved, the use environment requirement is reduced, the ionic conductivity of the anode material is increased, and the phase change and the interface side reaction are effectively inhibited; the lithium phosphate coated lithium ion battery high-nickel anode material has excellent discharge specific capacity and cycling stability, and can keep better electrochemical performance especially at high temperature.

Description

Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery cathode materials, relates to coating modification of a lithium ion battery high-nickel (the molar ratio Ni is more than or equal to 80%) cathode material, and particularly provides a composite phosphate coated lithium ion battery high-nickel cathode material and a preparation method thereof.
Background
In recent years, the problems of increasingly exhausted non-renewable energy sources, global greenhouse effect and the like all promote people to continuously develop and utilize clean energy sources; the lithium ion battery has the advantages of high energy density, light weight, environmental protection and the like, is increasingly popular with people, and is particularly used for new energy automobiles; the development of new energy automobiles becomes a main direction of transformation development of the global automobile industry and is also a strategic measure for coping with the crisis of climate change and promoting the development of green energy.
The development of high energy density lithium ion batteries has become a focus of attention in the battery industry, where the performance of the positive electrode material is directly determinedThe performance of the lithium ion battery is fixed. High nickel NCM ternary positive electrode material LiNi0.8Co0.1Mn0.1O2High nickel NCA ternary positive electrode material LiNi0.8Co0.15Al0.05O2And high nickel-cobalt binary anode material LiNi0.9Co0.1O2The layered high nickel cathode material as a representative is receiving increasing attention due to its lower cost and high energy density. At present, the high-nickel anode material still has some obvious defects, the processing performance is poor, the requirement on the use environment is strict, the anode material can generate irreversible phase change in the circulating process, side reactions are increased, and meanwhile, microcracks are continuously generated on the surface and the bulk phase to destroy the stability of an interface and a crystal boundary; in addition, carbon dioxide is released due to decomposition of residual lithium salt residual alkali, the CEI film is broken and Li is blocked+Diffusion channels, further reducing capacity; especially at high temperature, the electrochemical performance of the material is sharply reduced, resulting in poor safety and cycle life of the material.
Disclosure of Invention
The invention aims to provide a composite phosphate coated high-nickel positive electrode material for a lithium ion battery and a preparation method thereof, aiming at the defects of poor processing performance, strict requirements on a use environment, poor cycle stability, low coulomb efficiency in the first circle, rapid reduction of high-temperature performance, and poor safety and cycle life of the high-nickel positive electrode material for the lithium ion battery. In the present invention, yttrium metaphosphate Y (PO) is used3)3As a coating material, Y (PO) was passed3)3With residual alkali (LiOH, Li) on the surface of the parent material2CO3) The compound multifunctional phosphate coating layer is generated by the in-situ reaction, so that the lithium salt residue on the surface of the parent material is greatly reduced, the processing performance is improved, the use environment requirement is reduced, the ionic conductivity of the anode material is increased, and the phase change and the interface side reaction are effectively inhibited; the lithium phosphate coated lithium ion battery high-nickel anode material has excellent discharge specific capacity and cycling stability, and can keep better electrochemical performance especially at high temperature; in addition, the method also has the advantages of simple synthesis process, low manufacturing cost and the like, and is easy to realize large-scale industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that:
the composite phosphate coated high-nickel positive electrode material of the lithium ion battery is characterized in that the positive electrode material is composed of a parent material and a composite coating layer coated on the surface of the parent material, the parent material is a high-nickel (the molar ratio Ni is more than or equal to 80%) nickel-cobalt binary positive electrode material, a high-nickel (the molar ratio Ni is more than or equal to 80%) NCA ternary positive electrode material or a high-nickel (the molar ratio Ni is more than or equal to 80%) NCM ternary positive electrode material, the composite coating layer is of a two-layer structure, and the inner coating layer is a Li (nickel) coating layer3PO4The outer coating layer is YPO4/Y(PO3)3Compounding layers; the coating amount of the composite coating layer is 0.1-5 wt%.
Furthermore, the composite coating layer is generated by in-situ reaction of yttrium metaphosphate and residual alkali on the surface of the parent material.
The preparation method of the composite phosphate coated lithium ion battery high-nickel anode material comprises the following steps:
step 1, with Y (PO)3)3For coating the raw material, Y (PO)3)3Dispersing in absolute ethyl alcohol to form a solution;
step 2, adding the matrix material into the solution obtained in the step 1, stirring at room temperature for 30-40 min, heating to 60-100 ℃, and stirring again until the absolute ethyl alcohol is evaporated to form mixture powder;
step 3, putting the mixture powder obtained in the step 2 into an oven for drying to obtain a dried sample;
and 4, putting the dried sample obtained in the step 3 into a tubular furnace, heating to 500-650 ℃ at the speed of 1-10 ℃/min in the oxygen atmosphere, sintering for 6-12 h, naturally cooling to room temperature, and thus obtaining the composite phosphate coated lithium ion battery high-nickel anode material.
Further, in step 1, Y (PO)3)3The weight percentage of the material in the matrix material is 0.1-5 wt%.
Further, in step 3, the oven temperature is: and (3) drying at the temperature of 80-120 ℃ for the following time: 10-16 h.
Further, in the step 4, the flow rate of the oxygen in the oxygen atmosphere is 100-1000 ml/min.
Further, the matrix material is LiNi0.9Co0.1O2The preparation method comprises the following steps:
step 1, dissolving a lithium source raw material in deionized water, and adding Ni0.9Co0.1(OH)2The precursor is fully ground by using absolute ethyl alcohol as a dispersing agent and then dried to obtain mixture powder;
step 2, putting the mixture powder obtained in the step 1 into an oven for drying to obtain a dried sample;
and 3, putting the dried sample obtained in the step 2 into a tubular furnace, heating to 400-650 ℃ at the speed of 1-10 ℃/min in the oxygen atmosphere for pre-sintering for 6-15 h, heating to 700-950 ℃ at the speed of 1-10 ℃/min for roasting for 15-25 h, naturally cooling to room temperature, taking out the material, grinding and sieving to obtain the high-nickel cathode material LiNi of the lithium ion battery0.9Co0.1O2。
Further, the matrix material is LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2The preparation method comprises the following steps:
step 1, dissolving a lithium source raw material in deionized water, and adding Ni0.8Co0.15Al0.05(OH)2Precursor or Ni0.8Co0.1Mn0.1(OH)2The precursor is fully ground by using absolute ethyl alcohol as a dispersing agent and then dried to obtain mixture powder;
step 2, putting the mixture powder obtained in the step 1 into an oven for drying to obtain a dried sample;
and 3, putting the dried sample obtained in the step 2 into a tubular furnace, heating to 400-650 ℃ at the speed of 1-10 ℃/min for pre-sintering for 6-15 h in an oxygen atmosphere, heating to 700-950 ℃ at the speed of 1-10 ℃/min for roasting for 15-25 h, and finally naturally cooling to room temperature to obtain the high-nickel cathode material LiNi of the lithium ion battery0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2。
In terms of the working principle, the utility model,
parent material: lithium salt residual alkali remained on the surface of the high nickel (the molar ratio Ni is more than or equal to 80 percent) nickel-cobalt binary positive electrode material, the high nickel (the molar ratio Ni is more than or equal to 80 percent) NCA ternary positive electrode material or the high nickel (the molar ratio Ni is more than or equal to 80 percent) NCM ternary positive electrode material is mainly LiOH and Li2CO3(ii) a The invention adopts yttrium metaphosphate as a coating raw material, and very small amount of yttrium metaphosphate and lithium salt remained on the surface of the anode material are subjected to in-situ reaction to automatically generate a composite phosphate coating layer, as shown in figure 1, the specific reaction process is as follows:
6LiOH+Y(PO3)3→YPO4+2Li3PO4+3H2O
3Li2CO3+Y(PO3)3→YPO4+2Li3PO4+3CO2↑
reaction-produced Li3PO4Is a coating Y (PO)3)3Metaphosphate and surface residual alkali LiOH and Li2CO3First, the YPO is produced by forming an inner coating layer on the surface of a base material4And Y (PO)3)3The Yttrium Phosphate (YPO) generated when residual alkali is eliminated after the concentration of residual alkali on the surface is reduced or substantially eliminated4) With unreacted coating (Y (PO)3)3) Forming a composite layer as an outer coating layer;
the coating process not only reduces the alkalinity of the surface of the parent material and the pH value, but also effectively inhibits the corrosion action of hydrofluoric acid (HF) in the electrolyte on the cathode material, inhibits the dissolution of transition metal ions from crystal lattices, reduces interface side reactions, inhibits the generation of irreversible phase change and microcracks, improves the stability of the surface of the material, and improves the processing performance, thereby having excellent cycle stability and high-temperature electrochemical performance;
at the same time, Li is coated due to the inner layer3PO4Contains enough lithium ions to inhibit the first circulationIrreversible capacity loss caused by the formation of the SEI film can also provide and supplement lithium ions consumed by the formation of the SEI film, so that the lithium ions which can be charged and discharged reversibly can be effectively supplemented, and the coulombic efficiency and the specific discharge capacity of the first circle of the material can be improved; YPO with outer coating layer4/Y(PO3)3The material has higher ionic conductivity, and is beneficial to reducing the oxygen loss activity of the material under overcharge and high temperature, and the oxygen precipitation temperature is improved; thereby improving the safety and cycle life of the material.
In the present invention, the "coating amount" refers to the mass percentage of the coating raw material to the matrix material.
In conclusion, the beneficial effects of the invention are as follows:
1. the invention uses a very small amount of yttrium metaphosphate (Y (PO)3)3) Carrying out in-situ reaction with residual lithium salt and residual alkali on the surface of the positive electrode material to generate a composite phosphate coating layer; the precursor is used as the blending sintering of the base material, the target product particles are in a sphere-like shape, and the particle size distribution is uniform; moreover, the operation process is simple, the manufacturing cost is low, no toxic and harmful substances are generated in the preparation process, the green environmental protection and sustainable development concepts are met, and the large-scale industrial production is easy to realize;
2. according to the invention, the yttrium metaphosphate automatically generates the composite phosphate coating layer, so that the alkalinity of the material surface is reduced, the pH value is obviously reduced, the processing performance is obviously improved, the corrosion action of hydrofluoric acid (HF) in the electrolyte on the anode material is effectively inhibited, the dissolution of transition metal ions from crystal lattices is inhibited, the interface side reaction is reduced, the irreversible phase change and the microcrack generation are inhibited, and the stability of the surface and the crystal boundary is improved; in addition, irreversible capacity loss caused by the SEI film formed in the first cycle is inhibited, lithium ions consumed by the SEI film are provided and supplemented, and the coulombic efficiency and the specific discharge capacity of the material in the first cycle are improved; YPO with outer coating layer4/Y(PO3)3The Yttrium Phosphate (YPO) generated when residual alkali is eliminated after the concentration of residual alkali on the surface is reduced or substantially eliminated4) With unreacted coating yttrium metaphosphate (Y (PO)3)3) Due to its higher contentThe ionic conductivity of the material is favorable for reducing the oxygen loss activity of the material under overcharge and high temperature, and the oxygen precipitation temperature is improved; thereby improving the safety and cycle life of the material;
3. according to the composite phosphate coated lithium ion battery high-nickel anode material provided by the invention, through the larger excess of lithium by 10-20%, the lithium loss of the material at high temperature is compensated, the discharge specific capacity and the cycle performance of the material are increased, the surface residual alkali content of the material is not increased, and the processing performance of the material is not influenced;
4. the composite phosphate coated lithium ion battery high-nickel anode material provided by the invention has excellent cycle performance and high-temperature discharge and charge performance; LiNi coated with composite phosphate0.9Co0.1O2For example, when the charge-discharge cutoff voltage is 2.8-4.3V at room temperature of 25 ℃ +/-1 ℃, the first discharge specific capacity of the material reaches 202.3mAh/g under the charge-discharge rate of 0.5C, the first-turn coulombic efficiency is 81.7%, and the capacity retention rate is 96.8% after 100 cycles; when the charge-discharge cutoff voltage is 2.8-4.3V at 50 +/-1 ℃, the first discharge specific capacity of the material reaches 223.6mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency is 89.5%, and the capacity retention rate is 94.4% after 100 cycles of circulation. The specific capacity and the cycle performance are far higher than those of similar products. Lithium ion battery high-nickel anode material LiNi prepared by coating composite phosphate0.9Co0.1O2Not only the normal-temperature electrochemical performance is improved, but also the electrochemical performance at high temperature is obviously improved, so that the discharging safety of the material at high temperature is greatly improved;
5. the raw materials involved in the preparation process provided by the invention have wide sources and low price, are nontoxic and pollution-free, and are environment-friendly.
Drawings
Fig. 1 is a schematic diagram of the principle of the composite phosphate-coated lithium ion battery high-nickel positive electrode material of the present invention.
Fig. 2 shows a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2The preparation process flow chart of (1).
Fig. 3 shows a lithium ion battery high nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2The preparation process flow chart of (1).
Fig. 4 shows a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2XRD pattern of (a).
Fig. 5 shows a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2SEM image of (d).
Fig. 6 shows a composite phosphate coated lithium ion battery high nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2Graph of cycling performance at 25 ℃.
Fig. 7 shows a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2Charge and discharge curves at 25 ℃.
Fig. 8 shows a composite phosphate coated lithium ion battery high nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2Graph of cycling performance at 50 ℃.
Fig. 9 shows a composite phosphate coated lithium ion battery high nickel positive electrode material LiNi provided in embodiment 1 of the present invention0.9Co0.1O2Charge and discharge curves at 50 ℃.
Detailed Description
The present invention will be described in further detail with reference to specific examples, comparative examples and the accompanying drawings.
Example 1
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.9Co0.1O2Wherein, the lithium ion battery high nickel anode material LiNi0.9Co0.1O2As a matrix material, yttrium metaphosphate Y (PO) is used3)3For coating the raw material, from Y (PO)3)3With residual alkali (LiOH, Li) on the surface of the parent material2CO3) In situ reaction to formA phosphate coating layer; the coating amount of the yttrium metaphosphate is the matrix positive electrode material LiNi0.9Co0.1O22 wt% of (matrix material).
The composite phosphate-coated lithium ion battery high-nickel cathode material LiNi0.9Co0.1O2The preparation process is shown in fig. 2, and specifically comprises the following steps:
according to the coating amount, 0.04gY (PO)3)3Dispersing in 30-40 ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 10-30 min to form a suspension solution;
then 2.0g of parent anode material LiNi is added into the solution0.9Co0.1O2Stirring at room temperature for 30-40 min, heating to 90 ℃, and continuously stirring until the alcohol is evaporated to dryness to form mixture powder;
then, putting the mixture powder into an oven, and drying for 10-12 hours at 80-100 ℃ to obtain a dried sample;
finally, the dried sample is put into a tube furnace, the temperature is raised to 500 ℃ at the speed of 2 ℃/min under the oxygen atmosphere (the oxygen flow rate is 300ml/min), the sintering is carried out for 6h, the temperature is naturally reduced to the room temperature, the material is taken out, ground and sieved, and the composite phosphate coated high nickel anode material LiNi is obtained0.9Co0.1O2。
More specifically, the parent cathode material LiNi0.9Co0.1O2The preparation process is shown in fig. 3, and specifically comprises the following steps: 0.9231g of LiOH. H were weighed out in a molar ratio of 10% excess of the lithium source2Dissolving O in 10ml of deionized water, adding 1.8539g of precursor, fully and uniformly grinding to obtain mixed slurry, adding absolute ethyl alcohol serving as a dispersing agent, continuously and fully and uniformly grinding in an agate mortar, drying to obtain mixture powder, and drying in an oven (drying at 80-100 ℃ for 10-12 hours); finally, the dried sample is put into a tube furnace to be preheated for 6h at the speed of 2 ℃/min to 480 ℃ under the oxygen atmosphere (the oxygen flow rate is 300ml/min), then the temperature is raised to 720 ℃ at the speed of 2 ℃/min to be roasted for 20h, then the temperature is naturally reduced to the room temperature, the material is taken out and ground and sieved, and the high-nickel matrix anode material LiNi is obtained0.9Co0.1O2。
In this example, an uncoated parent positive electrode material LiNi was used0.9Co0.1O2As a comparative example, the lithium ion battery high nickel cathode material LiNi provided in this example was subjected to0.9Co0.1O2And tested in comparison with the comparative example. In this example, the XRD pattern and SEM pattern of the positive electrode material are shown in FIG. 4 and 5, respectively, and it can be seen from FIG. 4 that the material has alpha-NaFeO2The layered structure of the type, as can be seen from fig. 5, the material is spheroidal and has a uniform particle size distribution. The positive electrode material in the embodiment is subjected to constant current charge and discharge test, and the test results are shown in fig. 6-9, so that the positive electrode material has high specific discharge capacity, high first-cycle coulombic efficiency, excellent cycle stability and high-temperature performance, when the charge and discharge cutoff voltage is 2.8-4.3V at the room temperature of 25 +/-1 ℃, the first specific discharge capacity of the material reaches 202.3mAh/g at the charge and discharge rate of 0.5C, the first-cycle coulombic efficiency is 81.7%, and the capacity retention rate is 96.8% after 100 cycles; under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has a first discharge specific capacity of 223.6mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.5 percent, and the capacity retention rate of 94.4 percent after 100 cycles;
compared with the comparative example, when the charge-discharge cutoff voltage is 2.8-4.3V at the room temperature of 25 +/-1 ℃, the initial discharge specific capacity of the uncoated high-nickel anode material at the charge-discharge rate of 0.5C is only 190.1mAh/g, the first-turn coulombic efficiency is only 77.4%, and the capacity retention rate is only 89.3% after 100 cycles; under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has the first discharge specific capacity of 221.4mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.1 percent, and the capacity retention rate of only 84.8 percent after 100 cycles;
therefore, in the embodiment, the composite phosphate-coated lithium ion battery high-nickel cathode material LiNi0.9Co0.1O2The electrochemical performance of the alloy is comprehensively superior to that of a comparative example, and particularly, the alloy performs better at high temperature.
Example 2
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.9Co0.1O2The only difference from example 1 is that: the coating amount of the yttrium metaphosphate is the matrix positive electrode material LiNi0.9Co0.1O21 wt% of (matrix material); the principle and electrochemical performance of the cathode material provided by the embodiment are basically the same as those of the embodiment 1 after being tested.
Example 3
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.9Co0.1O2The only difference from example 1 is that: the coating amount of the yttrium metaphosphate is the matrix positive electrode material LiNi0.9Co0.1O23 wt% of (matrix material); the principle and electrochemical performance of the cathode material provided by the embodiment are basically the same as those of the embodiment 1 after being tested.
Example 4
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.9Co0.1O2The only difference from example 1 is that: the coating amount of the yttrium metaphosphate is the matrix positive electrode material LiNi0.9Co0.1O20.5 wt% of (base material); the principle and electrochemical performance of the cathode material provided by the embodiment are basically the same as those of the embodiment 1 after being tested.
Example 5
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.8Co0.15Al0.05O2；
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.8Co0.15Al0.05O2Wherein, the lithium ion battery high nickel anode material LiNi0.8Co0.15Al0.05O2As a matrix material, yttrium metaphosphate Y (PO) is used3)3For coating the raw material, from Y (PO)3)3With residual alkali (LiOH, Li) on the surface of the parent material2CO3) Generating a composite phosphate coating layer through in-situ reaction; the coating amount of the yttrium metaphosphate is the matrix positive electrode material LiNi0.8Co0.15Al0.05O22 wt% of (matrix material).
According to the coating amount, 0.04gY (PO)3)3Dispersing in 30-40 ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 10-30 min to form a suspension solution;
then 2.0g of parent anode material LiNi is added into the solution0.8Co0.15Al0.05O2Stirring at room temperature for 30-40 min, heating to 90 ℃, and continuously stirring until the alcohol is evaporated to dryness to form mixture powder;
then placing the mixture powder into an oven, and drying at 90-120 ℃ for 10-12 h to obtain a dried sample;
finally, the dried sample is put into a tube furnace, the temperature is raised to 500 ℃ at the speed of 2 ℃/min under the oxygen atmosphere (the oxygen flow rate is 300ml/min), the sintering is carried out for 6h, the temperature is naturally reduced to the room temperature, the material is taken out, ground and sieved, and the composite phosphate coated high nickel anode material LiNi is obtained0.8Co0.15Al0.05O2。
More specifically, the parent cathode material LiNi0.8Co0.15Al0.05O2The preparation process specifically comprises the following steps: 0.9231g of LiOH. H were weighed out in a molar ratio of 10% excess of the lithium source2Dissolving O in 10ml of deionized water, adding 1.8448g of precursor, fully and uniformly grinding to obtain mixed slurry, adding absolute ethyl alcohol as a dispersing agent, continuously and fully and uniformly grinding in an agate mortar, drying to obtain mixture powder, and drying in an oven (drying at 90-120 ℃ for 10-12 hours); finally, the dried sample is put into a tube furnace to be preheated for 6h at the speed of 2 ℃/min to 480 ℃ under the oxygen atmosphere (the oxygen flow rate is 300ml/min), then the temperature is raised to 725 ℃ at the speed of 2 ℃/min to be roasted for 20h, then the temperature is naturally reduced to room temperature, the material is taken out and ground and sieved, and the high-nickel matrix anode material LiNi is obtained0.8Co0.15Al0.05O2。
In this example, an uncoated parent positive electrode material LiNi was used0.8Co0.15Al0.05O2As a comparative example, the lithium ion battery provided in this example was high nickel positive electrodeLiNi as a polar material0.8Co0.15Al0.05O2Electrochemical performance tests were performed with the comparative examples. The positive electrode material in this example was subjected to constant current charge and discharge testing, and the test results were as follows: the positive electrode material has high specific discharge capacity, high first-cycle coulombic efficiency, excellent cycle stability and high-temperature stability, when the charge-discharge cutoff voltage is 2.8-4.3V at the room temperature of 25 +/-1 ℃, the first specific discharge capacity of the material reaches 196.5mAh/g under the charge-discharge rate of 0.5C, the first-cycle coulombic efficiency is 83.2%, and the capacity retention rate is 97.7% after 100 cycles of circulation; under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has the first discharge specific capacity of 202.7mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.8 percent, and the capacity retention rate of 98.4 percent after 100 cycles;
and aiming at the comparative example, under the room temperature of 25 +/-1 ℃, and the charge-discharge cut-off voltage is 2.8-4.3V, the uncoated high-nickel parent positive electrode material LiNi0.8Co0.15Al0.05O2The first discharge specific capacity under the charge-discharge rate of 0.5C is only 185.3mAh/g, the first-circle coulombic efficiency is only 77.8%, and the capacity retention rate is only 88.7% after 100 circles of circulation; under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has the first discharge specific capacity of 203.9mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.2 percent, and the capacity retention rate of only 85.4 percent after 100 cycles;
therefore, in the embodiment, the composite phosphate-coated lithium ion battery high-nickel cathode material LiNi0.8Co0.15Al0.05O2The electrochemical performance of the alloy is comprehensively superior to that of a comparative example, and particularly, the alloy performs better at high temperature.
Example 6
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.8Co0.1Mn0.1O2；
The embodiment provides a composite phosphate-coated lithium ion battery high-nickel positive electrode material LiNi0.8Co0.1Mn0.1O2Wherein, the lithium ion battery is a high nickel anodeLiNi material0.8Co0.1Mn0.1O2As a matrix material, yttrium metaphosphate Y (PO) is used3)3For coating the raw material, from Y (PO)3)3With residual alkali (LiOH, Li) on the surface of the parent material2CO3) Generating a composite phosphate coating layer through in-situ reaction; the coating amount of the yttrium metaphosphate is the matrix positive electrode material LiNi0.8Co0.1Mn0.1O22 wt% of (matrix material).
According to the coating amount, 0.04gY (PO)3)3Dispersing in 30-40 ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 10-30 min to form a suspension solution;
then 2.0g of parent anode material LiNi is added into the solution0.8Co0.1Mn0.1O2Stirring at room temperature for 30-40 min, heating to 90 ℃, and continuously stirring until the alcohol is evaporated to dryness to form mixture powder;
then, putting the mixture powder into an oven, and drying for 10-12 hours at 90-100 ℃ to obtain a dried sample;
finally, the dried sample is put into a tube furnace, the temperature is raised to 500 ℃ at the speed of 2 ℃/min under the oxygen atmosphere (the oxygen flow rate is 300ml/min), the sintering is carried out for 6h, the temperature is naturally reduced to the room temperature, the material is taken out, ground and sieved, and the composite phosphate coated high nickel anode material LiNi is obtained0.8Co0.1Mn0.1O2。
More specifically, the parent cathode material LiNi0.8Co0.1Mn0.1O2The preparation process specifically comprises the following steps: 0.9231g of LiOH. H were weighed out in a molar ratio of 10% excess of the lithium source2Dissolving O in 10ml of deionized water, adding 1.8479g of precursor, fully and uniformly grinding to obtain mixed slurry, adding absolute ethyl alcohol serving as a dispersing agent, continuously and fully and uniformly grinding in an agate mortar, drying to obtain mixture powder, and drying in an oven (drying at 90-100 ℃ for 10-12 hours); finally, the dried sample is put into a tube furnace to be preheated for 6h at the speed of 2 ℃/min to 480 ℃ under the oxygen atmosphere (the oxygen flow rate is 300ml/min), and then the temperature is raised to 750 ℃ at the speed of 2 ℃/min to be roasted for 20h, and then the temperature is naturally cooled to the temperatureTaking out the material at room temperature, grinding and sieving to obtain the high nickel matrix cathode material LiNi0.8Co0.1Mn0.1O2。
In this example, an uncoated parent positive electrode material LiNi was used0.8Co0.1Mn0.1O2As a comparative example, the lithium ion battery high nickel cathode material LiNi provided in this example was subjected to0.8Co0.1Mn0.1O2Electrochemical performance tests were performed with the comparative examples. The positive electrode material in this example was subjected to constant current charge and discharge testing, and the test results were as follows: the positive electrode material has high specific discharge capacity, high first-cycle coulombic efficiency, excellent cycle stability and high-temperature stability, the first specific discharge capacity of the material reaches 195.8mAh/g under the charge-discharge rate of 0.5C at room temperature of 25 +/-1 ℃ and the charge-discharge cutoff voltage of 2.8-4.3V, the first-cycle coulombic efficiency is 83.3%, and the capacity retention rate is 96.9% after 100 cycles of circulation; under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has the first discharge specific capacity of 198.8mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.3 percent, and the capacity retention rate of 96.5 percent after 100 cycles;
and aiming at the comparative example, under the room temperature of 25 +/-1 ℃, and the charge-discharge cut-off voltage is 2.8-4.3V, the uncoated high-nickel parent positive electrode material LiNi0.8Co0.1Mn0.1O2The first discharge specific capacity is only 183.8mAh/g under the charge-discharge rate of 0.5C, the first-circle coulombic efficiency is only 80.3%, and the capacity retention rate is only 80.7% after 100 circles of circulation; under 50 +/-1 ℃, when the charge-discharge cutoff voltage is 2.8-4.3V, the material has the first discharge specific capacity of 200.4mAh/g under the charge-discharge multiplying power of 0.5C, the first-turn coulombic efficiency of 89.1 percent, and the capacity retention rate of only 82.7 percent after 100 cycles;
therefore, in the embodiment, the composite phosphate-coated lithium ion battery high-nickel cathode material LiNi0.8Co0.1Mn0.1O2The electrochemical performance of the alloy is comprehensively superior to that of a comparative example, and particularly, the alloy performs better at high temperature.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.

Claims (7)

1. The composite phosphate coated high-nickel cathode material of the lithium ion battery is characterized in that the cathode material is composed of a parent material and a composite coating layer coated on the surface of the parent material, the parent material is a high-nickel-cobalt binary cathode material, a high-nickel NCA ternary cathode material or a high-nickel NCM ternary cathode material, the composite coating layer is of a two-layer structure, wherein the inner coating layer is a Li (nickel-cobalt) -based coating layer3PO4The outer coating layer is YPO4/Y(PO3)3Compounding layers; the coating amount of the composite coating layer is 0.1-5 wt%.
2. The composite phosphate coated lithium ion battery high nickel positive electrode material of claim 1, wherein the composite coating layer is generated by in-situ reaction of yttrium metaphosphate with surface residual alkali of the parent material.
3. The preparation method of the composite phosphate coated lithium ion battery high nickel anode material according to claim 1, comprising the following steps:
step 1, with Y (PO)3)3For coating the raw material, Y (PO)3)3Dispersing in absolute ethyl alcohol to form a suspension solution;
step 2, adding the matrix material into the suspension solution obtained in the step 1, stirring at room temperature for 30-40 min, heating to 60-100 ℃, and stirring again until the absolute ethyl alcohol is evaporated to form mixture powder;
step 3, putting the mixture powder obtained in the step 2 into an oven for drying to obtain a dried sample;
and 4, putting the dried sample obtained in the step 3 into a tubular furnace, heating to 500-650 ℃ at the speed of 1-10 ℃/min in the oxygen atmosphere, sintering for 6-12 h, naturally cooling to room temperature, and thus obtaining the composite phosphate coated lithium ion battery high-nickel anode material.
4. The method for preparing the composite phosphate-coated high-nickel cathode material for the lithium ion battery according to claim 3, wherein the matrix material is LiNi0.9Co0.1O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2The preparation method comprises the following steps:
step 1, dissolving a lithium source raw material in deionized water, and correspondingly adding Ni0.9Co0.1(OH)2Precursor, Ni0.8Co0.15Al0.05(OH)2Precursor or Ni0.8Co0.1Mn0.1(OH)2The precursor is fully ground by using absolute ethyl alcohol as a dispersing agent and then dried to obtain mixture powder;
step 2, putting the mixture powder obtained in the step 1 into an oven for drying to obtain a dried sample;
and 3, putting the dried sample obtained in the step 2 into a tubular furnace, heating to 400-650 ℃ at the speed of 1-10 ℃/min for pre-sintering for 6-15 h in an oxygen atmosphere, heating to 700-950 ℃ at the speed of 1-10 ℃/min for roasting for 15-25 h, and naturally cooling to room temperature to obtain the high-nickel cathode material LiNi of the lithium ion battery0.9Co0.1O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.8Co0.1Mn0.1O2。
5. The method for preparing the composite phosphate coated lithium ion battery high-nickel cathode material according to claim 3, wherein the dosage of the coating raw material is as follows: the coating raw material accounts for 0.1-5 wt% of the matrix material.
6. The preparation method of the composite phosphate coated lithium ion battery high nickel cathode material according to claim 3 or 4, characterized in that the temperature of the oven is: and (3) drying at the temperature of 80-120 ℃ for the following time: 10-16 h.
7. The preparation method of the composite phosphate coated lithium ion battery high-nickel cathode material according to claim 3 or 4, characterized in that the oxygen flow rate of the oxygen atmosphere is 100-1000 ml/min.
CN202110509371.2A 2021-05-11 2021-05-11 Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof Pending CN113346055A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110509371.2A CN113346055A (en) 2021-05-11 2021-05-11 Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110509371.2A CN113346055A (en) 2021-05-11 2021-05-11 Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113346055A true CN113346055A (en) 2021-09-03

Family

ID=77470542

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110509371.2A Pending CN113346055A (en) 2021-05-11 2021-05-11 Composite phosphate coated high-nickel anode material of lithium ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113346055A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057240A (en) * 2022-01-14 2022-02-18 英德市科恒新能源科技有限公司 High-nickel positive electrode material capable of reducing residual alkali content, processing method thereof and lithium secondary battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011106597A1 (en) * 2010-02-25 2011-09-01 Corning Incorporated Making xenotime ceramics by reactive ceramming
CN110534721A (en) * 2019-09-11 2019-12-03 中南大学 A kind of restorative procedure of the tertiary cathode material of performance degradation and the tertiary cathode material of acquisition
CN110790321A (en) * 2019-11-06 2020-02-14 四川富骅新能源科技有限公司 Doped high-voltage NCA positive electrode material of lithium ion battery and preparation method thereof
CN111446434A (en) * 2020-04-23 2020-07-24 华鼎国联四川电池材料有限公司 Metaphosphate modified anode material and preparation method thereof
CN111769267A (en) * 2020-06-30 2020-10-13 中国科学院上海微系统与信息技术研究所 Composite positive electrode material of lithium ion battery and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011106597A1 (en) * 2010-02-25 2011-09-01 Corning Incorporated Making xenotime ceramics by reactive ceramming
CN110534721A (en) * 2019-09-11 2019-12-03 中南大学 A kind of restorative procedure of the tertiary cathode material of performance degradation and the tertiary cathode material of acquisition
CN110790321A (en) * 2019-11-06 2020-02-14 四川富骅新能源科技有限公司 Doped high-voltage NCA positive electrode material of lithium ion battery and preparation method thereof
CN111446434A (en) * 2020-04-23 2020-07-24 华鼎国联四川电池材料有限公司 Metaphosphate modified anode material and preparation method thereof
CN111769267A (en) * 2020-06-30 2020-10-13 中国科学院上海微系统与信息技术研究所 Composite positive electrode material of lithium ion battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057240A (en) * 2022-01-14 2022-02-18 英德市科恒新能源科技有限公司 High-nickel positive electrode material capable of reducing residual alkali content, processing method thereof and lithium secondary battery

Similar Documents

Publication Publication Date Title
CN108598400B (en) Three-layer core-shell structure cathode material, preparation method and lithium ion battery
CN113328069A (en) Lithium phosphate coated high-nickel cathode material of lithium ion battery and preparation method of lithium phosphate coated high-nickel cathode material
WO2021253714A1 (en) Carbon/titanium phosphate composite material and preparation method therefor and use thereof
CN110581269A (en) Lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material and preparation method thereof
CN105655577A (en) Method for improving high-temperature solid-phase reaction of anode material of lithium ion battery by wet lithium mixing
CN111564622A (en) Lithium manganese iron phosphate cathode material and preparation method thereof
JP4185191B2 (en) Method for producing spinel type lithium manganate
CN112018344B (en) Carbon-coated nickel sulfide electrode material and preparation method and application thereof
CN111293288B (en) NaF/metal composite sodium-supplementing positive electrode active material, positive electrode, preparation method of positive electrode and application of positive electrode in sodium electrovoltaics
CN111710849B (en) ZnS/SnS @ NC hollow microsphere anode material for lithium ion/sodium ion battery anode and preparation method thereof
CN113929070B (en) Preparation method of high-rate lithium iron phosphate cathode material
CN105024065A (en) Lithium ion battery cathode material and preparation method thereof
CN113314700A (en) Dual-action modified high-nickel positive electrode material of lithium ion battery and preparation method of dual-action modified high-nickel positive electrode material
CN113104824A (en) Se doped Fe2Preparation method of P self-supporting sodium ion battery cathode material
CN112467139A (en) Lithium ion battery positive electrode pre-lithiation agent and preparation method and application thereof
CN111994890A (en) Vanadium phosphate sodium composite anode material and preparation method thereof
CN107946564B (en) Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof
CN114497694A (en) Lithium supplement agent for manufacturing lithium ion battery and preparation method thereof
CN102832381A (en) Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life
CN101901900B (en) Method for preparing carbon-coated phosphate composite material for negative electrode of lithium ion battery
CN103413918A (en) Synthetic method for cathode material lithium cobaltous phosphate used for lithium ion batteries
CN111384366B (en) alpha-MnO 2 Carbon/carbon composite electrode material and preparation method and application thereof
CN105789621B (en) A method of molten state lithium source surface tension is reduced so as to improve anode material for lithium-ion batteries high temperature solid-phase sintering process
CN111477872A (en) Water-based lithium/sodium ion battery with iron-doped sodium titanium phosphate as negative electrode active material and preparation method thereof
CN110620217A (en) Zinc-doped lithium iron phosphate/carbon composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination