CN108321366A - Coating method for improving electrochemical performance of high-nickel ternary nickel-cobalt-manganese positive electrode material - Google Patents
Coating method for improving electrochemical performance of high-nickel ternary nickel-cobalt-manganese positive electrode material Download PDFInfo
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- CN108321366A CN108321366A CN201711459381.XA CN201711459381A CN108321366A CN 108321366 A CN108321366 A CN 108321366A CN 201711459381 A CN201711459381 A CN 201711459381A CN 108321366 A CN108321366 A CN 108321366A
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- lithium
- nickel cobalt
- cobalt manganese
- anode material
- ternary nickel
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 11
- 229910052759 nickel Inorganic materials 0.000 title abstract description 9
- 239000007774 positive electrode material Substances 0.000 title abstract 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 63
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000010405 anode material Substances 0.000 claims description 74
- 239000000126 substance Substances 0.000 claims description 29
- 238000005253 cladding Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 claims description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 2
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 2
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 13
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 206010001497 Agitation Diseases 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000002908 manganese Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a coating method for improving the electrochemical performance of a high-nickel ternary nickel-cobalt-manganese positive electrode material, which comprises the following steps: dissolving a titanium source in a solvent to form a solution, adding a lithium source to dissolve the solution, and then adding citric acid to obtain a mixed solution; uniformly dispersing the high-nickel ternary nickel-cobalt-manganese positive electrode material in a solvent, adding the mixed solution, uniformly mixing, and then carrying out hydrothermal reaction or solvothermal reaction to obtain a reaction solution; evaporating the reaction solution to be gelatinous, and drying to obtain a positive electrode material mixture; and calcining the positive electrode material mixture to obtain the high-nickel ternary nickel cobalt manganese positive electrode material with the lithium titanate coating layer on the surface. The coating method for improving the electrochemical performance of the high-nickel ternary nickel-cobalt-manganese positive electrode material is simple in process, low in cost and good in repeatability, the obtained coating layer is high in crystallinity, small in particle size and good in uniformity, and the specific discharge capacity, the cycle performance and the rate performance of the high-nickel ternary nickel-cobalt-manganese positive electrode material are improved.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field more particularly to a kind of nickelic ternary nickel cobalt manganeses of raising just
The method for coating of pole material electrochemical performance.
Background technology
With the growth to high energy battery demand, it have stimulated researcher and lithium ion battery with high performance ground
Study carefully.Wherein, nickelic tertiary cathode material is attracted attention with the advantage of high-energy density, but high-nickel material is because of stringent storage item
The shortcomings of part, poor circulation and poor thermal stability, limits its practical application.
Surface cladding is a kind of effective ways for the problems such as solving battery irreversible capacity loss and cycle deterioration, clad
Presence, hinder to be in direct contact between electrolyte and active material, reduce side reaction, inhibit metal ion dissolving, reduce electrode
Degree of polarization maintains material structure to stablize, to improve the chemical property of electrode.
Li4Ti5O12With spinel structure, Fd3m space groups, diffusion coefficient 10-6cm2s-1, be conducive to as clad
Li+Diffusion, stability is high, has smooth discharge voltage plateau, anti-over-charging and over-discharge.In addition, Li4Ti5O12With " zero
The special construction feature of strain ", can be to avoid the destruction generated to its structure due to the variation of electrode volume repeatedly, even if in height
Also structural stability is able to maintain that under charging voltage.In addition to this, Li4Ti5O12Electrolyte decomposition can be avoided, metal ion
Dissolving, the formation of solid electrolyte interface film.In addition, Li4Ti5O12It is a kind of negative material, the one of positive electrode can be made up
A little defects, and portion capacity can be contributed, this is of great significance to improving battery capacity.
Researcher often uses the conventional methods such as ball-milling method, coprecipitation, sol-gal process to wrap the surface for carrying out material
It covers.But for these methods there are certain defect, such as presoma price height, preprocessing process complexity and industrialized production difficulty are big,
And the chemical property of positive electrode is very sensitive to crystallinity, the purity of phase, particle shape, homogeneity etc., these factors
It is again closely related with the synthetic method and synthesis condition of material.Such as the patent document that China Patent Publication No. is CN106450216A
In, a kind of modified nickel cobalt aluminium positive electrode and preparation method thereof is disclosed, the preparation of the nickel cobalt aluminium lithium tertiary cathode material includes：
Titanium source is mixed with nickel cobalt aluminium presoma first, then carries out hydro-thermal or solvent thermal reaction, amorphous is obtained by filtration washing
The nickel cobalt aluminium presoma of titanium oxide cladding, finally will obtain modified nickel after presoma, lithium source and solvent again mixed sintering
Cobalt aluminium positive electrode.But mixed again with lithium source by filtration washing after these technical steps, hydro-thermal or solvent thermal reaction, it obtains
The product uniformity arrived is bad, and clad is uneven.
Invention content
Technical problems based on background technology, the present invention propose a kind of nickelic ternary nickel cobalt manganese anode material of raising
The method for coating of chemical property, process is simple, at low cost, reproducible, and obtained clad crystallinity is high, particle diameter
It is small, homogeneity is good, improve specific discharge capacity, cycle performance and the high rate performance of nickelic ternary nickel cobalt manganese anode material, significantly
Optimize the chemical property of nickelic ternary nickel cobalt manganese anode material.
A kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property proposed by the present invention, including with
Lower step：
S1, it titanium source is dissolved in solvent forms solution, lithium source dissolving is added, citric acid is then added and obtains mixed solution；
S2, nickelic ternary nickel cobalt manganese anode material is dispersed in solvent, the mixed solution in S1 is added, mixing is equal
Hydro-thermal reaction is carried out after even or solvent thermal reaction obtains reaction solution；
S3, the reaction solution in S2 is evaporated to gel, positive electrode mixture is obtained after dry；
S4, the positive electrode mixture in S3 is calcined to obtain surface there is the nickelic ternary nickel cobalt manganese of lithium titanate clad
Positive electrode.
Preferably, in S1, the titanium source is positive four butyl ester of metatitanic acid, tetraethyl titanate, isopropyl titanate, titanium oxide, oxygen
Change the mixture of one or more of titanous, titanium tetrachloride, hexafluorotitanic acid, cobalt titanate, nickel titanate, manganese titanate；The lithium
Source is in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium fluoride, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate
One or more kinds of mixtures.
Preferably, in S1 and S2, the solvent is one kind in water, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, acetone
Or a variety of mixture.
Preferably, in S2, the nickelic ternary nickel cobalt manganese anode material chemical formula is LiNixCoyMn1-x-yO2, wherein
0.5≤x ＜ 1,0 ＜ y≤0.5,0<x+y<1.
Preferably, in S2, nickelic ternary nickel cobalt manganese anode material is dispersed in solvent, is added dropwise in S1
Magnetic agitation 30-60min after mixed solution, and magnetic stirring speed is 300-600rpm.
Preferably, in S2, the temperature of hydro-thermal reaction or solvent thermal reaction is 150-200 DEG C, time 12-24h.
Preferably, in S3, the reaction solution in S2 is stirred under conditions of 60-80 DEG C and is evaporated to gel.
Preferably, in S3, the drying is vacuum drying, and vacuum drying temperature is 60-100 DEG C, time 6-
12h。
Preferably, in S4, the concrete technology of the calcining is：Under air atmosphere or oxygen atmosphere, with 3-5 DEG C/
The heating rate of min is heated to 600-800 DEG C, calcines 3-8h.
Preferably, in S4, in the nickelic ternary nickel cobalt manganese anode material that surface has lithium titanate clad, lithium titanate
Mass ratio with nickelic ternary nickel cobalt manganese anode material is 0.005-0.1：1.
The method for coating of the present invention for improving nickelic ternary nickel cobalt manganese anode material chemical property, to existing lithium from
The method for preparing anode material of sub- battery surface cladding is improved, by titanium source and nickelic ternary nickel cobalt manganese anode material and lithium source
It is mixed under liquid phase, using hydro-thermal method or solvent-thermal method, is preparing the nickelic ternary nickel cobalt manganese of surface cladding lithium titanate just
Pole material.The nickelic ternary nickel cobalt manganese electrode material of surface cladding lithium titanate prepared by hydro-thermal method or solvent-thermal method, passes with using
The nickelic ternary nickel cobalt manganese anode material of surface cladding lithium titanate prepared by the sol-gal process of system is compared, advantage packet
It includes：
1, by carrying out surface coating modification to nickelic ternary nickel cobalt manganese anode material, electrolyte and active material can be hindered
It is in direct contact between material, reduces side reaction.
2, the lithium titanate clad with " zero strain " structure, Neng Gouwei are generated in the positive material surface of nickelic ternary nickel cobalt manganese
Electrode structure stabilization is held, Li is promoted+Diffusion inhibits metal ion dissolving, reduces electrode polarization degree.
3, it carries out nickelic ternary nickel cobalt manganese anode material surface using hydro-thermal method or solvent-thermal method to coat, be collected using evaporation
Product is added citric acid as chelating agent, directly coats on positive electrode surface, under high-temperature and high-pressure conditions, can prepare
The positive electrode that the small and uniform particle shape of pure phase, grain size with ideal highly crystalline, surface are evenly coated, significantly carries
High discharge capacity, cycle performance and the high rate performance of nickelic ternary nickel cobalt manganese anode material, first discharge specific capacity are up to
210mAh/g optimizes the electrification of nickelic ternary nickel cobalt manganese anode material higher than sample 15.1mAh/g prepared by sol-gal process
Learn performance.
4, the method for the present invention is simple, reproducible, has the height of lithium titanate clad with surface prepared by sol-gal process
Nickel ternary nickel cobalt manganese anode material is compared, and the specific discharge capacity, cycle performance and high rate performance of electrode material are improved.
Description of the drawings
Fig. 1 is nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O21 solvent-thermal method of embodiment coats 1wt% titaniums
XRD spectrum after sour lithium and 2 sol-gal process of embodiment cladding 1wt% lithium titanates；
Fig. 2 is nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O21 solvent-thermal method of embodiment coats 1wt% titaniums
Cycle performance figure after sour lithium and 2 sol-gal process of embodiment cladding 1wt% lithium titanates；
Fig. 3 is nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O21 solvent-thermal method of embodiment coats 1wt% titaniums
High rate performance figure after sour lithium and 2 sol-gal process of embodiment cladding 1wt% lithium titanates；
Fig. 4 is nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O21 solvent-thermal method of embodiment coats 1wt% titaniums
The AC impedance figure of sour lithium and 2 sol-gal process of embodiment cladding 1wt% lithium titanates cycle after 50 weeks.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property proposed by the present invention, including with
Lower step：
S1, according to lithium titanate：Nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O2Mass ratio be 1：100,
Positive four butyl ester of metatitanic acid is dissolved in 30ml absolute ethyl alcohols, forms solution after being dissolved under 400rpm magnetic agitations, lithium acetate is added
Then dissolving is added citric acid and obtains mixed solution；
S2, by the nickelic ternary nickel cobalt manganese anode material LiNi of 5g0.8Co0.1Mn0.1O2It is dispersed in 50ml absolute ethyl alcohols
In, magnetic force is sufficiently stirred 30min, and the mixed solution in S1, and magnetic agitation 30min is added dropwise, is transferred to after mixing
It in 100ml hydrothermal reaction kettles, is placed in drying box, is reacted at 180 DEG C and obtain reaction solution for 24 hours；
S3, the reaction solution taking-up in S2 is put into beaker, is placed on magnetic force heating stirring machine, under conditions of 70 DEG C
Stirring is evaporated to gel, is added in vacuum drying chamber, and dry 12h obtains positive electrode mixture at 80 DEG C；
S4, by the positive electrode mixture in S3 under air atmosphere, be heated to 800 DEG C with the heating rate of 5 DEG C/min,
5h is calcined, obtaining surface has the nickelic ternary nickel cobalt manganese anode material LiNi of 1wt% lithium titanate clads0.8Co0.1Mn0.1O2。
According to active material, (surface has the nickelic ternary nickel cobalt manganese anode material of 1wt% lithium titanate clads
LiNi0.8Co0.1Mn0.1O2), acetylene black, PVDF mass ratioes be 85:10:5 are coated, dry, by electrode material full of argon
In the glove box of gas atmosphere, CR2025 type button cells are assembled into, cathode is metal lithium sheet, diaphragm Celgard2300, electrolysis
(group becomes EC, EMC, DMC, volume ratio 1 to the LiPF6 that liquid is 1mol/L:1:1), using the blue electricity CT2001A circulating batteries in Wuhan
Test system carries out the constant current charge-discharge test of battery, and test results are shown in figure 2.
Embodiment 2
A kind of method for coating of nickelic ternary nickel cobalt manganese anode material chemical property, includes the following steps：
S1, according to lithium titanate：Nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O2Mass ratio be 1：100,
Positive four butyl ester of metatitanic acid is dissolved in 30ml absolute ethyl alcohols, forms solution after being dissolved under 400rpm magnetic agitations, lithium acetate is added
Then dissolving is added citric acid and obtains mixed solution；
S2, by the nickelic ternary nickel cobalt manganese anode material LiNi of 5g0.8Co0.1Mn0.1O2It is dispersed in 50ml absolute ethyl alcohols
In, magnetic force is sufficiently stirred 30min, the mixed solution in S1, and fully magnetic agitation 30min is added dropwise, in 70 DEG C of condition
Lower stirring is evaporated to gel, is added in vacuum drying chamber, and dry 12h obtains positive electrode mixture at 80 DEG C；
S3, by the positive electrode mixture in S2 under air atmosphere, be heated to 800 DEG C with the heating rate of 5 DEG C/min,
5h is calcined, obtaining surface has the nickelic ternary nickel cobalt manganese anode material LiNi of 1wt% lithium titanate clads0.8Co0.1Mn0.1O2。
According to active material (the nickelic ternary nickel cobalt manganese anode material with 1wt% lithium titanate clads
LiNi0.8Co0.1Mn0.1O2), acetylene black, PVDF mass ratioes be 85:10:5 are coated, dry, by electrode material full of argon
In glove box in the atmosphere of gas, it being assembled into CR2025 type button cells, cathode is metal lithium sheet, diaphragm Celgard2300,
(group becomes EC, EMC, DMC, volume ratio 1 to the LiPF6 that electrolyte is 1mol/L:1:1), using the blue electricity CT2001A batteries in Wuhan
Loop test system carries out the constant current charge-discharge test of battery, and test results are shown in figure 2.
Surface prepared by embodiment 1 and embodiment 2 has the nickelic ternary nickel cobalt manganese anode of 1wt% lithium titanate clads
Material carries out XRD tests, and the results are shown in Figure 1 by XRD, and as shown in Figure 1, the sample that embodiment 1 and embodiment 2 obtain all has
Good layer structure, XRD spectra lattice parameter are as shown in table 1：
Table 1 is XRD spectra lattice parameter
As can be seen from Table 1, sample I (003)/I (104) bigger of 1 solvent-thermal method of embodiment cladding, cationic mixing degree
Smaller, lattice structure are more stablized.
As seen from Figure 2, the surface that prepared by 1 solvent-thermal method of embodiment has nickelic the three of 1wt% lithium titanate clads
First nickel cobalt manganese anode material discharging specific capacity is coated higher than surface prepared by 2 sol-gal process of embodiment with 1wt% lithium titanates
The nickelic ternary nickel cobalt manganese anode material of layer, the sample capacity conservation rate that after 1C is recycled 50 weeks prepared by 1 solvent-thermal method of embodiment are
91.1%, sample capacity conservation rate prepared by 2 sol-gal process of embodiment is 88%, surface prepared by 1 solvent-thermal method of embodiment
Nickelic ternary nickel cobalt manganese anode material LiNi with 1wt% lithium titanate clads0.8Co0.1Mn0.1O2Cycle performance is more excellent.
Fig. 3 is nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O21 solvent-thermal method of embodiment coats 1wt% titaniums
High rate performance figure after sour lithium and 2 sol-gal process of embodiment cladding 1wt% lithium titanates, as seen from Figure 3, solvent-thermal method packet
The LiNi covered0.8Co0.1Mn0.1O2High rate performance is better than sol-gal process, and specific discharge capacity is above the latter under each multiplying power, greatly
Under multiplying power discharging, material capacity decaying prepared by sol-gal process is serious, material prepared by solvent-thermal method, and discharge ratio under 5C multiplying powers
Capacity is higher than the latter 18.9mAh/g, shows excellent high rate performance.
Fig. 4 is nickelic ternary nickel cobalt manganese anode material LiNi0.8Co0.1Mn0.1O21 solvent-thermal method of embodiment coats 1wt% titaniums
The AC impedance figure of sour lithium and 2 sol-gal process of embodiment cladding 1wt% lithium titanates cycle after 50 weeks, it is as seen from Figure 4, molten
The LiNi of the hot method cladding of agent0.8Co0.1Mn0.1O2Charge-transfer resistance and SEI membrane impedances are respectively less than sol-gal process cladding
LiNi0.8Co0.1Mn0.1O2, it was demonstrated that solvent-thermal method coats the Charge-transfer resistance and SEI membrane impedances that can reduce electrode material, tool
Standby higher Li+Diffusivity, more electrode kinetics behavior.
Compared to sol-gal process, solvent-thermal method is in nickelic tertiary cathode material LiNi0.8Co0.1Mn0.1O2Upper cladding metatitanic acid
Lithium has more uniform clad, higher Li+Deintercalation efficiency, the Li of bigger+Diffusivity and smaller impedance, improve lithium
The nickelic tertiary cathode material LiNi of ion battery0.8Co0.1Mn0.1O2Chemical property.
Embodiment 3
A kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property proposed by the present invention, including with
Lower step：
S1, it titanium source is dissolved in solvent forms solution, lithium source dissolving is added, citric acid is then added and obtains mixed solution；
S2, nickelic ternary nickel cobalt manganese anode material is dispersed in solvent, the mixed solution in S1 is added, mixing is equal
Hydro-thermal reaction is carried out after even obtains reaction solution；
S3, the reaction solution in S2 is evaporated to gel, positive electrode mixture is obtained after dry；
S4, the positive electrode mixture in S3 is calcined to obtain surface there is the nickelic ternary nickel cobalt manganese of lithium titanate clad
Positive electrode.
Embodiment 4
A kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property proposed by the present invention, including with
Lower step：
S1, by titanium source formation solution soluble in water, lithium source dissolving is added, citric acid is then added and obtains mixed solution；Its
In, the titanium source is the mixture of tetraethyl titanate, isopropyl titanate, and the weight ratio of tetraethyl titanate, isopropyl titanate is
3：2；The lithium source is lithium dihydrogen phosphate；
S2, nickelic ternary nickel cobalt manganese anode material is dispersed in water, magnetic after the mixed solution in S1 is added dropwise
Power stirs 30min, and magnetic stirring speed is 600rpm, is transferred in hydrothermal reaction kettle, is carried out at 150 DEG C after mixing
Hydro-thermal reaction obtains reaction solution for 24 hours；Wherein, the nickelic ternary nickel cobalt manganese anode material chemical formula is
LiNi0.6Co0.2Mn0.2O2；
S3, it the reaction solution in S2 is stirred under conditions of 60 DEG C is evaporated to gel, 6h is dried in vacuo at 100 DEG C
After obtain positive electrode mixture；
S4, by the positive electrode mixture in S3 under air atmosphere, be heated to 600 DEG C with the heating rate of 5 DEG C/min,
Calcining 8h, which obtains surface, has the nickelic ternary nickel cobalt manganese anode material of lithium titanate clad；Wherein, there is lithium titanate on surface
In the nickelic ternary nickel cobalt manganese anode material of clad, the mass ratio of lithium titanate and nickelic ternary nickel cobalt manganese anode material is
0.005：1.
Embodiment 5
A kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property proposed by the present invention, including with
Lower step：
S1, it titanium source is dissolved in ethyl alcohol forms solution, lithium source dissolving is added, citric acid is then added and obtains mixed solution；
Wherein, the titanium source is positive four butyl ester of metatitanic acid；The lithium source is the mixture of lithium carbonate, lithium nitrate, and lithium carbonate, lithium nitrate
Weight ratio is 3:2；
S2, nickelic ternary nickel cobalt manganese anode material is dispersed in ethyl alcohol, after the mixed solution in S1 is added dropwise
Magnetic agitation 60min, and magnetic stirring speed be 300rpm, be transferred in hydrothermal reaction kettle after mixing, at 200 DEG C into
Row solvent thermal reaction 12h obtains reaction solution；Wherein, the nickelic ternary nickel cobalt manganese anode material chemical formula is
LiNi0.6Co0.2Mn0.2O2；
S3, it the reaction solution in S2 is stirred under conditions of 80 DEG C is evaporated to gel, 12h is dried in vacuo at 60 DEG C
After obtain positive electrode mixture；
S4, by the positive electrode mixture in S3 under oxygen atmosphere, be heated to 800 DEG C with the heating rate of 3 DEG C/min,
Calcining 3h, which obtains surface, has the nickelic ternary nickel cobalt manganese anode material of lithium titanate clad；Wherein, there is lithium titanate on surface
In the nickelic ternary nickel cobalt manganese anode material of clad, the mass ratio of lithium titanate and nickelic ternary nickel cobalt manganese anode material is 0.1：
1。
Embodiment 6
A kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property proposed by the present invention, including with
Lower step：
S1, it titanium source is dissolved in solvent forms solution, lithium source dissolving is added, citric acid is then added and obtains mixed solution；
Wherein, the titanium source be positive four butyl ester of metatitanic acid, cobalt titanate, nickel titanate mixture, and positive four butyl ester of metatitanic acid, cobalt titanate, metatitanic acid
The weight ratio of nickel is 3:4:2；The lithium source is the mixture of lithium carbonate, lithium acetate, lithium phosphate, and lithium carbonate, lithium acetate, phosphoric acid
The weight ratio of lithium is 4：3：2；The solvent is the mixture of ethyl alcohol, isopropanol, and the volume ratio of ethyl alcohol, isopropanol is 3:2；
S2, nickelic ternary nickel cobalt manganese anode material is dispersed in solvent, after the mixed solution in S1 is added dropwise
Magnetic agitation 50min, and magnetic stirring speed be 500rpm, be transferred in hydrothermal reaction kettle after mixing, at 170 DEG C into
Row solvent thermal reaction 20h obtains reaction solution；Wherein, the nickelic ternary nickel cobalt manganese anode material chemical formula is
LiNi0.8Co0.1Mn0.1O2；The solvent is the mixture of ethyl alcohol, isopropanol, and the volume ratio of ethyl alcohol, isopropanol is 3:2；
S3, it the reaction solution in S2 is stirred under conditions of 70 DEG C is evaporated to gel, 10h is dried in vacuo at 80 DEG C
After obtain positive electrode mixture；
S4, by the positive electrode mixture in S3 under oxygen atmosphere, be heated to 700 DEG C with the heating rate of 4 DEG C/min,
Calcining 6h, which obtains surface, has the nickelic ternary nickel cobalt manganese anode material of lithium titanate clad；Wherein, there is lithium titanate on surface
In the nickelic ternary nickel cobalt manganese anode material of clad, the mass ratio of lithium titanate and nickelic ternary nickel cobalt manganese anode material is
0.06:1。
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property, which is characterized in that including following
Step：
S1, it titanium source is dissolved in solvent forms solution, lithium source dissolving is added, citric acid is then added and obtains mixed solution；
S2, nickelic ternary nickel cobalt manganese anode material is dispersed in solvent, the mixed solution in S1 is added, after mixing
It carries out hydro-thermal reaction or solvent thermal reaction obtains reaction solution；
S3, the reaction solution in S2 is evaporated to gel, positive electrode mixture is obtained after dry；
S4, the positive electrode mixture in S3 is calcined to obtain nickelic ternary nickel cobalt manganese anode of the surface with lithium titanate clad
Material.
2. improving the method for coating of nickelic ternary nickel cobalt manganese anode material chemical property, feature according to claim 1
It is, in S1, the titanium source is positive four butyl ester of metatitanic acid, tetraethyl titanate, isopropyl titanate, titanium oxide, oxidation titanous, tetrachloro
Change the mixture of one or more of titanium, hexafluorotitanic acid, cobalt titanate, nickel titanate, manganese titanate；The lithium source is hydroxide
One kind in lithium, lithium carbonate, lithium nitrate, lithium acetate, lithium chloride, lithium fluoride, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate or
A variety of mixtures.
3. the method for coating according to claim 1 or claim 2 for improving nickelic ternary nickel cobalt manganese anode material chemical property, special
Sign is, in S1 and S2, the solvent is one or more of water, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, acetone
Mixture.
4. according to the cladding sides for improving nickelic ternary nickel cobalt manganese anode material chemical property any one of claim 1-3
Method, which is characterized in that in S2, the nickelic ternary nickel cobalt manganese anode material chemical formula is LiNixCoyMn1-x-yO2, wherein 0.5
≤ x ＜ 1,0 ＜ y≤0.5,0<x+y<1.
5. according to the cladding sides for improving nickelic ternary nickel cobalt manganese anode material chemical property any one of claim 1-4
Method, which is characterized in that in S2, nickelic ternary nickel cobalt manganese anode material is dispersed in solvent, is added dropwise in S1
Magnetic agitation 30-60min after mixed solution, and magnetic stirring speed is 300-600rpm.
6. according to the cladding sides for improving nickelic ternary nickel cobalt manganese anode material chemical property any one of claim 1-5
Method, which is characterized in that in S2, the temperature of hydro-thermal reaction or solvent thermal reaction is 150-200 DEG C, time 12-24h.
7. according to the cladding sides for improving nickelic ternary nickel cobalt manganese anode material chemical property any one of claim 1-6
Method, which is characterized in that in S3, the reaction solution in S2 is stirred under conditions of 60-80 DEG C and is evaporated to gel.
8. according to the cladding sides for improving nickelic ternary nickel cobalt manganese anode material chemical property any one of claim 1-7
Method, which is characterized in that in S3, the drying is vacuum drying, and vacuum drying temperature is 60-100 DEG C, time 6-12h.
9. according to the cladding sides for improving nickelic ternary nickel cobalt manganese anode material chemical property any one of claim 1-8
Method, which is characterized in that in S4, the concrete technology of the calcining is：Under air atmosphere or oxygen atmosphere, with 3-5 DEG C/
The heating rate of min is heated to 600-800 DEG C, calcines 3-8h.
10. according to any one of the claim 1-9 claddings for improving nickelic ternary nickel cobalt manganese anode material chemical property
Method, which is characterized in that in S4, in the nickelic ternary nickel cobalt manganese anode material that surface has lithium titanate clad, metatitanic acid
The mass ratio of lithium and nickelic ternary nickel cobalt manganese anode material is 0.005-0.1：1.
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| CN113363478A (en) * | 2021-03-30 | 2021-09-07 | 万向一二三股份公司 | Coating agent for coating high-nickel ternary cathode material, preparation method and lithium ion battery |
| CN113113588A (en) * | 2021-04-09 | 2021-07-13 | 合肥工业大学 | Method for preparing lithium fast ion conductor material coated high-nickel ternary layered oxide by using covalent interface engineering strategy |
| CN113113588B (en) * | 2021-04-09 | 2022-11-08 | 合肥工业大学 | Method for preparing lithium fast ion conductor material coated high-nickel ternary layered oxide by using covalent interface engineering strategy |
| CN113293441A (en) * | 2021-04-15 | 2021-08-24 | 江苏大学 | Preparation method of strontium titanate coated single crystal nickel-rich ternary cathode material |
| CN113346081A (en) * | 2021-05-27 | 2021-09-03 | 南京市永信合智能科技有限公司 | Method for preparing carbon-coated ternary cathode nano material by alkyne oxidation |
| CN113437273B (en) * | 2021-06-28 | 2022-10-11 | 北京理工大学 | All-solid-state lithium ion battery positive electrode material with coating layer on outer layer and preparation method thereof |
| CN113437273A (en) * | 2021-06-28 | 2021-09-24 | 北京理工大学 | All-solid-state lithium ion battery positive electrode material with coating layer on outer layer and preparation method thereof |
| CN113839040A (en) * | 2021-08-31 | 2021-12-24 | 蜂巢能源科技有限公司 | High-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN114050240A (en) * | 2021-11-05 | 2022-02-15 | 合肥国轩高科动力能源有限公司 | Titanium-doped porous ternary material and preparation method thereof, half battery and lithium ion battery |
| CN114050240B (en) * | 2021-11-05 | 2023-03-14 | 合肥国轩高科动力能源有限公司 | Titanium-doped porous ternary material, preparation method thereof, half battery and lithium ion battery |
| CN114843484A (en) * | 2022-05-24 | 2022-08-02 | 惠州锂威新能源科技有限公司 | High-nickel ternary positive electrode material modified by titanium dioxide and lithium aluminate, preparation method thereof and lithium battery |
| CN114843484B (en) * | 2022-05-24 | 2023-09-22 | 惠州锂威新能源科技有限公司 | High-nickel ternary positive electrode material modified by titanium dioxide and lithium aluminate, preparation method thereof and lithium battery |
| EP4322259A4 (en) * | 2022-06-16 | 2024-06-12 | Contemporary Amperex Technology Co., Limited | Positive electrode material, manufacturing method therefor, and secondary battery having same |
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