CN117038938B - Positive electrode lithium supplementing agent and preparation method and application thereof - Google Patents
Positive electrode lithium supplementing agent and preparation method and application thereof Download PDFInfo
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- CN117038938B CN117038938B CN202311281444.2A CN202311281444A CN117038938B CN 117038938 B CN117038938 B CN 117038938B CN 202311281444 A CN202311281444 A CN 202311281444A CN 117038938 B CN117038938 B CN 117038938B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 81
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical class O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 claims abstract description 42
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 25
- 150000002641 lithium Chemical class 0.000 claims abstract description 25
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 239000006258 conductive agent Substances 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 10
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- HQRWWHIETAKIMO-UHFFFAOYSA-N 1-phenylbutan-1-ol Chemical compound CCCC(O)C1=CC=CC=C1 HQRWWHIETAKIMO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 239000002002 slurry Substances 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000013589 supplement Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 3
- 238000007719 peel strength test Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LDZLXQFDGRCELX-UHFFFAOYSA-N 4-phenylbutan-1-ol Chemical compound OCCCCC1=CC=CC=C1 LDZLXQFDGRCELX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
-
- 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
The application belongs to the technical field of positive electrode materials of lithium ion batteries, and particularly relates to a positive electrode lithium supplementing agent, a preparation method and application thereof. The positive electrode lithium supplementing agent provided by the application comprises lithium oxide and a coating layer; the coating layer is coated on the surface of the lithium oxide; the coating is dibenzo-18-crown-6 derivative; the application also provides a positive plate which comprises a positive current collector and a positive material layer; wherein the positive electrode material layer comprises a positive electrode active material, a modified lithium polyacrylate binder, a conductive agent and a positive electrode lithium supplementing agent; the positive electrode lithium supplementing agent prepared by the method has good stability, can release enough lithium ions, is used for supplementing lithium ions consumed in the circulation process, has good lithium supplementing effect, can effectively improve the first coulomb efficiency and the overall electrochemical performance of the battery, and prolongs the service life of the battery.
Description
Technical Field
The application belongs to the technical field of positive electrode materials of lithium ion batteries, and particularly relates to a positive electrode lithium supplementing agent, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of longer cycle service life, higher energy density, environmental protection and the like, is widely paid attention to society, and along with the rapid development of new energy automobile markets, the requirements of people on the vehicle endurance and the energy density of the lithium ion battery are higher and higher. But lithium ionDuring the first charge of the battery, the surface of the negative electrode is usually accompanied by the formation of a solid electrolyte film SEI film, which consumes a large amount of Li + Meaning Li extracted from the positive electrode material + Part of the battery is irreversibly consumed, and the reversible specific capacity of the corresponding battery cell is reduced. Usually, a small amount of lithium supplementing agent is added in the pulping process of the anode material, and a large amount of Li is added in the charging process + Is separated from the lithium supplementing agent, thereby supplementing the reversible capacity loss of the battery caused by first charge and discharge.
The existing positive electrode lithium supplementing agent has the problems that the air is unstable, the reversible capacity of a battery is reduced and the like; patent application number 201811091563.0 discloses a lithium ion battery anode lithium supplementing material Li 5 FeO 4 The preparation method and the application of the lithium-containing material are that the lithium-containing material is used as a lithium source, the iron-containing material is used as an iron source, the complexing agent and the solvent are used as raw materials to synthesize stable sol, the sol is dried to obtain xerogel, and the xerogel is sintered to obtain the anode lithium-supplementing material Li 5 FeO 4 The prepared material has the characteristics of large charging capacity and small discharge capacity when used as a lithium ion battery anode lithium supplementing material, but has the defects of severe environmental adaptability, large surface residual alkali, difficult processing and the like; the patent with the application number of 202210278685.0 discloses a carbon-coated lithium ferrite material and a preparation method thereof, alkane mixed gas is adopted as a carbon source for vapor deposition to obtain the carbon-coated lithium ferrite material, and the formed carbon coating can relieve the contact between lithium ferrite and water in the air, so that the stability of the material is improved; however, the carbon coating is difficult to thoroughly isolate from contact with water in the air, which leads to deterioration and failure of the material.
Therefore, it is necessary to find a positive electrode lithium-supplementing agent with better stability to supplement the reversible capacity loss of the battery, thereby obtaining a battery with higher energy density and cycle stability.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides the positive electrode lithium supplementing agent, and the preparation method and application thereof.
The technical scheme adopted by the application for achieving the purpose is as follows:
a positive electrode lithium supplementing agent comprises lithium oxide and a coating layer; the coating layer is coated on the surface of the lithium oxide; the coating is dibenzo-18-crown-6 derivative; the thickness of the coating layer is 30-50nm.
Further, the preparation method of the dibenzo-18-crown-6 derivative comprises the following steps: sequentially adding dibenzo-18-crown-6 and phenylbutanol into polyphosphoric acid, heating to 70-80 ℃, reacting for 6-8h, naturally cooling to room temperature after the reaction is completed, slowly dripping water into the reaction liquid, stirring for 15-20min, adding dichloromethane for extraction, washing an organic phase with 20-30% sodium hydroxide solution for 2-3 times, washing with distilled water to neutrality, concentrating under reduced pressure to obtain a crude product, and recrystallizing with toluene and n-heptane to obtain the product.
Further, the molar ratio of the dibenzo-18-crown-6 to the phenylbutanol is 1:0.4-0.5; the dosage of the polyphosphoric acid is 8-10 times of the mass of the dibenzo-18-crown ether-6; the volume ratio of toluene to n-heptane is 1:1-2.
Further, the dibenzo-18-crown-6 derivative is a mixture of a compound 1 and a compound 2, and the synthetic route is as follows:
；
the application provides a preparation method of a positive electrode lithium supplementing agent, which comprises the steps of adding dibenzo-18-crown ether-6 derivatives into dichloromethane, stirring for 10-15min, adding lithium oxide, stirring until the lithium oxide is uniformly dispersed, centrifuging, removing supernatant, and drying to obtain the positive electrode lithium supplementing agent; wherein the mass ratio of the dibenzo-18-crown-6 derivative to the lithium oxide is 3-5:100.
The application provides application of the positive electrode lithium supplementing agent, namely the positive electrode lithium supplementing agent is used for preparing a positive electrode plate, and the positive electrode plate comprises a positive electrode current collector and a positive electrode material layer; the positive electrode material layer comprises a positive electrode active material, a modified lithium polyacrylate binder, a conductive agent and the positive electrode lithium supplementing agent.
Further, the positive electrode active material is lithium cobaltate; the conductive agent is one or more of carbon black, carbon nano tube and graphene; the mass of the positive electrode lithium supplementing agent is 3-5% of the mass of the positive electrode material layer.
Further, the preparation method of the modified lithium polyacrylate binder comprises the following steps:
s1, adding methacrylic acid and lithium hydroxide into water, and reacting for 1-2 hours at room temperature to obtain lithium methacrylate; wherein the molar ratio of the methacrylic acid to the lithium hydroxide is 1:1; the reaction process is as follows:
；
s2, adding lithium methacrylate and phenyl acrylate into a mixed solvent, heating to 80-90 ℃, dropwise adding an ammonium persulfate aqueous solution with the mass fraction of 40-50%, and continuing to react for 6-8 hours after the completion of the dropwise adding, so as to obtain a modified lithium polyacrylate binder; wherein the molar ratio of the lithium methacrylate to the phenyl acrylate is 1:1-1.1; the mass fraction of the lithium methacrylate is 30-50%; the dosage of the ammonium persulfate is 6-8% of the mass of the lithium methacrylate; the mixed solvent is ethanol and water with the volume ratio of 1:1-1.5; the reaction process is as follows:
。
the application also provides a battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte.
The application has the following beneficial effects:
according to the application, dibenzo-18-crown ether-6 is taken as a raw material and reacts with phenylbutanol to obtain a dibenzo-18-crown ether-6 derivative with stronger hydrophobicity, the dibenzo-18-crown ether-6 derivative is used for coating lithium oxide of a lithium supplementing material to prepare the positive electrode lithium supplementing agent with better stability, the coating layer of the positive electrode lithium supplementing agent is the dibenzo-18-crown ether-6 derivative, and the hydrophobic group on the molecular surface of the positive electrode lithium supplementing agent is phenylpropyl, so that on one hand, the deterioration caused by the reaction of lithium oxide in the positive electrode lithium supplementing agent with water, carbon dioxide and the like during long-term storage and use can be prevented, and the stability of the positive electrode lithium supplementing agent is improved; in addition, when the positive electrode slurry is prepared, the positive electrode lithium supplementing agent can be distributed in the aqueous solvent more uniformly, so that the performance of the positive electrode plate is improved, and the performance of the battery is improved.
According to the application, lithium methacrylate and phenyl acrylate are used as monomers, and the modified lithium polyacrylate binder is obtained through polymerization, and contains more ester groups in the molecule, so that more intermolecular hydrogen bonds can be formed with other components, and the binding force among the components is increased; the modified lithium polyacrylate molecular chain is introduced with branched chains containing rigid benzene ring groups, so that the molecular chains can be mutually staggered and wound, the viscosity is increased, the adhesive force between the positive electrode material layer and the aluminum foil is equivalently enhanced, and the peeling strength between the positive electrode material layer and the aluminum foil in the positive electrode plate is improved; the positive electrode plate can also be mutually staggered and wound with the hydrophobic group phenylpropyl on the surface of the positive electrode lithium supplementing agent, so that acting force between the positive electrode plate and the hydrophobic group phenylpropyl is increased, each component in the positive electrode plate is combined more tightly, and the cycle performance of the battery is improved. Compared with the traditional PVDF adhesive, the prepared modified lithium polyacrylate adhesive has better adhesive effect and is more environment-friendly.
The positive electrode lithium supplementing agent prepared by the method has good stability, can release enough lithium ions, is used for supplementing lithium ions consumed in the circulation process, has good lithium supplementing effect, can effectively improve the first coulomb efficiency and the overall electrochemical performance of the battery, and prolongs the service life of the battery.
Drawings
Fig. 1 is a graph showing a cycle of 200 weeks at 0.5C for the positive electrode sheet-assembled batteries prepared in examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Dibenzo-18-crown-6 CAS No. 14187-32-7; benzene butanol CAS number 3360-41-6; polyphosphoric acid CAS number 8017-16-1; methacrylic acid CAS No. 79-41-4; lithium hydroxide CAS number 1310-65-2; phenyl acrylate CAS number 937-41-7; toluene CAS number 108-88-3; n-heptane CAS number 142-82-5; ethanol CAS number 64-17-5; dichloromethane CAS number 75-09-2;4.5V lithium cobaltate, available from Flexible (Wuhan) technologies Co; all chemical reagents are commercially available.
Example 1
A positive electrode lithium supplementing agent comprises lithium oxide and a coating layer; the coating layer is coated on the surface of the lithium oxide; wherein the coating is dibenzo-18-crown-6 derivative; wherein the thickness of the coating layer is 50nm.
Adding dibenzo-18-crown ether-6 derivative into dichloromethane, stirring for 15min, adding lithium oxide, stirring until the mixture is uniformly dispersed, centrifuging, removing supernatant, and drying to obtain the positive electrode lithium supplement; wherein the mass ratio of the dibenzo-18-crown ether-6 derivative to the lithium oxide is 5:100; wherein the dosage of the methylene dichloride is 5 times of the mass of the lithium oxide.
The preparation method of the dibenzo-18-crown ether-6 derivative comprises the following steps: 36.0g of dibenzo-18-crown-6 and 7.50g of phenylbutanol are sequentially added into 360.0g of polyphosphoric acid, the temperature is raised to 80 ℃, the reaction is carried out for 8 hours, after the reaction is completed, the temperature is naturally reduced to room temperature, 200mL of water is slowly added dropwise into the reaction solution, after stirring for 20 minutes, 400mL of dichloromethane is added for extraction, an organic phase is firstly washed 3 times with 30% of sodium hydroxide solution and then is washed to be neutral with distilled water, the concentration under reduced pressure is carried out to obtain 51.5g of crude product, and 50mL of toluene and 100mL of n-heptane are used for recrystallization, thus 42.8g of dibenzo-18-crown-6 derivative is obtained. Wherein the molar ratio of the dibenzo-18-crown ether-6 to the phenylbutanol is 1:0.5; the dosage of the polyphosphoric acid is 10 times of the mass of the dibenzo-18-crown ether-6; the volume ratio of toluene to n-heptane is 1:2; the dibenzo-18-crown-6 derivative is a mixture of a compound 1 and a compound 2, wherein the compound 1 and the compound 2 are isomers, and the synthetic route is as follows:
；
dibenzo-18-crown derivatives: ESI (m/z): 625.3[ M+H ]] + ， 1 H-NMR(600MHz，DMSO-d 6 ，δppm)：7.19-7.24（m，10H），6.84（d，J=7.8Hz，2H），6.81（d，J=7.6Hz，2H），6.76（s，2H），3.95-4.10（m，16H），2.64-2.68（m，8H），1.56-1.60（m，8H）。
The application provides application of the positive electrode lithium supplementing agent, namely the positive electrode plate is prepared, wherein the positive electrode plate comprises a positive electrode current collector and a positive electrode material layer; the positive electrode material layer comprises a positive electrode active material, a modified lithium polyacrylate binder, a conductive agent and a positive electrode lithium supplementing agent; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the positive electrode lithium supplementing agent is 5% of the mass of the positive electrode material layer.
The preparation method of the modified lithium polyacrylate adhesive comprises the following steps:
s1, adding 43.0g of methacrylic acid and 12.0g of lithium hydroxide into 1000mL of water, reacting for 2 hours at room temperature, adjusting pH to be neutral after the reaction is completed, and removing water to obtain lithium methacrylate; wherein the molar ratio of methacrylic acid to lithium hydroxide is 1:1; the reaction process is as follows:
；
lithium methacrylate: ESI (m/z): 93.0[ M+H ]] + ， 1 H-NMR(600MHz，DMSO-d 6 ，δppm)：7.01-6.98（m，1H），5.89-5.85（m，1H），1.88（d，J=6.4Hz，3H）。
S2, adding lithium methacrylate and phenyl acrylate into a mixed solvent, heating to 90 ℃, dropwise adding an ammonium persulfate aqueous solution with the mass fraction of 50%, continuously reacting for 6-8 hours after the completion of the dripping, naturally cooling to room temperature, filtering, and drying filter residues to obtain a modified lithium polyacrylate binder; wherein the modified lithium polyacrylate adhesive has fluorescence absorption under an ultraviolet lamp (256 nm); the molar ratio of the lithium methacrylate to the phenyl acrylate is 1:1; the mass fraction of the lithium methacrylate is 50%; the dosage of the ammonium persulfate is 8% of the mass of the lithium methacrylate; the mixed solvent is ethanol and water with the volume ratio of 1:1.5; the reaction process is as follows:
。
the preparation method of the positive plate comprises the following steps: adding an anode active material (4.5V lithium cobaltate), a conductive agent (carbon black), a modified lithium polyacrylate binder and an anode lithium supplementing agent into a container according to the mass ratio of 90:2:3:5, adding deionized water and N, N-dimethylformamide, stirring until the materials are uniformly mixed to obtain slurry, controlling the solid content of the slurry to be 60%, coating the slurry on an anode current collector (aluminum foil), drying the slurry in a vacuum drying oven at 60 ℃ for 24 hours, rolling and punching the slurry into a wafer with the thickness of 12mm under the pressure of 5MPa, and finally drying the wafer in the vacuum drying oven at 120 ℃ for 10 hours to obtain the anode sheet.
Example 2
A positive electrode lithium supplementing agent comprises lithium oxide and a coating layer; the coating layer is coated on the surface of the lithium oxide; wherein the coating is dibenzo-18-crown-6 derivative; wherein the thickness of the coating layer is 40nm.
Adding dibenzo-18-crown ether-6 derivative into dichloromethane, stirring for 10min, adding lithium oxide, stirring until the mixture is uniformly dispersed, centrifuging, removing supernatant, and drying to obtain the positive electrode lithium supplement; wherein the mass ratio of the dibenzo-18-crown ether-6 derivative to the lithium oxide is 4:100; wherein the dosage of the methylene dichloride is 4 times of the mass of the lithium oxide.
The application provides application of the positive electrode lithium supplementing agent, namely the positive electrode plate is prepared, wherein the positive electrode plate comprises a positive electrode current collector and a positive electrode material layer; the positive electrode material layer comprises a positive electrode active material, a modified lithium polyacrylate binder, a conductive agent and a positive electrode lithium supplementing agent; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the positive electrode lithium supplementing agent is 4% of the mass of the positive electrode material layer.
The preparation method of the dibenzo-18-crown-6 derivative and the modified lithium polyacrylate binder is the same as in example 1.
The preparation method of the positive plate comprises the following steps: adding a positive electrode active material (4.5V lithium cobaltate), a conductive agent (carbon black), a modified lithium polyacrylate binder and a positive electrode lithium supplementing agent into a container according to the mass ratio of 90:2:4:4, adding deionized water and N, N-dimethylformamide, stirring until the materials are uniformly mixed to obtain slurry, controlling the solid content of the slurry to be 60%, coating the slurry on a positive electrode current collector (aluminum foil), drying the slurry in a vacuum drying oven at 60 ℃ for 24 hours, rolling and punching the slurry into a wafer with the thickness of 12mm under the pressure of 5MPa, and finally drying the wafer in the vacuum drying oven at 120 ℃ for 10 hours to obtain the positive electrode plate.
Example 3
A positive electrode lithium supplementing agent comprises lithium oxide and a coating layer; the coating layer is coated on the surface of the lithium oxide; wherein the coating is dibenzo-18-crown-6 derivative; wherein the thickness of the coating layer is 30nm.
Adding dibenzo-18-crown ether-6 derivative into dichloromethane, stirring for 15min, adding lithium oxide, stirring until the mixture is uniformly dispersed, centrifuging, removing supernatant, and drying to obtain the positive electrode lithium supplement; wherein the mass ratio of the dibenzo-18-crown ether-6 derivative to the lithium oxide is 3:100; wherein the dosage of the methylene dichloride is 3 times of the mass of the lithium oxide.
The application provides application of the positive electrode lithium supplementing agent, namely the positive electrode plate is prepared, wherein the positive electrode plate comprises a positive electrode current collector and a positive electrode material layer; the positive electrode material layer comprises a positive electrode active material, a modified lithium polyacrylate binder, a conductive agent and a positive electrode lithium supplementing agent; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the positive electrode lithium supplementing agent is 3% of the mass of the positive electrode material layer.
The preparation method of the dibenzo-18-crown-6 derivative and the modified lithium polyacrylate binder is the same as in example 1.
The preparation method of the positive plate comprises the following steps: adding an anode active material (4.5V lithium cobaltate), a conductive agent (carbon black), a modified lithium polyacrylate binder and an anode lithium supplementing agent into a container according to the mass ratio of 90:2:5:3, adding deionized water and N, N-dimethylformamide, stirring until the materials are uniformly mixed to obtain slurry, controlling the solid content of the slurry to be 60%, coating the slurry on an anode current collector (aluminum foil), drying the slurry in a vacuum drying oven at 60 ℃ for 24 hours, rolling and punching the slurry into a wafer with the thickness of 12mm under the pressure of 5MPa, and finally drying the wafer in the vacuum drying oven at 120 ℃ for 10 hours to obtain the anode sheet.
Comparative example 1
In comparison with example 1, the coating layer was different.
A positive electrode lithium supplementing agent comprises lithium oxide and a coating layer; the coating layer is coated on the surface of the lithium oxide; wherein the coating layer is dibenzo-18-crown-6; wherein the thickness of the coating layer is 50nm.
Adding dibenzo-18-crown ether-6 into dichloromethane, stirring for 15min, adding lithium oxide, stirring until the mixture is uniformly dispersed, centrifuging, removing supernatant, and drying to obtain the positive electrode lithium supplement; wherein the mass ratio of the dibenzo-18-crown ether-6 to the lithium oxide is 5:100; wherein the dosage of the methylene dichloride is 5 times of the mass of the lithium oxide.
The application provides application of the positive electrode lithium supplementing agent, namely the positive electrode plate is prepared, wherein the positive electrode plate and the preparation method thereof are the same as those of the embodiment 1.
Comparative example 2
In which the binder in the positive electrode material layer is different as compared with example 1.
A positive electrode lithium supplementing agent and a preparation method thereof are the same as in example 1.
The application provides application of the positive electrode lithium supplementing agent, namely the positive electrode plate is prepared, wherein the positive electrode plate comprises a positive electrode current collector and a positive electrode material layer positioned on the positive electrode current collector; the positive electrode material layer comprises a positive electrode active material, a PVDF binder, a conductive agent and a positive electrode lithium supplementing agent; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the positive electrode lithium supplementing agent is 5% of the mass of the positive electrode material layer.
The preparation method of the positive plate comprises the following steps: adding a positive electrode active material (4.5V lithium cobaltate), a conductive agent (carbon black), a PVDF binder and a positive electrode lithium supplementing agent into a container according to the mass ratio of 90:2:3:5, adding N, N-dimethylformamide, stirring until the materials are uniformly mixed to obtain slurry, controlling the solid content of the slurry to be 60%, coating the slurry on a positive electrode current collector (aluminum foil), drying for 24 hours at 60 ℃ in a vacuum drying box, rolling and punching into a 12mm wafer under the pressure of 5MPa, and finally drying for 10 hours at 120 ℃ in the vacuum drying box to obtain the positive electrode plate.
Correlation testing
1. Peel strength test of positive plate
The positive electrode sheets prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to peel strength test, pressed and firmly adhered by using an adhesive tape having a width of 40mm, then tested by using a CMT6104 type electronic stretcher at a stretching speed of 100mm/min for 3 times, and averaged; the test results are shown in Table 1.
Table 1 results of peel strength test of positive electrode sheet
As is clear from the results in Table 1, the modified lithium polyacrylate binders used in examples 1-3 and comparative example 1 are used, the peel strength of the prepared positive electrode sheet is greater than 1.00N/cm, the peel strength of example 1 is as high as 1.25N/cm, and compared with comparative example 2 (PVDF binder is used), the modified lithium polyacrylate binder used in example 1 is obtained by polymerizing phenyl acrylate and lithium methacrylate, and contains more ester groups in the molecule, can form more intermolecular hydrogen bonds with other components, and increases the bonding force between the components; and the modified lithium polyacrylate molecular chain is introduced with branched chains containing rigid benzene ring groups, so that the molecular chains can be mutually staggered and wound, the viscosity is increased, the adhesive force between the positive electrode material layer and the aluminum foil is equivalently enhanced, and the peeling strength between the positive electrode material layer and the aluminum foil in the positive electrode plate is improved.
2. Electrochemical performance test
The positive electrode sheets prepared in examples 1-3 and comparative examples 1-2 were assembled into CR 2032 half-cells, respectively, wherein the cells included a positive electrode sheet, a negative electrode sheet, and a separator and electrolyte between the positive and negative electrode sheets; the negative plate is a lithium plate, the diaphragm is a polypropylene diaphragm, the electrolyte is high-voltage secondary electrolyte (LB-363), and the battery is assembled in a glove box filled with argon, water and oxygen with the concentration of less than 0.1 ppm; and respectively carrying out electrochemical performance test by using the assembled batteries; the test voltage range is 3.0-4.5V, the first charge and discharge specific capacity, the first coulombic efficiency, the multiplying power and the cycle data are shown in Table 2; the 200 week cycle curve at 0.5C is shown in FIG. 1.
TABLE 2 electrochemical Performance test results
As can be seen from the results in Table 2, the battery prepared from the positive electrode sheets of examples 1-3 has higher initial coulombic efficiency, specific capacity after 200 weeks discharge and discharge capacity retention rate, which are far superior to those of comparative examples 1-2, and FIG. 1 can also show that the battery prepared from the positive electrode sheets of examples 1-3 has much higher specific capacity after 200 weeks discharge than those of comparative examples 1-2, which indicates that the battery prepared by the application has better electrochemical performance; compared with comparative example 1 (the coating layer is dibenzo-18-crown ether-6), the coating layer used in example 1 is dibenzo-18-crown ether-6 derivative, hydrophobic group phenylpropyl is introduced on the molecule, so that the lithium oxide in the positive electrode lithium supplement can be prevented from being deteriorated due to reaction with water, carbon dioxide and the like during long-term storage and use, the stability of the positive electrode lithium supplement is improved, and further the performance of a battery is improved; compared with comparative example 2 (PVDF binder is adopted), the modified lithium polyacrylate binder used in example 1 has a better bonding effect, and the branched chain of the rigid benzene ring group on the molecular chain can be intertwined with the hydrophobic group phenylpropyl on the surface of the positive electrode lithium supplement agent, so that the acting force between the two is increased, the components in the positive electrode sheet can be combined more tightly, and the cycle performance of the battery is improved.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus; although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A positive electrode sheet, characterized in that the positive electrode sheet comprises a positive electrode current collector and a positive electrode material layer; the positive electrode material layer comprises a positive electrode active material, a modified lithium polyacrylate binder, a conductive agent and a positive electrode lithium supplementing agent;
the preparation method of the modified lithium polyacrylate binder comprises the following steps:
s1, adding methacrylic acid and lithium hydroxide into water, and reacting for 1-2 hours at room temperature to obtain lithium methacrylate; the molar ratio of the methacrylic acid to the lithium hydroxide is 1:1;
s2, adding lithium methacrylate and phenyl acrylate into a mixed solvent, heating to 80-90 ℃, dropwise adding an ammonium persulfate aqueous solution with the mass fraction of 40-50%, and continuing to react for 6-8 hours after the completion of the dropwise adding, so as to obtain a modified lithium polyacrylate binder; the molar ratio of the lithium methacrylate to the phenyl acrylate is 1:1-1.1; the mass fraction of the lithium methacrylate is 30-50%; the dosage of the ammonium persulfate is 6-8% of the mass of the lithium methacrylate; the mixed solvent is ethanol and water with the volume ratio of 1:1-1.5;
the positive electrode lithium supplementing agent comprises lithium oxide and a coating layer; the coating layer is coated on the surface of the lithium oxide; the coating is dibenzo-18-crown-6 derivative;
the preparation method of the dibenzo-18-crown ether-6 derivative comprises the following steps: sequentially adding dibenzo-18-crown-6 and phenylbutanol into polyphosphoric acid, heating to 70-80 ℃, reacting for 6-8h, naturally cooling to room temperature after the reaction is completed, slowly dripping water into the reaction liquid, stirring for 15-20min, adding dichloromethane for extraction, washing an organic phase with 20-30% sodium hydroxide solution for 2-3 times, washing with distilled water to neutrality, concentrating under reduced pressure to obtain a crude product, and recrystallizing with toluene and n-heptane to obtain the product; the molar ratio of the dibenzo-18-crown ether-6 to the phenylbutanol is 1:0.4-0.5; the dosage of the polyphosphoric acid is 8-10 times of the mass of the dibenzo-18-crown ether-6; the volume ratio of toluene to n-heptane is 1:1-2.
2. A positive electrode sheet according to claim 1, wherein the thickness of the coating layer is 30-50nm.
3. The positive electrode sheet according to claim 1, wherein the positive electrode lithium supplementing agent is prepared by the following steps: adding the dibenzo-18-crown ether-6 derivative into dichloromethane, stirring for 10-15min, adding lithium oxide, stirring until the mixture is uniformly dispersed, centrifuging, removing supernatant, and drying to obtain the positive electrode lithium supplementing agent.
4. A positive electrode sheet according to claim 3, wherein the mass ratio of dibenzo-18-crown-6 derivative to lithium oxide is 3-5:100.
5. A positive electrode sheet according to claim 1, wherein the positive electrode active material is lithium cobaltate; the conductive agent is one or more of carbon black, carbon nano tube and graphene; the mass of the positive electrode lithium supplementing agent is 3-5% of the mass of the positive electrode material layer.
6. A battery comprising the positive electrode sheet, the negative electrode sheet, the separator, and the electrolyte according to any one of claims 1 to 5.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012089399A (en) * | 2010-10-21 | 2012-05-10 | Konica Minolta Holdings Inc | Electrode plate for lithium-ion secondary battery and lithium-ion secondary battery |
| WO2017190355A1 (en) * | 2016-05-06 | 2017-11-09 | 深圳先进技术研究院 | Electrolyte solution, secondary battery containing electrolyte solution and preparation method therefor |
| DE102016224044A1 (en) * | 2016-12-02 | 2018-06-07 | Robert Bosch Gmbh | Anode Active Material Particles with Artificial Kronether SEI Layer |
| CN108155370A (en) * | 2016-12-02 | 2018-06-12 | 罗伯特·博世有限公司 | There are the anode active material particles of SEI layers of synthesis by the polymerization of main chain method is grafted to |
| CN112909224A (en) * | 2019-12-04 | 2021-06-04 | 华为技术有限公司 | Lithium ion battery electrode material and preparation method thereof |
| CN115746207A (en) * | 2022-11-24 | 2023-03-07 | 元锂(上海)新材料技术有限责任公司 | Lithium ion battery binder, preparation method thereof and lithium ion battery pole piece |
| CN115911610A (en) * | 2022-11-18 | 2023-04-04 | 楚能新能源股份有限公司 | Anode lithium supplement material, preparation method and application thereof |
Family Cites Families (1)
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| KR20220152784A (en) * | 2021-05-10 | 2022-11-17 | 에스케이온 주식회사 | Anode active material for secondary battery, secondary battery including the same and method of preparing the same |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012089399A (en) * | 2010-10-21 | 2012-05-10 | Konica Minolta Holdings Inc | Electrode plate for lithium-ion secondary battery and lithium-ion secondary battery |
| WO2017190355A1 (en) * | 2016-05-06 | 2017-11-09 | 深圳先进技术研究院 | Electrolyte solution, secondary battery containing electrolyte solution and preparation method therefor |
| DE102016224044A1 (en) * | 2016-12-02 | 2018-06-07 | Robert Bosch Gmbh | Anode Active Material Particles with Artificial Kronether SEI Layer |
| CN108155370A (en) * | 2016-12-02 | 2018-06-12 | 罗伯特·博世有限公司 | There are the anode active material particles of SEI layers of synthesis by the polymerization of main chain method is grafted to |
| CN112909224A (en) * | 2019-12-04 | 2021-06-04 | 华为技术有限公司 | Lithium ion battery electrode material and preparation method thereof |
| CN115911610A (en) * | 2022-11-18 | 2023-04-04 | 楚能新能源股份有限公司 | Anode lithium supplement material, preparation method and application thereof |
| CN115746207A (en) * | 2022-11-24 | 2023-03-07 | 元锂(上海)新材料技术有限责任公司 | Lithium ion battery binder, preparation method thereof and lithium ion battery pole piece |
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