CN119059526B - Amorphous lithium hexafluorosilicate and preparation method thereof, graphite negative electrode sheet and preparation method thereof and application thereof - Google Patents
Amorphous lithium hexafluorosilicate and preparation method thereof, graphite negative electrode sheet and preparation method thereof and application thereof Download PDFInfo
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- CN119059526B CN119059526B CN202411547557.7A CN202411547557A CN119059526B CN 119059526 B CN119059526 B CN 119059526B CN 202411547557 A CN202411547557 A CN 202411547557A CN 119059526 B CN119059526 B CN 119059526B
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- -1 lithium hexafluorosilicate Chemical compound 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 63
- 239000010439 graphite Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 239000007770 graphite material Substances 0.000 claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 239000003125 aqueous solvent Substances 0.000 claims abstract 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 23
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 3
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 claims description 3
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 238000004904 shortening Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 28
- 239000002904 solvent Substances 0.000 description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 12
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000009777 vacuum freeze-drying Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007847 structural defect Effects 0.000 description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910012258 LiPO Inorganic materials 0.000 description 2
- 229910004074 SiF6 Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/027—Negative 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to amorphous lithium hexafluorosilicate, a preparation method thereof, a graphite negative electrode sheet, a preparation method thereof and application thereof, wherein the preparation method of the amorphous lithium hexafluorosilicate comprises the steps of placing a silicon source, a fluorine source and a lithium source in a non-aqueous solvent in a protective gas atmosphere to prepare a mixed solution; and (3) placing the mixed solution in a low-temperature environment below 0 ℃ for reaction, and separating after the reaction is finished to obtain the amorphous lithium hexafluorosilicate. The graphite negative electrode sheet comprises a current collector and a graphite material layer attached to the surface of the current collector, and amorphous lithium hexafluorosilicate is also attached to the surface of the graphite material layer. The amorphous lithium hexafluorosilicate provided by the invention is used on the surface of the graphite negative electrode plate, and the transmission rate of lithium ions can be accelerated by eliminating the limit of grain boundaries, increasing the diffusion path of lithium ions, shortening the path and the like, so that the quick charge performance and the electrochemical performance of the graphite negative electrode plate are improved.
Description
Technical Field
The invention relates to the technical field of energy storage, in particular to amorphous lithium hexafluorosilicate, a preparation method thereof, a graphite negative electrode sheet, a preparation method thereof and application thereof.
Background
At present, the negative electrode of the lithium ion battery is mainly made of graphite materials, and the graphite materials have the problems of slow ion diffusion kinetics process, lithium dendrite growth in the circulation process and the like, so that the quick charging capability of the lithium ion battery is restricted. Therefore, there is a need to improve the fast charge capability of graphite negative electrode sheets by an efficient method.
Disclosure of Invention
Based on the above, there is a need to provide an amorphous lithium hexafluorosilicate and a preparation method thereof, a graphite negative electrode sheet and a preparation method and application thereof, wherein the preparation method can obtain the amorphous lithium hexafluorosilicate, and the rapid charging capability and electrochemical performance of the graphite negative electrode sheet can be effectively improved when the amorphous lithium hexafluorosilicate is used for the graphite negative electrode sheet.
A method for preparing amorphous lithium hexafluorosilicate, comprising the following steps:
placing a silicon source, a fluorine source and a lithium source in a nonaqueous solvent in a protective gas atmosphere to prepare a mixed solution;
And (3) placing the mixed solution in a low-temperature environment below 0 ℃ for reaction, and separating after the reaction is finished to obtain the amorphous lithium hexafluorosilicate.
In one embodiment, the low temperature environment has a temperature of-40 ℃ to 0 ℃.
In one embodiment, the mixed solution is subjected to ultrasonic treatment when the mixed solution is subjected to a reaction in a low-temperature environment of 0 ℃ or less.
In one embodiment, the frequency of the sonication is from 20KHz to 120KHz.
In one embodiment, the silicon source is selected from at least one of elemental silicon, silicon dioxide, silicic acid, hexafluorosilicic acid, silicon tetrafluoride, silicon tetrachloride, silicate, methylchlorosilane, trichloromethylsilane, trichlorosilane, tetravinyl silane, or tetraethyl orthosilicate;
and/or the fluorine source is at least one selected from lithium fluoride, hydrogen fluoride, hexafluorosilicic acid, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bis (trifluoromethanesulfonyl) imide or lithium bis (fluorosulfonyl) imide;
And/or the lithium source is at least one of simple substance lithium, lithium fluoride, lithium hydroxide, lithium carbonate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bis (trifluoromethanesulfonyl) imide or lithium bis (fluorosulfonyl) imide;
and/or the nonaqueous solvent is at least one selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraglyme, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, butyronitrile, benzonitrile, ethanedinitrile or acrylonitrile.
Said non-crystallization of lithium hexafluorosilicate amorphous lithium hexafluorosilicate prepared by the preparation method.
The graphite negative plate comprises a current collector and a graphite material layer attached to the surface of the current collector, wherein amorphous lithium hexafluorosilicate is also attached to the surface of the graphite material layer.
In one embodiment, the amorphous lithium hexafluorosilicate is used in an amount of 2 to 20 times the mass of graphite in the layer of graphite material.
The preparation method of the graphite negative plate comprises the following steps:
Providing a prefabricated graphite negative electrode plate, wherein the prefabricated graphite negative electrode plate comprises a current collector and a graphite material layer attached to the surface of the current collector;
dispersing amorphous lithium hexafluorosilicate in a nonaqueous solvent to obtain a dispersion liquid, placing the dispersion liquid on the surface of a graphite material layer of the prefabricated graphite negative electrode plate, and drying to obtain the graphite negative electrode plate.
A lithium ion battery comprises the graphite negative plate.
In the preparation method, the low-temperature environment limits the diffusion rate and reaction kinetics of molecules, atoms or ions, inhibits the nucleation and growth processes of crystals, and thus realizes the preparation of amorphous lithium hexafluorosilicate, and the amorphous lithium hexafluorosilicate consists of short-range disordered crystal-like domains, vacancies, pores and other structural defects, wherein the short-range disordered crystal-like domains can greatly reduce the migration energy barrier of lithium ions, the vacancies, the pores and other structural defects can provide more channels for lithium ion transmission and shorten the transmission distance, and the amorphous structure eliminates the limit of grain boundaries, so that ions can be continuously transmitted, the transmission rate of lithium ions can be accelerated, and the ion conductivity of the amorphous lithium hexafluorosilicate is improved.
Therefore, the amorphous lithium hexafluorosilicate is used on the surface of the graphite negative electrode plate, and the transmission rate of lithium ions can be accelerated by eliminating the limit of crystal boundary, increasing the diffusion path of lithium ions, shortening the path and the like, so that the quick charge performance and the electrochemical performance of the graphite negative electrode plate are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments or the conventional techniques of the present application, the drawings required for the descriptions of the embodiments or the conventional techniques will be briefly described below, and it is apparent that the drawings in the following descriptions are only some embodiments of the present application, and other drawings may be obtained according to the drawings without inventive effort for those skilled in the art.
FIG. 1 is a graph of the first circle GCD of 0.1C of the graphite negative electrode sheet prepared in application example 5, wherein A is a discharge curve and B is a charge curve;
FIG. 2 is a graph of 200 cycles at 1C of the graphite negative electrode sheet prepared in application example 5;
FIG. 3 is a graph of the first circle GCD of 0.1C of the graphite negative electrode sheet prepared in comparative example 2, wherein A is a discharge curve and B is a charge curve;
FIG. 4 is a graph of 200 cycles at 1C of a graphite negative electrode sheet prepared by comparative example 2;
FIG. 5 is a graph of the first GCD curve of the graphite negative electrode sheet 0.1C prepared by blank example, wherein A is a discharge curve and B is a charge curve;
fig. 6 is a graph of 200 cycles under the graphite negative electrode sheet 1C prepared using the blank example.
Detailed Description
The present invention will be described in more detail below in order to facilitate understanding of the present invention. It should be understood, however, that the invention may be embodied in many different forms and should not be limited to the implementations or embodiments described herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention. As used herein, the optional scope of the term "and/or" includes any one of the two or more related listed items, as well as any and all combinations of related listed items, including any two or more of the related listed items, or all combinations of related listed items.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The preparation method of the amorphized lithium hexafluorosilicate provided by the invention comprises the following steps:
s11, placing a silicon source, a fluorine source and a lithium source in a nonaqueous solvent in a protective gas atmosphere to prepare a mixed solution;
And S12, placing the mixed solution in a low-temperature environment below 0 ℃ for reaction, and separating after the reaction is finished to obtain the amorphous lithium hexafluorosilicate.
In step S11, the shielding gas is at least one selected from nitrogen and inert gas, the inert gas is selected from argon, and when the silicon source, the fluorine source and the lithium source are placed in a nonaqueous solvent, the lithium source, the silicon source and the fluorine source are proportioned according to the molar mass ratio of the reactants.
The silicon source is at least one selected from silicon salt and organic silicon source, and specifically can be at least one selected from simple substance silicon (Si), silicon dioxide (SiO 2), silicic acid (H 2SiO3), hexafluorosilicic acid (H 2SiF6), silicon tetrafluoride (SiF 4), silicon tetrachloride (SiCl 4), silicate, methyl chlorosilane (CH 3 ClSi), trichloromethyl silane (Cl 3SiCH3), trichlorosilane (SiHCl 3), tetravinyl silane (C 8H12 Si) and tetraethyl orthosilicate (TEOS).
The fluorine source is at least one selected from lithium fluoride (LiF), hydrogen Fluoride (HF), hexafluorosilicic acid (H 2SiF6), lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium difluorophosphate (LiPO 2F2), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and lithium bis (fluorosulfonyl) imide (LiLiFSI).
The lithium source is at least one selected from simple substance lithium (Li), lithium fluoride (LiF), lithium hydroxide (LiOH), lithium carbonate (Li 2CO3), lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium difluorophosphate (LiPO 2F2), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and lithium bis (fluoro-sulfonyl) imide (LiLiSI).
The nonaqueous solvent is at least one selected from AN ester solvent, AN ether solvent and a nitrile solvent, and specifically can be at least one selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl Ether (DE), ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DCE), tetraglyme (TGDE), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-Me-THF), acetonitrile (ACN), nitrile (NBR), benzonitrile (BN), ethanedinitrile (EDN) and Acrylonitrile (AN).
In step S12, when the mixed solution is placed in a low-temperature environment below 0 ℃ to perform reaction, the low-temperature environment limits the diffusion rate and reaction kinetics of molecules, atoms or ions, and inhibits the nucleation and growth process of crystals, thereby realizing the preparation of amorphous lithium hexafluorosilicate.
Further, the temperature of the low temperature environment is preferably-40 ℃ to 0 ℃, including but not limited to-40 ℃, -35 ℃, -30 ℃, -25 ℃, -20 ℃, -15 ℃, -10 ℃, -5 ℃ or 0 ℃, which can not only realize the preparation of amorphous lithium hexafluorosilicate, but also reduce the cost of realizing the low temperature environment.
Optionally, when the mixed solution is placed under a low-temperature environment below 0 ℃ for reaction, ultrasonic treatment is further performed, so that not only can components in a reaction system be uniformly dispersed, agglomeration be avoided, particle size and the like be controlled, but also the reaction rate can be further reduced, and the frequency of ultrasonic treatment is preferably 20KHz to 120KHz, including but not limited to 20KHz、25KHz、30KHz、35KHz、40KHz、45KHz、50KHz、55KHz、60KHz、65KHz、70KHz、75KHz、80KHz、85KHz、90KHz、95KHz、100KHz、105KHz、110KHz、115KHz or 120KHz.
It will be appreciated that after the reaction has ended, the amorphous lithium hexafluorosilicate may be isolated by centrifugation and washing sequentially to remove unreacted material and the autogenous impurities of the reactants, followed by drying to remove the residual solvent. Alternatively, the drying treatment is preferably a vacuum freeze-drying treatment at a temperature of-40 ℃ to-5 ℃ and a vacuum degree of 10 - Pa to 10 -4 Pa for a time of 10h to 20h.
The invention also provides the amorphous lithium hexafluorosilicate prepared by the preparation method of the amorphous lithium hexafluorosilicate, which consists of short-range disordered crystal-like domains, vacancies, pores and other structural defects, wherein the short-range disordered crystal-like domains can greatly reduce the migration energy barrier of lithium ions, the vacancies, the pores and other structural defects can provide more channels for lithium ion transmission and shorten the transmission distance, and the amorphous structure eliminates the limit of grain boundaries, so that ions can be continuously transmitted, the transmission rate of lithium ions can be accelerated, and the ion conductivity of the amorphous lithium hexafluorosilicate is improved.
The invention also provides a graphite negative plate which comprises a current collector and a graphite material layer attached to the surface of the current collector, wherein amorphous lithium hexafluorosilicate is also attached to the surface of the graphite material layer. Wherein the graphite material layer is prepared from graphite, binder, conductive agent, etc. in proportion.
Optionally, the amorphous lithium hexafluorosilicate is used in an amount of 2-20 times the mass of graphite in the graphite material layer.
The surface of the graphite negative electrode plate is provided with the amorphous lithium hexafluorosilicate, so that the transmission rate of lithium ions can be accelerated by eliminating the limit of crystal boundaries, increasing the diffusion path of lithium ions, shortening the path and the like, and the graphite negative electrode plate has better quick charge performance and electrochemical performance.
The invention also provides a preparation method of the graphite negative plate, which comprises the following steps:
S21, providing a prefabricated graphite negative electrode plate, wherein the prefabricated graphite negative electrode plate comprises a current collector and a graphite material layer attached to the surface of the current collector;
S22, dispersing the amorphous lithium hexafluorosilicate in a nonaqueous solvent to obtain a dispersion liquid, then placing the dispersion liquid on the surface of a graphite material layer of the prefabricated graphite negative electrode plate, and drying to obtain the graphite negative electrode plate.
It can be understood that the prefabricated graphite negative electrode sheet in the step S21, namely the conventional graphite negative electrode sheet, is obtained by mixing graphite, a conductive agent, a binder and other components to prepare slurry, coating the slurry on a current collector, drying and slicing, and processing the conventional graphite negative electrode sheet by using amorphous lithium hexafluorosilicate.
Optionally, the nonaqueous solvent in step S22 is at least one selected from dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraglyme, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, butyronitrile, benzonitrile, ethanedinitrile or acrylonitrile, and the manner of placing the dispersion on the surface of the graphite material layer of the prefabricated graphite negative-electrode sheet may be coating, dripping or the like.
The invention also provides a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the negative plate is the graphite negative plate.
The amorphous lithium hexafluorosilicate is used on the surface of the graphite negative plate used in the lithium ion battery, so that the transmission rate of lithium ions can be accelerated by eliminating the limit of a crystal boundary, increasing the diffusion path of the lithium ions, shortening the path and the like, and therefore, the lithium ion battery has better quick charge performance and electrochemical performance.
Hereinafter, the amorphous lithium hexafluorosilicate and the preparation method thereof, the graphite negative electrode sheet and the preparation method and application thereof will be further described by the following specific examples.
Example 1
In a glove box under argon atmosphere, silicon powder, lithium hydroxide and hydrogen fluoride with the molar mass ratio of 1:2:6 are added into acetonitrile solvent and sealed to obtain mixed solution, and then the mixed solution is subjected to ultrasonic treatment at the temperature of 0 ℃ with the ultrasonic frequency of 80KHz. After the reaction, separating out a crystal product by a vacuum filtration device, washing the crystal product by acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 2
In a glove box under argon atmosphere, adding silicon dioxide, lithium hydroxide and hydrogen fluoride with the molar mass ratio of 1:2:6 into acetonitrile solvent and sealing to obtain mixed solution, and then carrying out ultrasonic treatment on the mixed solution at-4 ℃ with the ultrasonic frequency of 75KHz. After the reaction is finished, separating out a crystal product by a vacuum filtering device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 3
In a glove box under argon atmosphere, adding silicon dioxide, lithium hexafluorophosphate and hydrogen fluoride with the molar mass ratio of 1:1:6 into a mixed solvent and sealing to obtain a mixed solution, and then carrying out ultrasonic treatment on the mixed solution at-9 ℃ with the ultrasonic frequency of 70KHz. After the reaction is finished, separating out a crystal product by a vacuum filtering device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 4
In a glove box under argon atmosphere, silicic acid, lithium fluoride and hydrogen fluoride with the molar mass ratio of 1:6:3 are added into a mixed solvent and sealed to obtain a mixed solution, and then the mixed solution is subjected to ultrasonic treatment at-14 ℃ with the ultrasonic frequency of 60KHz. After the reaction is finished, separating out a crystal product by a vacuum filtering device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 5
In a glove box under argon atmosphere, hexafluorosilicic acid and lithium hydroxide with the molar mass ratio of 1:2 are added into a mixed solvent and sealed to obtain a mixed solution, and then the mixed solution is subjected to ultrasonic treatment at-18 ℃ with the ultrasonic frequency of 50KHz. After the reaction is finished, separating out a crystal product by a vacuum filtering device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 6
In a glove box under argon atmosphere, hexafluorosilicic acid and lithium carbonate with a molar mass ratio of 1:1 are added into a mixed solvent and sealed to obtain a mixed solution, and then the mixed solution is subjected to ultrasonic treatment at-22 ℃ with an ultrasonic frequency of 45KHz. After the reaction is finished, separating out a crystal product by a vacuum filtering device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 7
In a glove box under argon atmosphere, adding silicon tetrachloride and lithium fluoride with a molar mass ratio of 1:6 into a mixed solvent, sealing to obtain a mixed solution, and then carrying out ultrasonic treatment on the mixed solution at-30 ℃ with an ultrasonic frequency of 40KHz. After the reaction is finished, separating out a crystal product by a vacuum filtering device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 8
In a glove box under argon atmosphere, tetraethyl orthosilicate, lithium fluoride and hydrogen fluoride with the molar mass ratio of 1:2:6 are added into a mixed solvent and sealed to obtain a mixed solution, and then the mixed solution is subjected to ultrasonic treatment at-35 ℃ with the ultrasonic frequency of 30KHz. After the reaction is finished, separating out a crystal product by a vacuum filtering device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the amorphous lithium hexafluorosilicate.
Example 9
Example 9 differs from example 5 only in that no sonication was performed during the reaction.
Comparative example 1
In a glove box under argon atmosphere, silicic acid, lithium fluoride and hydrofluoric acid with the molar mass ratio of 1:6:3 are placed in a reaction kettle, a proper amount of acetonitrile is added, the mixture is uniformly mixed and then sealed, and the temperature is kept at 100 ℃ for 5 hours. After cooling, separating out a crystal product by a vacuum filtration device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the lithium hexafluorosilicate crystal.
Comparative example 2
In a glove box under argon atmosphere, hexafluorosilicic acid and lithium hydroxide with the molar mass ratio of 1:2 are placed in a reaction kettle, a proper amount of acetonitrile is added, the mixture is uniformly mixed and then sealed, and the temperature is kept at 100 ℃ for 5 hours. After cooling, separating out a crystal product by a vacuum filtration device, washing the crystal product for a plurality of times by using acetonitrile solution, and then performing vacuum freeze drying at-35 ℃ with the vacuum degree of 10 -3 Pa and the drying time of 15 hours to obtain the lithium hexafluorosilicate crystal.
Application blank example
320Mg of artificial graphite material, 40mg of conductive carbon black and 40mg of carboxymethyl cellulose are weighed, a proper amount of deionized water is added, a planetary ball mill is used for ball milling for 2 hours, the ball-milled slurry is coated on a current collector, and the current collector is dried for 12 hours at 80 ℃ in vacuum and then cut into graphite negative electrode plates with the diameter of 12mm, and the loading capacity is 3mg/cm 2.
Then, metal lithium is used as a counter electrode and a reference electrode, a PP diaphragm is used as the diaphragm, liPF 6 with the concentration of 1mol/L is used as the electrolyte, a mixed solution of diethyl carbonate and ethylene carbonate with the volume ratio of 1:1 is used as the solvent, and the button cell is assembled in a glove box in argon atmosphere.
Application example 1 to application example 9
Application examples 1 to 9 and application blank examples are different in that amorphous lithium hexafluorosilicate prepared in examples 1 to 9 is uniformly dispersed in dimethyl carbonate and ethylene carbonate solvents mixed in a volume ratio of 1:1, and then is respectively dropped on the surface of a graphite negative electrode sheet.
Application comparative example 1 to application comparative example 2
The difference between application comparative example 1 to application comparative example 2 and application blank example is that lithium hexafluorosilicate crystals prepared in comparative example 1 to application comparative example 2 were uniformly dispersed in dimethyl carbonate and ethylene carbonate solvents mixed in a volume ratio of 1:1, and then were respectively dropped on the surface of a graphite negative electrode sheet.
Electrochemical performance tests were performed on the button cell obtained above, in which the voltage range of charge and discharge was 0.005V-2V, the current density was 0.1c, 1c=372 mA/g, and the test results are shown in fig. 1 to 6 and table 1.
TABLE 1
As can be seen from fig. 1 to 6 and table 1, the amorphous lithium hexafluorosilicate prepared by the method of the present invention shows higher ionic conductivity before and after the battery cycle, and meanwhile, the charge and discharge performance of 1C high current is better, so that the lithium hexafluorosilicate prepared by the present invention can accelerate the ion transmission rate, and improve the fast charge performance and electrochemical performance of the graphite negative electrode sheet.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
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| FR2585346B1 (en) * | 1985-07-26 | 1987-10-16 | Pechiney Aluminium | PROCESS FOR THE PREPARATION OF CALCIUM FLUOSILICATE AS A RAW MATERIAL FOR THE PRODUCTION OF CALCIUM FLUORIDE AND PURE FLUOSILICIC ACID |
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