CN114843500A - Construction method and application of lithium-rich manganese-based positive electrode material stable interface of lithium ion battery - Google Patents
Construction method and application of lithium-rich manganese-based positive electrode material stable interface of lithium ion battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011572 manganese Substances 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 title claims description 15
- 238000010276 construction Methods 0.000 title abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 238000007614 solvation Methods 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 74
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 15
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910018557 Si O Inorganic materials 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 239000011267 electrode slurry Substances 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- 239000006245 Carbon black Super-P Substances 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 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 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract description 9
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 18
- 239000004743 Polypropylene Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910008626 Li1.2Ni0.13Co0.13Mn0.54O2 Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a construction method and application of a lithium-rich manganese-based anode material stable interface of a lithium ion battery. According to the construction method of the lithium-rich manganese-based anode material stable interface, fluorosilane is added into electrolysis as an additive, hydrofluoric acid (HF) can be removed when the lithium-rich manganese-based anode material is used in a lithium ion battery system, a lithium ion solvation structure is changed, a layer of thin, firm, compact and LiF-rich CEI is formed on the surface of a lithium-rich manganese-based (LRMO) electrode, the cycling stability of the battery is improved, and the service life of a high-capacity rechargeable lithium ion battery can be effectively prolonged.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a construction method and application of a lithium-rich manganese-based positive electrode material stable interface of a lithium ion battery.
Background
With the explosive growth of portable electronic devices and pure/hybrid vehicles, the development of high-energy, high-power-density rechargeable lithium ion batteries is imminent. Due to the limitations of the cathode materials, the energy density of commercial lithium ion batteries has reached a bottleneck. Therefore, it is crucial for next generation lithium ion batteries to find or optimize high capacity cathode materials. Lithium-rich manganese-based (LRMO) cathode materials are one of the most promising cathode materials due to their higher theoretical specific capacity and wide voltage plateau. However, low first-week efficiency, poor rate performance, and sustained voltage decay and capacity loss during charge and discharge are key issues limiting commercialization of lithium-rich manganese-based (LRMO) cathode materials due to first-week irreversible oxygen loss, transition metal ion migration, and corrosion by hydrofluoric acid. In order to solve these problems, surface coating and ion doping have been mainly performed on the material itself, and studies have been made on a binder and conductive carbon for an electrode structure, and research has been conducted on an electrolyte solution. Among them, the electrolyte additive is a simple and easily commercialized method.
Trace amount of water in the lithium ion battery electrolyte can cause lithium hexafluorophosphate to decompose to generate hydrofluoric acid, corrode the surface of an electrode and a current collector, and meanwhile, under high pressure, irreversible loss of oxygen and side reaction of the electrolyte and the surface of the electrode can also cause the structure of the lithium-rich manganese-based positive electrode material to change, thereby causing voltage attenuation and capacity loss. Therefore, the hydrofluoric acid removal and a stable CEI can effectively improve the electrochemical performance of the lithium-rich manganese-based positive electrode material. There are studies that show that siloxanes can protect the positive electrode as HF scavengers [ Nano Energy,2020,6: 105065; ACS Appl. Mater. interfaces,2016,8, 18439-; the inherent electrochemical stability of lithium fluoride-rich interfacial films prevents further side reactions between the electrode electrolytes [ adv. energy mate, 2020; 10,1903186]. On the basis, the inventor removes hydrofluoric acid (HF) in the electrolyte through an electrolyte additive, changes a lithium ion solvation structure, and simultaneously forms a layer of thin, firm, compact and LiF-rich CEI in situ in the charge-discharge cycle process, thereby realizing the improvement of the electrochemical performance of the lithium-rich manganese-based (LRMO) anode material.
Disclosure of Invention
One of the purposes of the invention is to provide a construction method of a lithium-rich manganese-based positive electrode material stable interface of a lithium ion battery, so that the electrochemical performance of the lithium-rich manganese-based (LRMO) positive electrode material is improved, and the service life of a high-capacity rechargeable lithium ion battery is prolonged.
The second purpose of the invention is to provide a preparation method of the lithium ion battery, and the cycle stability of the prepared lithium ion battery is improved under different current densities and wider voltage ranges.
The scheme adopted by the invention for realizing one purpose is as follows: a method for constructing a lithium-rich manganese-based anode material stable interface of a lithium ion battery utilizes fluorosilane as an additive of electrolyte, removes hydrofluoric acid in the electrolyte, changes a lithium ion solvation structure, and simultaneously forms a layer of CEI rich in LiF in situ in the charge-discharge cycle process.
The thickness of the formed CEI is 2-6 nm.
Preferably, the positive electrode material is lithium-rich manganese-based Li [ Li ] x M 1-x-y Mn y ]O 2 Wherein x + y is more than 0 and less than 1, and M is at least one of Ni, Co, Cr and Fe.
Preferably, the fluorosilane is fluorosilane containing Si-O bonds and C-F bonds.
Preferably, the fluorosilane is at least one of trimethoxy (3,3, 3-trifluoropropyl) silane, trimethoxy (1H, 2H-tridecafluoro-n-butyl) silane, dimethoxy (methyl) (3,3, 3-trifluoropropyl) silane.
Preferably, the number ratio of Si-O bonds to C-F bonds in the fluorosilane is 1: 1-5.
Preferably, the volume ratio of the additive to the electrolyte is (0.5-2): (98-99.5).
Preferably, the lithium salt in the electrolyte is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium bis-fluorosulfonyl imide, lithium bis (trifluoromethylsulfonyl) imide, lithium oxalyldifluoroborate, lithium difluorophosphate and lithium bis-fluorosulfonyl amide, and the corresponding solvent adopted in the electrolyte is an ester solvent and an ether solvent.
Preferably, the ester solvent is at least one of ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, fluoroethylene carbonate and 3,3, 3-fluoroethylene carbonate, and the ether solvent is ethylene glycol dimethyl ether and/or hydrofluoroether.
The second scheme adopted by the invention for achieving the purpose is as follows: the preparation method of the lithium ion battery adopts the electrolyte added with the fluorosilane as the electrolyte, and comprises the following steps:
step 1, preparing a lithium-rich manganese-based positive pole piece: mixing the lithium-rich manganese-based active material with conductive carbon, a binder and a solvent to obtain positive electrode slurry, coating the positive electrode slurry on the surface of a current collector, and drying to obtain a lithium-rich manganese-based positive electrode piece;
Preferably, in step 1, the conductive carbon is at least one of conductive carbon black BP2000, a carbon nanotube and conductive carbon black super P, the binder is any one or more of sodium carboxymethyl cellulose, sodium alginate, polyacrylic acid and polyolefin, the current collector is an aluminum foil, and the mass ratio of the lithium-rich manganese-based active material to the conductive carbon to the binder is (20-40): 12: 8.
preferably, in the step 2, the lithium ion battery is a CR2016 type button battery.
The diaphragm is a polyolefin film or glass fiber, and the polyolefin film is any one of a polypropylene single-layer film (PP), a polyethylene single-layer film (PE) and a polypropylene/polyethylene/polypropylene three-layer composite film (PP/PE/PP).
The invention has the following advantages and beneficial effects:
1. according to the construction method of the lithium-rich manganese-based anode material stable interface, fluorosilane is added into electrolysis as an additive, hydrofluoric acid (HF) can be removed when the lithium-rich manganese-based anode material is used in a lithium ion battery system, a lithium ion solvation structure is changed, a layer of thin, firm, compact and LiF-rich CEI is formed on the surface of a lithium-rich manganese-based (LRMO) electrode, the cycling stability of the battery is improved, and the service life of a high-capacity rechargeable lithium ion battery can be effectively prolonged.
2. The lithium ion battery prepared by the preparation method of the invention has improved cycling stability under different current densities and wider voltage ranges, and the cycling stability of the battery is improved.
3. The method of the invention has simple process and easy operation, and is beneficial to realizing commercial production.
Drawings
FIG. 1 shows the electrolyte prepared in example 1 of the present invention-1.0 vol% TMTFS and a base electrolyte of a control group 7 Li and 19 f nuclear magnetic spectrum, wherein, FIG. 1(a) 7 Li nuclear magnetic spectrum, FIG. 1(b) 19 F, nuclear magnetic spectrum;
FIG. 2 is a TEM image of a lithium manganese rich base (LRMO) prepared in example 1 of the present invention after being circulated in a base electrolyte and an electrolyte-1.0 vol% TMTFS, wherein FIG. 2(a) is a TEM image of a lithium manganese rich base (LRMO) after being circulated in a base electrolyte, and FIG. 2(b) is a TEM image of a lithium manganese rich base (LRMO) after being circulated in an electrolyte-1.0 vol% TMTFS;
fig. 3 is an X-ray photoelectron spectrum of a lithium manganese rich base (LRMO) prepared in example 1 of the present invention after being circulated in a base electrolyte and an electrolyte-1.0 vol% TMTFS, wherein fig. 3(a) and 3(C) are C1s and F1s spectrums of the lithium manganese rich base (LRMO) after being circulated in the base electrolyte, respectively, and fig. 3(b) and 3(d) are C1s and F1s spectrums of the lithium manganese rich base (LRMO) after being circulated in the electrolyte-1.0 vol% TMTFS, respectively;
FIG. 4 is a graph of electrochemical data of a lithium manganese rich base (LRMO) prepared in example 1 of the present invention cycled in a base electrolyte and an electrolyte of-1.0 vol% TMTFS, wherein FIGS. 4(a), 4(b) and 4(c) represent comparative graphs of cycling stability tests at different current densities, and FIG. 4(d) represents comparative graphs of cycling stability tests at a wide voltage range;
fig. 5 is a comparison graph of cycle stability tests of batteries assembled from the electrolytes prepared in examples 1 and 2 and comparative examples 1 to 3.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
The basic electrolyte adopted in the embodiment of the invention is a commercial electrolyte, and the lithium-rich manganese base adopted is Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 。
Example 1
The preparation method of the lithium ion battery comprises the following specific steps:
step 1): in a glove box, 990 μ L of base electrolyte and 10 μ L of trimethoxy (3,3, 3-trifluoropropyl) silane (TMTFS) are transferred into a reagent bottle by a pipette gun, and are uniformly mixed in a vibrator by shaking to obtain electrolyte-1.0 vol% TMTFS (in other embodiments, the volume ratio of the additive to the electrolyte is (0.5-2): 98-99.5), and in the embodiment, the volume ratio of the additive to the electrolyte is preferably 1: 99);
step 2): mixing lithium-rich manganese (LRMO) with conductive carbon black (super P) and a binder (PVDF) according to a mass ratio of 80: 12: 8, uniformly mixing to obtain slurry, coating the slurry on a current collector aluminum foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a positive electrode plate;
step 3): and (2) assembling the CR2016 type button cell by taking the obtained positive electrode plate as a positive electrode, a metal lithium plate as a counter electrode, a polypropylene membrane as a diaphragm, the electrolyte obtained in the step 1) as an electrolyte and the basic electrolyte as a control group electrolyte in a glove box filled with argon.
The electrolyte prepared in this example was subjected to 7 Li and 19 f nuclear magnetic spectrum characterization and comparison with the basic electrolyte used in step 1) of this example. FIG. 1(a) is a drawing 7 Li nuclear magnetic spectrum, FIG. 1(b) 19 F nuclear magnetic spectrum. As can be seen from fig. 1(a), when TMTFS is added to the electrolyte, 7 the Li peak shifts to a high frequency, indicating Li + The interaction with the solvent is weakened, leading to Li + The surrounding electron density decreases. This means that there are fewer solvent molecules around the lithium ions, which can move faster in the electrolyte during charging and discharging. As can be seen from FIG. 1(b), a new peak of HF (-192ppm) appeared after the addition of the aqueous HF solution to the base electrolyte. Addition of HF to a base electrolyte containing 1.0 vol% TMTFS, no HF being detectable 19 And F peak. 19 The results of the F nuclear magnetic spectrum show that the TMTFS additive can remove HF in the electrolyte.
The morphology and composition of the electrode material prepared in this example were characterized after cycling in the base electrolyte and electrolyte-1.0 vol% TMTFS. As shown in FIG. 2, 2(a) and 2(b) are TEM images of the lithium manganese rich base (LRMO) prepared in this example after being circulated in the base electrolyte and the electrolyte-1.0 vol% TMTFS, respectively, and it can be seen that a thin CEI layer with a uniform thickness is formed on the surface of the lithium manganese rich base (LRMO) after being circulated in the electrolyte-1.0 vol% TMTFS. FIGS. 3(a), 3(C) and 3(b), 3(d) are XPS spectra of lithium manganese rich (LRMO) circulated in the base electrolyte and electrolyte-1.0 vol% TMTFS, respectively, and in C1s spectra, RO-CO on the surface of lithium manganese rich (LRMO) circulated in electrolyte-1.0 vol% TMTFS 2 Li/Li 2 CO 3 The (290.8eV), C ═ O (287.9eV), and C — O (286.2eV) peak intensities were lower, indicating less solvolysis. Meanwhile, in the F1s spectrum, the peak intensity of LiF (685.3eV) on the surface of the lithium-rich manganese base (LRMO) circulated in the electrolyte-1.0 vol% TMTFS is much higher than that of the lithium-rich manganese base (LRMO) circulated in the base electrolyte, which indicates that the CEI-rich LiF is formed on the surface of the lithium-rich manganese base (LRMO) circulated in the electrolyte-1.0 vol% TMTFS. The above results show that with the base electrolyte solution of TMTF, the lithium manganese rich base (LRMO) forms a thin, strong, dense and LiF rich CEI (positive electrolyte interphase) after cycling in it.
The battery assembled with the electrode material and the electrolyte prepared in this example was subjected to a cycle stability test and compared with the battery assembled with the base electrolyte of comparative example 1 at 100mA g -1 ，200mA g -1 ，500mA g -1 Current densityThe charge-discharge cycling results at this time are shown in fig. 4, and the battery using the base electrolyte showed overcharge and a faster rate of battery capacity fade, while the battery performance in the electrolyte-1.0 vol% TMTFS was significantly improved.
Example 2
The preparation method of the lithium ion battery comprises the following specific steps:
step 1): in a glove box, 990 μ L of base electrolyte and 10 μ L of trimethoxy (1H, 2H-tridecafluoro-n-butyl) silane (PFTMS) are transferred into a reagent bottle by a pipette gun, and are uniformly mixed in a shaker to obtain electrolyte-1.0 vol% PFTMS (in other embodiments, the volume ratio of the additive to the electrolyte is (0.5-2): 98-99.5, and in this embodiment, the volume ratio of the additive to the electrolyte is preferably 1: 99);
step 2): mixing lithium-rich manganese (LRMO) with conductive carbon black (super P) and a binder (PVDF) according to a mass ratio of 80: 12: 8, uniformly mixing to obtain slurry, coating the slurry on a current collector aluminum foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a positive electrode plate;
step 3): and (2) assembling the CR2016 type button cell by taking the electrode plate obtained as a positive electrode, a metal lithium sheet as a counter electrode and a polypropylene membrane as a diaphragm and the electrolyte obtained in the step 1) as an electrolyte in a glove box filled with argon.
Comparative example 1
The preparation method of the lithium ion battery comprises the following specific steps:
step 1): mixing lithium-rich manganese (LRMO) with conductive carbon black (super P) and a binder (PVDF) according to a mass ratio of 80: 12: 8, uniformly mixing to obtain slurry, coating the slurry on a current collector aluminum foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a positive electrode plate;
step 2): the electrode sheet obtained above was used as the positive electrode, the metal lithium sheet was used as the counter electrode, the polypropylene film was used as the separator, the base electrolyte without any additive was used as the electrolyte, and the CR2016 type button cell was assembled in a glove box filled with argon gas.
Comparative example 2
The preparation method of the lithium ion battery comprises the following specific steps:
step 1): in a glove box, a pipetting gun is used for pipetting 990 muL of LB-372 electrolyte and 10 muL of (trifluoromethyl) trimethylsilane (TFMTMS) into a reagent bottle, and the mixture is shaken and mixed evenly in an oscillator to obtain electrolyte-1.0 vol% PFTMS;
step 2): mixing lithium-rich manganese (LRMO) with conductive carbon black (super P) and a binder (PVDF) according to a mass ratio of 80: 12: 8, uniformly mixing to obtain slurry, coating the slurry on a current collector aluminum foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a positive electrode plate;
step 3): and (2) assembling the CR2016 type button cell by taking the electrode plate obtained as a positive electrode, a metal lithium sheet as a counter electrode and a polypropylene membrane as a diaphragm and the electrolyte obtained in the step 1) as an electrolyte in a glove box filled with argon.
Comparative example 3
The preparation method of the lithium ion battery comprises the following specific steps:
step 1): in a glove box, 990. mu.L of LB-372 electrolyte and 10. mu.L of n-propyl trimethoxy silane (n-PrTMS) are transferred into a reagent bottle by a liquid transfer gun, and are vibrated and mixed uniformly in an oscillator to obtain electrolyte-1.0 vol% PFTMS;
step 2): mixing lithium-rich manganese (LRMO) with conductive carbon black (super P) and a binder (PVDF) according to a mass ratio of 80: 12: 8, uniformly mixing to obtain slurry, coating the slurry on a current collector aluminum foil, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a positive electrode plate;
and step 3): and (2) assembling the CR2016 type button cell by taking the electrode plate obtained as a positive electrode, a metal lithium sheet as a counter electrode and a polypropylene membrane as a diaphragm and the electrolyte obtained in the step 1) as an electrolyte in a glove box filled with argon.
The batteries assembled with the electrolytes prepared in comparative examples 1, 2 and 3 were subjected to a cycle stability test (current density 100mAh g) -1 Voltage 2.0-4.8V) and compared with the batteries assembled with the electrolytes prepared in examples 1 and 2, the test results are shown in fig. 5, in which 4 different fluorosilanes were addedThe circulation stability of the battery assembled by the electrolyte of the agent and the base electrolyte is compared, and the circulation stability of the additive containing both C-F and Si-O (PFTMS and TMTFS) is better than that of the additive containing only Si-O (n-PrTMS) and that of the additive containing only Si-O is better than that of the additive containing only C-F (TFMTMS) from the figure, which shows that the synergistic action of C-F and Si-O is more than that of Si-O more than C-F, namely the synergistic effect of removing hydrofluoric acid and the CEI rich in LiF > the effect of removing hydrofluoric acid alone > the effect of forming the CEI rich in LiF alone, but the fluorosilane alone containing C-F or Si-O does not enhance the cycle stability of the lithium battery compared to the cycle stability of the lithium battery of the base electrolyte without any additive.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A method for constructing a lithium-rich manganese-based positive electrode material stable interface of a lithium ion battery is characterized by comprising the following steps of: fluorosilane is used as an additive of the electrolyte, hydrofluoric acid in the electrolyte is removed, a lithium ion solvation structure is changed, and a layer of CEI rich in LiF is formed in situ in the charge-discharge cycle process.
2. The method for constructing the lithium-rich manganese-based positive electrode material stable interface of the lithium ion battery according to claim 1, wherein the method comprises the following steps: the anode material is rich lithium manganese Li x M 1-x-y Mn y ]O 2 Wherein x + y is more than 0 and less than 1, and M is at least one of Ni, Co, Cr and Fe.
3. The method for constructing the lithium-rich manganese-based positive electrode material stable interface of the lithium ion battery according to claim 1, wherein the method comprises the following steps: the fluorosilane is fluorosilane containing Si-O bonds and C-F bonds.
4. The method for constructing the lithium-rich manganese-based positive electrode material stable interface of the lithium ion battery according to claim 3, wherein: the fluorosilane is at least one of trimethoxy (3,3, 3-trifluoropropyl) silane, trimethoxy (1H,1H,2H, 2H-tridecafluoro-n-butyl) silane and dimethoxy (methyl) (3,3, 3-trifluoropropyl) silane.
5. The method for constructing the lithium-rich manganese-based positive electrode material stable interface of the lithium ion battery according to claim 1, wherein the method comprises the following steps: the volume ratio of the additive to the electrolyte is (0.5-2): (98-99.5).
6. The method for constructing the lithium-rich manganese-based positive electrode material stable interface of the lithium ion battery according to claim 1, wherein the method comprises the following steps: the lithium salt in the electrolyte is at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluosulfonyl imide, lithium bis (trifluoromethylsulfonyl) imide, lithium oxalyldifluoroborate, lithium difluorophosphate and lithium difluosulfonyl amide, and the solvent adopted by the electrolyte is an ester solvent and an ether solvent.
7. The method for constructing the lithium-rich manganese-based positive electrode material stable interface of the lithium ion battery according to claim 6, wherein: the ester solvent is at least one of ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, fluoroethylene carbonate and 3,3, 3-fluoroethylene carbonate, and the ether solvent is ethylene glycol dimethyl ether and/or hydrofluoroether.
8. A preparation method of a lithium ion battery is characterized by comprising the following steps: the method for preparing an electrolyte using the electrolyte to which fluorosilane is added according to any one of claims 1 to 7 as an electrolyte, comprising the steps of:
step 1, preparing a lithium-rich manganese-based positive pole piece: mixing the lithium-rich manganese-based active material with conductive carbon, a binder and a solvent to obtain positive electrode slurry, coating the positive electrode slurry on the surface of a current collector, and drying to obtain a lithium-rich manganese-based positive electrode piece;
step 2, preparing the lithium ion battery: and (3) taking the lithium-rich manganese-based positive pole piece obtained in the step (1) as a positive pole, taking a metal lithium piece as a counter electrode, taking the electrolyte added with fluorosilane as an electrolyte, and assembling the lithium ion battery in an inert atmosphere.
9. The method of claim 8, wherein: in the step 1, the conductive carbon is at least one of conductive carbon black BP2000, carbon nano tube and conductive carbon black super P, the binder is any one or more of sodium carboxymethylcellulose, sodium alginate, polyacrylic acid and polyolefin, the current collector is aluminum foil, and the mass ratio of the lithium-rich manganese-based active material to the conductive carbon to the binder is (20-40): 12: 8.
10. the method of claim 9, wherein: in the step 2, the lithium ion battery is a CR2016 type button battery.
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| CN112952199A (en) * | 2021-04-22 | 2021-06-11 | 远景动力技术(江苏)有限公司 | Electrolyte and lithium ion battery comprising same |
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| JP2010205474A (en) * | 2009-03-02 | 2010-09-16 | Sanwa Yuka Kogyo Kk | Nonaqueous electrolyte and lithium ion secondary battery including the same |
| CN112952199A (en) * | 2021-04-22 | 2021-06-11 | 远景动力技术(江苏)有限公司 | Electrolyte and lithium ion battery comprising same |
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