CN116914247A - Semi-solid battery and in-situ curing method thereof - Google Patents
Semi-solid battery and in-situ curing method thereof Download PDFInfo
- Publication number
- CN116914247A CN116914247A CN202310860225.3A CN202310860225A CN116914247A CN 116914247 A CN116914247 A CN 116914247A CN 202310860225 A CN202310860225 A CN 202310860225A CN 116914247 A CN116914247 A CN 116914247A
- Authority
- CN
- China
- Prior art keywords
- lithium
- carbonate
- electrolyte
- battery
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 27
- 238000001723 curing Methods 0.000 title abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 72
- 238000007711 solidification Methods 0.000 claims abstract description 11
- 230000008023 solidification Effects 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 69
- -1 lithium 5-trifluoromethylpyridine-trimethylborate Chemical compound 0.000 claims description 63
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 57
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 56
- 239000002904 solvent Substances 0.000 claims description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 39
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims description 23
- 159000000002 lithium salts Chemical class 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 18
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 18
- 239000004020 conductor Substances 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 14
- 239000006230 acetylene black Substances 0.000 claims description 14
- 239000004917 carbon fiber Substances 0.000 claims description 14
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000002174 Styrene-butadiene Substances 0.000 claims description 7
- 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 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 7
- 229920000126 latex Polymers 0.000 claims description 7
- 239000004816 latex Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- 239000011115 styrene butadiene Substances 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910013872 LiPF Inorganic materials 0.000 claims 2
- 101150058243 Lipf gene Proteins 0.000 claims 2
- 239000003759 ester based solvent Substances 0.000 claims 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 20
- 239000007774 positive electrode material Substances 0.000 abstract description 18
- 239000000654 additive Substances 0.000 abstract description 15
- 230000000996 additive effect Effects 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 14
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002000 Electrolyte additive Substances 0.000 abstract description 4
- 230000001588 bifunctional effect Effects 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 55
- 238000002360 preparation method Methods 0.000 description 30
- 239000011888 foil Substances 0.000 description 26
- 239000006258 conductive agent Substances 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 20
- 239000002033 PVDF binder Substances 0.000 description 20
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- 239000007773 negative electrode material Substances 0.000 description 16
- 239000007784 solid electrolyte Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000002808 molecular sieve Substances 0.000 description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000003660 carbonate based solvent Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000027455 binding Effects 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000013538 functional additive Substances 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 229910001947 lithium oxide Inorganic materials 0.000 description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 229910018040 Li 1+x Ni Inorganic materials 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IDBGOYRUMQFHNM-UHFFFAOYSA-N dilithium methoxy(dioxido)borane Chemical compound [Li+].[Li+].COB([O-])[O-] IDBGOYRUMQFHNM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000009461 vacuum packaging 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
-
- 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
- H01M4/62—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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a semi-solid battery and an in-situ solidification method thereof. The invention uses 5-trifluoromethyl pyridine-trimethyl lithium borate (LiTFMP) as a bifunctional electrolyte additive, and the additive is decomposed into 5-trifluoromethyl pyridine-2-oxo-anions (TFP) through bond breaking reaction under the action of transition metal ions ‑ ) And trimethyl borate (TMB), TMB asThe film forming additive for the positive electrode is polymerized on the surface of the active substance of the positive electrode preferentially to form a uniform and compact protective film, the positive electrode is passivated, the continuous oxidation and deposition of electrolyte on the positive electrode are restrained, a low-impedance interfacial film is constructed, the generation of HF is restrained subsequently, and the stability of the positive electrode material is improved. The in-situ curing method can effectively improve interface compatibility, improve ion conductivity of the battery, and keep stability of the anode material, so that the lithium ion battery is promoted to show excellent multiplying power performance and cycle performance, and the safety of the battery can be improved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a semi-solid battery and an in-situ curing method thereof.
Background
The lithium ion battery is used as a commercial secondary battery, has the advantages of high working voltage, long cycle life, high specific energy density and the like, and is widely applied to the fields of electric automobiles, 3C electronics, aerospace and the like. With the continuous development of advanced technology and the increasing demand for high energy density energy storage systems, the development of high energy density lithium ion batteries has become a hotspot for research.
Commercial lithium ion batteries rely to a large extent on liquid organic carbonates as electrolytes, the components of which are mainly methyl ethyl carbonate, dimethyl carbonate, ethylene carbonate, etc. However, carbonate electrolyte systems are volatile and flammable, which can easily cause safety problems during battery charging and discharging, and solid state polymer electrolytes (SSEs) are an effective strategy to improve the high safety, high voltage window of batteries. The traditional curing method comprises a photo-thermal polymerization method, a slurry coating method, a hot pressing method and the like, but the operation of the solid electrolyte prepared by the methods is complex, and meanwhile, the problems of low ionic conductivity, large interface resistance and the like caused by insufficient contact between SSE and an electrode prevent the development of the solid electrolyte.
The electrolyte is solidified into solid or semi-solid electrolyte in situ in the battery as a simple and easy method, which can improve the interface problem of the solid electrolyte and effectively reduce the interface resistance. However, how to form a high-quality solid or semi-solid electrolyte in situ inside the battery to significantly improve the structural stability of the lithium ion cathode material and the cycle performance of the battery has yet to be studied.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a semi-solid battery and an in-situ curing method thereof. The semi-solid battery has good interfacial compatibility, so that the ionic conductivity of the semi-solid battery can be improved, the stability of the cathode material is kept, the semi-solid battery is promoted to show excellent multiplying power performance and cycle performance, and the safety of the battery can be improved. The in-situ curing method is simple and effective.
The invention aims at realizing the following technical scheme:
a battery comprising a positive plate, a negative plate, a separator, and an electrolyte; the electrolyte comprises lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP); the separator includes a separator substrate and a conductive carbon layer disposed on at least one side surface of the separator substrate.
The invention has the beneficial effects that:
the invention provides a semi-solid battery and an in-situ solidification method thereof. The invention uses 5-trifluoromethyl pyridine-trimethyl lithium borate (LiTFMP) as a bifunctional electrolyte additive, and the additive is decomposed into 5-trifluoromethyl pyridine-2-oxo-anions (TFP) through bond breaking reaction under the action of transition metal ions - ) And trimethyl borate (TMB), wherein TMB is used as an anode film forming additive to preferentially polymerize on the surface of an anode active substance to form a uniform and compact protective film, passivate the anode, inhibit continuous oxidation deposition of electrolyte on the anode, construct a low-impedance interfacial film, subsequently inhibit generation of HF and promote stability of an anode material. TMB can also be combined with PF 6 - Form stronger binding action and further bind F - Inhibit the formation of HF, thereby reducing the elution of transition metal ions. On the basis, the membrane containing the conductive carbon layer provides a large number of reaction sites for indirect oxidative polymerization of carbonate solvents, and TFP - Generating TFP by oxidation reaction, which can be used as an initiator to indirectly and continuously oxidize carbonic ester solvent and form polymer on the surface of the membrane containing the conductive carbon layer, so that electrolyte is semi-solidified, and the electrolyte after solidification is higher than liquid energyCan reduce the occurrence of interfacial side reaction and inhibit the gradual decomposition of the carbonic ester solvent into small molecule gas. The in-situ curing method can effectively improve interface compatibility, improve ion conductivity of the battery, and keep stability of the anode material, so that the lithium ion battery is promoted to show excellent multiplying power performance and cycle performance, and the safety of the battery can be improved.
Drawings
Fig. 1 is a graph showing the comparison of the test performed at room temperature for 360 cycles of 0.5C for the NCM622/Li batteries of example 1 and comparative example 1.
Fig. 2 is a graph comparing impedance tests after 360 cycles of 0.5C for NCM622/Li batteries of example 1 and comparative example 1.
Fig. 3 is a Scanning Electron Microscope (SEM) image and a High Resolution Transmission Electron Microscope (HRTEM) test image of the NCM622/Li battery of example 1 and comparative example 1 after 360 cycles of 0.5C.
Fig. 4 is a GC-MS plot of NCM622/Li batteries of example 1 and comparative example 1 charged to 4.5V at a current of 0.2C.
FIG. 5 is a diagram of the mechanism of action of the bi-functional additive in situ catalytic electrolyte of the present invention in preparing a solid polymer electrolyte.
FIG. 6 is a graph showing that the NCM622/Li cells of example 4 and comparative example 7, comparative example 5 and comparative example 8, comparative example 6 and comparative example 9 were at 0.5mV s -1 Cyclic voltammogram at sweep rate.
Detailed Description
< Battery >
As described above, the present invention provides a battery including a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte; the electrolyte comprises lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP); the separator includes a separator substrate and a conductive carbon layer disposed on at least one side surface of the separator substrate.
According to an embodiment of the invention, the lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP) can be used as a positive electrode film forming additive and also can be used as an electrolyte semi-curing initiator, and can realize in-situ curing of the electrolyte.
According to an embodiment of the invention, the 5-trifluoromethylpyridine-trisThe structural formula of lithium methylborate (LiTFMP) is as follows:
according to an embodiment of the present invention, the mass percentage of the 5-trifluoromethylpyridine-trimethyllithium borate (LiTFMP) is 0.2 to 5.0%, for example, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8% or 5% of the total mass of the electrolyte.
According to an embodiment of the invention, the electrolyte further comprises a lithium salt and a carbonate solvent.
According to an embodiment of the invention, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) At least one of lithium tetrafluoroborate, lithium trifluoromethane sulfonate, lithium perchlorate, lithium difluorooxalate borate, lithium hexafluoroarsenate and lithium difluorophosphate.
According to an embodiment of the present invention, the concentration of the lithium salt in the electrolyte is 0.8 to 2mol/L, for example, 1.0 to 1.5mol/L.
According to an embodiment of the present invention, the carbonate-based solvent is selected from any one or more of a linear carbonate-based solvent and a cyclic carbonate-based solvent. Wherein the cyclic carbonate solvent is selected from any one or more of Ethylene Carbonate (EC), fluoroethylene carbonate (FEC) and Propylene Carbonate (PC); the linear carbonate solvent is selected from any one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC).
According to an embodiment of the invention, the separator substrate is selected from polyethylene and/or polypropylene.
According to an embodiment of the invention, the conductive carbon layer has a thickness of 5 to 50 μm, for example 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm.
According to an embodiment of the invention, the conductive carbon layer comprises a conductive material and a bonding material.
According to an embodiment of the present invention, the conductive material is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
According to an embodiment of the present invention, the binding material is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
According to an embodiment of the invention, the mass ratio of the conductive material to the adhesive material is 5 to 10:1, for example 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.
According to an embodiment of the invention, the conductive carbon layer provides a reaction site for lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP), inducing in situ solidification of the electrolyte on the conductive carbon layer.
According to an embodiment of the present invention, the battery further includes a positive electrode sheet including a positive electrode current collector and a positive electrode active material layer coated on one or both side surfaces of the positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the positive electrode active material layer comprises the following components in percentage by mass: 80-99.8wt% of positive electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder.
Preferably, the positive electrode active material layer comprises the following components in percentage by mass: 90-99.6wt% of positive electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
According to an embodiment of the present invention, the battery further includes a negative electrode tab including a negative electrode current collector and a negative electrode active material layer coated on one or both side surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the mass percentage of each component in the anode active material layer is: 80-99.8wt% of negative electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder.
Preferably, the mass percentage of each component in the anode active material layer is as follows: 90-99.6wt% of negative electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
According to an embodiment of the present invention, the conductive agent is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
According to an embodiment of the present invention, the binder is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
According to an embodiment of the present invention, the negative electrode active material is selected from at least one of artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon, soft carbon, metallic lithium, silicon carbon negative electrode material, silicon oxygen negative electrode material.
According to an embodiment of the present invention, the positive electrode active material is selected from one or more of transition metal lithium oxide, lithium iron phosphate, and lithium manganate; the chemical formula of the transition metal lithium oxide is Li 1+x Ni y Co z M (1-y-z) O 2 Wherein, -0.1 is less than or equal to x is less than or equal to 1; y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y+z is more than or equal to 0 and less than or equal to 1; wherein M is at least one of Mg, zn, ga, ba, al, fe, cr, sn, V, mn, sc, ti, nb, mo, zr.
< semi-solid Battery >
As described above, the present invention also provides a semi-solid battery formed by in situ solidification of an electrolyte comprising lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP).
According to an embodiment of the invention, the lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP) can be used as a positive electrode film forming additive and also can be used as an electrolyte semi-curing initiator, and can realize in-situ curing of the electrolyte.
According to an embodiment of the present invention, the structural formula of the 5-trifluoromethylpyridine-lithium trimethylborate (LiTFMP) is as follows:
according to an embodiment of the present invention, the mass percentage of the 5-trifluoromethylpyridine-trimethyllithium borate (LiTFMP) is 0.2 to 5.0%, for example, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8% or 5% of the total mass of the electrolyte.
According to an embodiment of the invention, the electrolyte further comprises a lithium salt and a carbonate solvent.
According to an embodiment of the invention, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) At least one of lithium tetrafluoroborate, lithium trifluoromethane sulfonate, lithium perchlorate, lithium difluorooxalate borate, lithium hexafluoroarsenate and lithium difluorophosphate.
According to an embodiment of the present invention, the concentration of the lithium salt in the electrolyte is 0.8 to 2mol/L, for example, 1 to 1.5mol/L.
According to an embodiment of the present invention, the carbonate-based solvent is selected from any one or more of a linear carbonate-based solvent and a cyclic carbonate-based solvent. Wherein the cyclic carbonate solvent is selected from any one or more of Ethylene Carbonate (EC), fluoroethylene carbonate (FEC) and Propylene Carbonate (PC); the linear carbonate solvent is selected from any one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC).
According to an embodiment of the present invention, the semi-solid battery further includes a separator including a separator substrate and a conductive carbon layer disposed on at least one side surface of the separator substrate.
According to an embodiment of the invention, the separator substrate is selected from polyethylene and/or polypropylene.
According to an embodiment of the invention, the conductive carbon layer has a thickness of 5 to 50 μm, for example 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm.
According to an embodiment of the invention, the conductive carbon layer comprises a conductive material and a bonding material.
According to an embodiment of the present invention, the conductive material is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
According to an embodiment of the present invention, the binding material is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
According to an embodiment of the invention, the mass ratio of the conductive material to the adhesive material is 5 to 10:1, for example 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.
According to an embodiment of the invention, the conductive carbon layer provides a reaction site for lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP), inducing in situ solidification of the electrolyte on the conductive carbon layer.
According to an embodiment of the present invention, the semi-solid battery further includes a positive electrode sheet including a positive electrode current collector and a positive electrode active material layer coated on one or both side surfaces of the positive electrode current collector, the positive electrode active material layer including a positive electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the positive electrode active material layer comprises the following components in percentage by mass: 80-99.8wt% of positive electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder.
Preferably, the positive electrode active material layer comprises the following components in percentage by mass: 90-99.6wt% of positive electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
According to an embodiment of the present invention, the semi-solid battery further includes a negative electrode sheet including a negative electrode current collector and a negative electrode active material layer coated on one or both side surfaces of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
According to an embodiment of the present invention, the mass percentage of each component in the anode active material layer is: 80-99.8wt% of negative electrode active material, 0.1-10wt% of conductive agent, and 0.1-10wt% of binder.
Preferably, the mass percentage of each component in the anode active material layer is as follows: 90-99.6wt% of negative electrode active material, 0.2-5wt% of conductive agent, and 0.2-5wt% of binder.
According to an embodiment of the present invention, the conductive agent is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
According to an embodiment of the present invention, the binder is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
According to an embodiment of the present invention, the negative electrode active material is selected from at least one of artificial graphite, natural graphite, mesophase carbon microspheres, hard carbon, soft carbon, metallic lithium, silicon carbon negative electrode material, silicon oxygen negative electrode material.
According to an embodiment of the present invention, the positive electrode active material is selected from one or more of transition metal lithium oxide, lithium iron phosphate, and lithium manganate; the chemical formula of the transition metal lithium oxide is Li 1+x Ni y Co z M (1-y-z) O 2 Wherein, -0.1 is less than or equal to x is less than or equal to 1; y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y+z is more than or equal to 0 and less than or equal to 1; wherein M is at least one of Mg, zn, ga, ba, al, fe, cr, sn, V, mn, sc, ti, nb, mo, zr.
< method for producing Battery >
The invention also provides a preparation method of the battery, which comprises the following steps:
assembling a positive plate, a negative plate and a diaphragm into a non-injected battery cell, wherein the diaphragm comprises a diaphragm substrate and a conductive carbon layer arranged on at least one side surface of the diaphragm substrate;
and placing the battery core in an outer package, and injecting electrolyte to prepare the battery, wherein the electrolyte comprises 5-trifluoromethyl pyridine-trimethyllithium borate (LiTFMP).
According to an embodiment of the invention, the assembly is for example winding or lamination.
According to an embodiment of the invention, the separator substrate is selected from polyethylene and/or polypropylene.
According to an embodiment of the invention, the conductive carbon layer has a thickness of 5 to 50 μm, for example 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm.
According to an embodiment of the invention, the conductive carbon layer comprises a conductive material and a bonding material.
According to an embodiment of the present invention, the conductive material is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
According to an embodiment of the present invention, the binding material is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
According to an embodiment of the invention, the mass ratio of the conductive material to the adhesive material is 5 to 10:1, for example 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.
According to an embodiment of the invention, the conductive carbon layer provides a reaction site for lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP), inducing in situ solidification of the electrolyte on the conductive carbon layer.
< method of in-situ solidification of semi-solid Battery >
The invention also provides an in-situ solidification method of the semi-solid battery, which comprises the following steps:
assembling the positive plate, the negative plate and the diaphragm into an un-injected battery cell;
placing the battery core in an outer package, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and sorting procedures to obtain the semi-solid battery, wherein the electrolyte comprises 5-trifluoromethyl pyridine-lithium trimethylborate (LiTFMP).
According to an embodiment of the invention, the assembly is for example winding or lamination.
According to an embodiment of the present invention, the separator includes a separator substrate and a conductive carbon layer disposed on at least one side surface of the separator substrate.
According to an embodiment of the invention, the separator substrate is selected from polyethylene and/or polypropylene.
According to an embodiment of the invention, the conductive carbon layer has a thickness of 5 to 50 μm, for example 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm.
According to an embodiment of the invention, the conductive carbon layer comprises a conductive material and a bonding material.
According to an embodiment of the present invention, the conductive material is at least one selected from conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, metal powder, and carbon fiber.
According to an embodiment of the present invention, the binding material is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene, and polyethylene oxide.
According to an embodiment of the invention, the mass ratio of the conductive material to the adhesive material is 5 to 10:1, for example 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.
According to an embodiment of the invention, the conductive carbon layer provides a reaction site for lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP), inducing in situ solidification of the electrolyte on the conductive carbon layer.
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Test methods for batteries of the following examples and comparative examples:
(1) The NCM622/Li battery was placed in a blue charge-discharge meter at room temperature for a long cycle test of 200 cycles at 0.5C and 360 cycles at a voltage range of 3.0 to 4.5V.
(2) After 360 circles of 0.5CThe NCM622/Li battery of (2) is placed in a PGSTAT-30Autolab multichannel electrochemical station for impedance testing, and the frequency range is set to be 10 5 ～10 -2 Hz, voltage amplitude was 5mV.
(3) The NCM622/Li battery after 360 circles of 0.5C circulation is disassembled in a glove box, and Scanning Electron Microscope (SEM) and high-resolution transmission electron microscope (HRTEM) tests are carried out on the disassembled electrode.
(4) At 0.5mV s on an EC-lab (PGSTAT 302N) electrochemical workstation -1 Cyclic Voltammetry (CV) was performed on NCM622/Li cells to obtain the CV curve of the electrolyte.
(5) Gas phase mass spectrometry using ECC-Air CELL (EL-CELL, germany) in HPR-40DEMS mass spectrometer (HIDEN Analytical, UK), assembling the electrode sheet and electrolyte in an in situ gas test module, charging to 4.5V with 0.2C current, and on-line detecting CO 2 。
Example 1:
(1) Preparation of electrolyte: the method comprises the steps of mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to a mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and adding 1% LiTFMP after lithium salt is completely dissolved.
(2) Preparing a pole piece: liNi is added to 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), polyvinylidene fluoride adhesive (PVDF) and conductive agent acetylene black are dissolved in a proper amount of N-methyl pyrrolidone (NMP) according to the mass ratio of 8:1:1, the slurry is uniformly coated on a current collector aluminum foil, firstly, the current collector aluminum foil is dried in an oven at 80 ℃ for 1h, and then, the current collector aluminum foil is transferred to 120 ℃ for vacuum drying for 12h, so that a pole piece with the diameter of 12mm is cut for standby.
(3) Preparation of the separator: dissolving conductive agent Super-p and polyvinylidene fluoride adhesive (PVDF) in a mass ratio of 6:1 into a proper amount of N-methyl pyrrolidone (NMP), uniformly coating the slurry on Celgard 2500 membrane, firstly drying in an oven at 80 ℃ for 30min, subsequently transferring to 70 ℃ for vacuum drying for 12h, and making the membrane (SP) cut into a conductive carbon membrane (18 mm in diameter) for standby, wherein the thickness of the conductive carbon layer is 20 mu m.
(4) Preparation of a lithium ion battery: the prepared NCM622 electrode sheet was used as a positive electrode, a lithium foil was used as a negative electrode, a separator was SP, and 2025 type coin cells were assembled in a high purity argon glove box, and about 60 μl of electrolyte was injected into each cell.
Example 2:
(1) Preparation of electrolyte: the method comprises the steps of mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to a mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and adding 0.2% LiTFMP after lithium salt is completely dissolved.
(2) The preparation of the electrode sheet, separator and lithium ion battery was identical to example 1.
Example 3:
(1) Preparation of electrolyte: mixing a cyclic carbonate solvent Ethylene Carbonate (EC) and a linear carbonate solvent methyl ethyl carbonate (EMC) according to a mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and adding 2% LiTFMP after the lithium salt is completely dissolved.
(2) The preparation of the electrode sheet, separator and lithium ion battery was identical to example 1.
Comparative example 1:
(1) Preparation of electrolyte: mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to the mass ratio EC: EMC=3:7, purifying by using a molecular sieve, and then adding 1mol/L lithium hexafluorophosphate until lithium salt is completely dissolved to obtain the common electrolyte.
(2) Preparing a pole piece: liNi is added to 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), polyvinylidene fluoride adhesive (PVDF) and conductive agent acetylene black are dissolved in a proper amount of N-methyl pyrrolidone (NMP) according to the mass ratio of 8:1:1, the slurry is uniformly coated on a current collector aluminum foil, firstly, the current collector aluminum foil is dried in an oven at 80 ℃ for 1h, and then, the current collector aluminum foil is transferred to 120 ℃ for vacuum drying for 12h, so that a pole piece with the diameter of 12mm is cut for standby.
(3) Preparation of a lithium ion battery: the prepared NCM622 electrode sheet was used as a positive electrode, a lithium foil was used as a negative electrode, a separator was Celgard 2500, and 2025 type coin cells were assembled in a high purity argon glove box, and about 60 μl of electrolyte was injected into each cell.
Comparative example 2:
(1) Preparation of electrolyte: mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to the mass ratio EC: EMC=3:7, purifying by using a molecular sieve, and then adding 1mol/L lithium hexafluorophosphate until lithium salt is completely dissolved to obtain the common electrolyte.
(2) Preparing a pole piece: liNi is added to 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), polyvinylidene fluoride adhesive (PVDF) and conductive agent acetylene black are dissolved in a proper amount of N-methyl pyrrolidone (NMP) according to the mass ratio of 8:1:1, the slurry is uniformly coated on a current collector aluminum foil, firstly, the current collector aluminum foil is dried in an oven at 80 ℃ for 1h, and then, the current collector aluminum foil is transferred to 120 ℃ for vacuum drying for 12h, so that a pole piece with the diameter of 12mm is cut for standby.
(3) Preparation of the separator: dissolving conductive agent Super-p and polyvinylidene fluoride adhesive (PVDF) in a mass ratio of 6:1 into a proper amount of N-methyl pyrrolidone (NMP), uniformly coating the slurry on Celgard 2500 membrane, firstly drying in an oven at 80 ℃ for 30min, subsequently transferring to 70 ℃ for vacuum drying for 12h, and making the membrane (SP) cut into a conductive carbon membrane (18 mm in diameter) for standby, wherein the thickness of the conductive carbon layer is 20 mu m.
(4) Preparation of a lithium ion battery: the prepared NCM622 electrode sheet was used as a positive electrode, a lithium foil was used as a negative electrode, a separator was SP, and 2025 type coin cells were assembled in a high purity argon glove box, and about 60 μl of electrolyte was injected into each cell.
Comparative example 3:
(1) Preparation of electrolyte: the method comprises the steps of mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to a mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and adding 1% LiTFMP after lithium salt is completely dissolved.
(2) Preparing a pole piece: liNi is added to 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), polyvinylidene fluoride adhesive (PVDF) and conductive agent acetylene black are dissolved in a proper amount according to the mass ratio of 8:1:1In N-methyl pyrrolidone (NMP), the slurry is uniformly coated on a current collector aluminum foil, firstly, the slurry is dried in an oven at 80 ℃ for 1h, and then is transferred to 120 ℃ for vacuum drying for 12h, so that a pole piece with the diameter of 12mm is cut for standby.
(3) Preparation of a lithium ion battery: the prepared NCM622 electrode sheet was used as a positive electrode, a lithium foil was used as a negative electrode, a separator was Celgard 2500, and 2025 type coin cells were assembled in a high purity argon glove box, and about 60 μl of electrolyte was injected into each cell.
Comparative example 4:
(1) Preparation of electrolyte: mixing a cyclic carbonate solvent Ethylene Carbonate (EC) and a linear carbonate solvent methyl ethyl carbonate (EMC) according to a mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and adding 2% LiTFMP after the lithium salt is completely dissolved.
(2) The preparation of the pole pieces and lithium ion battery was identical to comparative example 3.
TABLE 1 results of composition and performance tests of batteries of examples 1-3 and comparative examples 1-4
As can be seen from table 1, the combined use of the conductive carbon separator and LiTFMP additive achieves better cycle capacity retention than conventional PP separator or conductive carbon separator batteries.
Since no additive was introduced in comparative examples 1 and 2, the prepared batteries were still conventional batteries containing liquid electrolytes, and there were no problems of low ionic conductivity, large interfacial resistance, etc., which affect the cycle performance of the batteries due to insufficient interfacial contact between the solid electrolyte and the electrode. Such a battery of comparative example 1 obtained 73.4% of the cycle capacity retention after 200 cycles of 0.5C, and a battery of comparative example 2 obtained 75.2% of the cycle capacity retention after 200 cycles of 0.5C.
Although the additives were introduced in comparative examples 3 and 4, the obtained battery was still a conventional battery containing a liquid electrolyte since it did not use a conductive carbon separator, and there were no problems that the battery cycle performance was affected due to low ionic conductivity, large interfacial resistance, and the like, which were caused by insufficient interfacial contact between a solid electrolyte and an electrode. The obtained battery of comparative example 3 obtained a cycle capacity retention of 82.6% after 200 cycles at 0.5C, and the battery of comparative example 4 obtained a cycle capacity retention of 79.8% after 200 cycles at 0.5C. The cycle performance of the batteries of comparative example 3 and comparative example 4 was due to the battery of comparative example 1, mainly due to the introduction of the additive forming a solid electrolyte membrane on the positive electrode surface of the battery.
The batteries of examples 1-3 incorporate a bifunctional electrolyte additive that forms a polymer on the surface of the separator containing the conductive carbon layer, semi-solidifies the electrolyte to obtain a semi-solid battery, and the obtained semi-solid battery after 200 cycles of 0.5C respectively obtains a cycle capacity retention of 86.5%, 84.3% and 84.5%, which is sufficient to demonstrate that the combined use of the bifunctional electrolyte additive and the conductive carbon separator achieves a synergistic effect, and improves the problems of low ionic conductivity, large interfacial resistance and the like affecting the battery cycle performance due to insufficient interfacial contact between the solid electrolyte and the electrode, and significantly improves the capacity retention of the semi-solid battery.
As can be seen from the comparison of comparative example 3 and comparative example 4, when the PP separator is used, the resistance of the reaction increases as the concentration of the additive increases, and thus the circulation capacity gradually decreases. When the SP separator is used, a low concentration is insufficient to form a semi-solid electrolyte, and a high concentration is excessively polymerized, resulting in an increase in impedance of the formed semi-solid electrolyte, and thus, 1% LiTFMP additive exhibits good electrochemical performance.
Fig. 1 is a graph showing the comparison of the test performed at room temperature for 360 cycles of 0.5C for the NCM622/Li batteries of example 1 and comparative example 1. As can be seen from fig. 1, example 1 also has a capacity retention of 80.2% after 360 cycles of electrolyte in situ curing at 3-4.5V, while the battery of comparative example 1 has only 59.1%, which demonstrates that the dual function additive significantly improves the cycle performance of the battery after positive electrode film formation and electrolyte in situ curing.
Fig. 2 is a graph comparing impedance tests after 360 cycles of 0.5C for NCM622/Li batteries of example 1 and comparative example 1. As can be seen from fig. 3, after 360 cycles of 0.5C at 3-4.5V, the interface impedance of example 1 is significantly smaller than that of the comparative example, which indicates that the interface membrane formed by the example has small impedance, and the interface compatibility of the generated solid electrolyte system is better, which is more favorable for diffusion of lithium ions.
Fig. 3 is a Scanning Electron Microscope (SEM) image and a High Resolution Transmission Electron Microscope (HRTEM) test image of the NCM622/Li battery of example 1 and comparative example 1 after 360 cycles of 0.5C. As can be seen from the figure, the battery of comparative example 1 had thicker decomposition product deposited on the positive electrode after cycling, and the positive electrode material particles were broken up and converted into primary particles, and the HRTEM image also showed that the materials were phase-changed. In contrast, example 1 showed less material surface deposition after 360 cycles of 0.5C, the structure remained intact, forming a solid electrolyte interface film as thin as 26.1nm on the positive electrode, whose HRTEM image showed the same complete lattice as the fresh pole piece, indicating the introduction of the bi-functional additive, on the one hand, forming a good interface passivation film on the positive electrode, inhibiting electrolyte decomposition and product deposition, and on the other hand forming a solid electrolyte providing high cycling stability.
Fig. 4 is a GC-MS plot of NCM622/Li batteries of example 1 and comparative example 1 charged to 4.5V at a current of 0.2C. Compared with comparative example 1, example 1 shows a smoother curve during charging, indicating that indirect oxidative decomposition does not produce CO 2 While comparative example 1 has a distinct peak around 3.9V, indicating that EC gradually becomes small molecule during decomposition, partly with CO 2 In the form of (2) release, the effectiveness of the bi-functional additive in forming an in-situ solid electrolyte is verified, and the electrolyte is semi-solidified due to the indirect oxidative decomposition of EC to form a polymer, so that the gradual decomposition of EC into CO is inhibited 2 The safety of the electrolyte is improved.
FIG. 5 is a diagram of the mechanism of action of the bi-functional additive in situ catalytic electrolyte of the present invention in preparing a solid polymer electrolyte. As shown in the figure, liTFMP additive breaks bond under the action of transition metal ion and becomes TFP - And TMB molecule, on the one hand TFP - OxidationThe EC can be further oxidized and polymerized indirectly and with LiPF 6 The polymer is formed by combination, and the electrolyte is solidified, thereby reducing the generation of interfacial side reaction and reducing the gradual decomposition of EC into micromolecular CO 2 And the like. On the other hand, TMB oxidation products can dimerize to form a good passivation film to protect the positive electrode, and combine with F - Thereby suppressing the formation of HF. The two components act together to improve the cycle stability and safety of the battery.
Comparative example 5:
(1) Preparation of electrolyte: purifying a linear carbonate solvent methyl ethyl carbonate (EMC) by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and obtaining a basic electrolyte after the lithium salt is completely dissolved.
(2) Preparing a pole piece: liNi is added to 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), polyvinylidene fluoride adhesive (PVDF) and conductive agent acetylene black are dissolved in proper amount of N-methyl pyrrolidone (NMP) according to the mass ratio of 1:1:1, the slurry is uniformly coated on a current collector aluminum foil, firstly, the current collector aluminum foil is dried in an oven at 80 ℃ for 1h, and then, the current collector aluminum foil is transferred to 120 ℃ for vacuum drying for 12h, so that a pole piece with the diameter of 12mm is cut for standby.
(3) Preparation of a lithium ion battery: the prepared NCM622 electrode sheet was used as a positive electrode, a lithium foil was used as a negative electrode, a separator was Celgard 2500, and 2025 type coin cells were assembled in a high purity argon glove box, and about 60 μl of electrolyte was injected into each cell.
Comparative example 6:
(1) Preparation of electrolyte: mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to the mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and obtaining a basic electrolyte after the lithium salt is completely dissolved.
(2) The preparation of the electrode sheet, separator and lithium ion battery was identical to comparative example 5.
Comparative example 7:
(1) Preparation of electrolyte: the method comprises the steps of mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to a mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and adding 1% LiTFMP after lithium salt is completely dissolved.
(2) The preparation of the electrode sheet, separator and lithium ion battery was identical to comparative example 5.
Comparative example 8:
(1) Preparation of electrolyte: the linear carbonate solvent methyl ethyl carbonate (EMC) was purified with molecular sieves, 1mol/L lithium hexafluorophosphate was added, and after complete dissolution of the lithium salt, 1% LTFP was added.
(2) Preparing a pole piece: liNi is added to 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), polyvinylidene fluoride adhesive (PVDF) and conductive agent acetylene black are dissolved in proper amount of N-methyl pyrrolidone (NMP) according to the mass ratio of 1:1:1, the slurry is uniformly coated on a current collector aluminum foil, firstly, the current collector aluminum foil is dried in an oven at 80 ℃ for 1h, and then, the current collector aluminum foil is transferred to 120 ℃ for vacuum drying for 12h, so that a pole piece with the diameter of 12mm is cut for standby.
(3) Preparation of a lithium ion battery: the prepared NCM622 electrode sheet was used as a positive electrode, a lithium foil was used as a negative electrode, a separator was Celgard 2500, and 2025 type coin cells were assembled in a high purity argon glove box, and about 60 μl of electrolyte was injected into each cell.
Comparative example 9:
(1) Preparation of electrolyte: the cyclic carbonate solvent Ethylene Carbonate (EC) and the linear carbonate solvent methyl ethyl carbonate (EMC) are mixed according to the mass ratio EC: EMC=3:7, and are purified by using a molecular sieve, then 1mol/L of lithium hexafluorophosphate is added, and after the lithium salt is completely dissolved, 1% of LTFP (5-trifluoromethyl pyridine-2-oxylithium) is added.
(2) The preparation of the electrode sheet, separator and lithium ion battery was identical to comparative example 5.
Example 4:
(1) Preparation of electrolyte: mixing cyclic carbonate solvent Ethylene Carbonate (EC) and linear carbonate solvent methyl ethyl carbonate (EMC) according to the mass ratio EC: EMC=3:7, purifying by using a molecular sieve, adding 1mol/L lithium hexafluorophosphate, and adding 1% LiTFMP after the lithium salt is completely dissolved.
(2) Pole pieceIs prepared from the following steps: liNi is added to 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), polyvinylidene fluoride adhesive (PVDF) and conductive agent acetylene black are dissolved in proper amount of N-methyl pyrrolidone (NMP) according to the mass ratio of 1:1:1, the slurry is uniformly coated on a current collector aluminum foil, firstly, the current collector aluminum foil is dried in an oven at 80 ℃ for 1h, and then, the current collector aluminum foil is transferred to 120 ℃ for vacuum drying for 12h, so that a pole piece with the diameter of 12mm is cut for standby.
(3) Preparation of the separator: dissolving conductive agent Super-p and polyvinylidene fluoride adhesive (PVDF) in a mass ratio of 6:1 into proper amount of N-methyl pyrrolidone (NMP), uniformly coating the slurry on Celgard 2500 membrane, oven-drying at 80 ℃ for 30min, transferring to 70 ℃ and vacuum drying for 12h, and cutting into conductive carbon membrane (SP) with diameter of 18mm for later use.
(4) Preparation of a lithium ion battery: the prepared NCM622 electrode sheet was used as a positive electrode, a lithium foil was used as a negative electrode, a separator was SP, and 2025 type coin cells were assembled in a high purity argon glove box, and about 60 μl of electrolyte was injected into each cell.
Table 2 composition of the batteries of example 4 and comparative examples 5 to 9
| Naming the name | Solvent(s) | Additive agent | Diaphragm | |
| Comparative example 5 | EMC-PP | EMC | 0 | Common diaphragm PP |
| Comparative example 6 | EC/EMC-PP | EC:EMC＝3:7 | 0 | Common diaphragm PP |
| Comparative example 7 | 1％LiTFMP-PP | EC:EMC＝3:7 | LiTFMP 1% | Common diaphragm PP |
| Comparative example 8 | LTFP/EMC-PP | EMC | 1% LTFP | Common diaphragm PP |
| Comparative example 9 | LTFP/EC/EMC-PP | EC:EMC＝3:7 | 1% LTFP | Common diaphragm PP |
| Example 4 | 1％LiTFMP-SP | EC:EMC＝3:7 | LiTFMP 1% | Conductive diaphragm SP |
FIG. 6 is example 4 andNCM622/Li cells of comparative example 7, comparative example 5 and comparative example 8, comparative example 6 and comparative example 9 were at 0.5mV s -1 Cyclic voltammogram at sweep rate. Comparison shows that EMC is unfavorable for positive electrode lithium removal, and lithium removal becomes easy after addition of LTFP. The EC is favorable for positive electrode lithium removal, and catalytic current of LTFP/LiTFMP on EC oxidative decomposition can be observed between 4.0 and 4.5V in the system containing LTFP. This current is difficult to observe in EC solutions, indicating that LiTFMP is primarily catalytic for oxidative decomposition of EC.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A battery comprising a positive plate, a negative plate, a separator, and an electrolyte; the electrolyte comprises lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP); the separator includes a separator substrate and a conductive carbon layer disposed on at least one side surface of the separator substrate.
2. The battery according to claim 1, wherein the mass of the 5-trifluoromethylpyridine-lithium trimethylborate (LiTFMP) is 0.2 to 5.0% by mass of the total mass of the electrolyte.
3. The battery according to claim 1 or 2, wherein the electrolyte further comprises a lithium salt and a carbonate solvent;
the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) At least one of lithium tetrafluoroborate, lithium trifluoromethane sulfonate, lithium perchlorate, lithium difluorooxalate borate, lithium hexafluoroarsenate and lithium difluorophosphate;
and/or the carbonate solvent is selected from any one or more of linear carbonate solvents and cyclic carbonate solvents; wherein the cyclic carbonate solvent is selected from any one or more of Ethylene Carbonate (EC), fluoroethylene carbonate (FEC) and Propylene Carbonate (PC); the linear carbonate solvent is selected from any one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC).
4. A battery according to any of claims 1-3, wherein the separator substrate is selected from polyethylene and/or polypropylene;
and/or the conductive carbon layer comprises a conductive material and a bonding material.
5. The battery of claim 4, wherein the conductive material is at least one selected from the group consisting of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotubes, metal powder, and carbon fiber;
and/or the bonding material is at least one selected from sodium carboxymethyl cellulose, styrene-butadiene latex, polytetrafluoroethylene and polyethylene oxide;
and/or the mass ratio of the conductive material to the bonding material is 5-10:1.
6. A semi-solid battery, wherein the semi-solid battery is formed by in situ solidification of an electrolyte comprising lithium 5-trifluoromethylpyridine-trimethylborate (LiTFMP).
7. The semisolid battery according to claim 6, characterized in that the mass of the 5-trifluoromethylpyridine-trimethyllithium borate (LiTFMP) is 0.2-5.0% of the total mass of the electrolyte.
8. The semi-solid battery according to claim 6 or 7, wherein the electrolyte further comprises a lithium salt and a carbonate solvent;
the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) At least one of lithium tetrafluoroborate, lithium trifluoromethane sulfonate, lithium perchlorate, lithium difluorooxalate borate, lithium hexafluoroarsenate and lithium difluorophosphate;
the carbonic ester solvent is selected from any one or more of linear carbonic ester solvents and cyclic carbonic ester solvents; wherein the cyclic carbonate solvent is selected from any one or more of Ethylene Carbonate (EC), fluoroethylene carbonate (FEC) and Propylene Carbonate (PC); the linear carbonate solvent is selected from any one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC).
9. The semi-solid state battery of any one of claims 6-8, further comprising a separator substrate and a conductive carbon layer disposed on at least one side surface of the separator substrate.
10. The semi-solid battery according to any one of claims 6-9, wherein the separator substrate is selected from polyethylene and/or polypropylene;
and/or the conductive carbon layer comprises a conductive material and a bonding material, wherein the mass ratio of the conductive material to the bonding material is 5-10:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310860225.3A CN116914247A (en) | 2023-07-13 | 2023-07-13 | Semi-solid battery and in-situ curing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310860225.3A CN116914247A (en) | 2023-07-13 | 2023-07-13 | Semi-solid battery and in-situ curing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116914247A true CN116914247A (en) | 2023-10-20 |
Family
ID=88366153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310860225.3A Pending CN116914247A (en) | 2023-07-13 | 2023-07-13 | Semi-solid battery and in-situ curing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116914247A (en) |
-
2023
- 2023-07-13 CN CN202310860225.3A patent/CN116914247A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110265627B (en) | Positive electrode plate and lithium ion secondary battery | |
| CN109309226B (en) | Electrochemical energy storage device | |
| JP2021536112A (en) | Lithium ion secondary battery | |
| CN109728340B (en) | Lithium ion battery | |
| CN111883839B (en) | High-voltage electrolyte and lithium ion battery based on same | |
| CN112242551B (en) | Secondary battery | |
| CN108232296B (en) | Electrolyte solution and lithium secondary battery | |
| CN111640985A (en) | Non-aqueous electrolyte and high-voltage lithium ion battery containing same | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| JP7106762B2 (en) | Positive electrode sheet, manufacturing method thereof, and lithium ion secondary battery | |
| CN111200162A (en) | Lithium ion battery electrolyte and preparation method thereof | |
| JP6904982B2 (en) | Positive electrode plate, its manufacturing method and lithium ion battery | |
| CN112582579A (en) | Positive electrode, electrochemical device, and electronic device | |
| CN109802176B (en) | Electrolyte and lithium ion battery containing electrolyte | |
| CN110649317B (en) | Silicon-based lithium ion battery electrolyte and lithium ion secondary battery | |
| CN116914247A (en) | Semi-solid battery and in-situ curing method thereof | |
| CN113196525A (en) | Negative electrode composite material and application thereof | |
| EP4383397A1 (en) | Electrolyte, secondary battery, and power device | |
| CN117878382A (en) | Battery cell | |
| CN118016997A (en) | Electrolyte and battery | |
| CN117096419A (en) | Electrolyte and battery comprising same | |
| CN117438535A (en) | Negative pole piece, secondary battery and electric equipment | |
| CN117673467A (en) | Electrolyte and battery comprising same | |
| CN116093432A (en) | Electrolyte and battery comprising same | |
| CN116344942A (en) | Electrolyte and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |