CN109309254B - Electrolyte and electrochemical energy storage device - Google Patents
Electrolyte and electrochemical energy storage device Download PDFInfo
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- CN109309254B CN109309254B CN201710626357.4A CN201710626357A CN109309254B CN 109309254 B CN109309254 B CN 109309254B CN 201710626357 A CN201710626357 A CN 201710626357A CN 109309254 B CN109309254 B CN 109309254B
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- electrolyte
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- salt
- quaternary ammonium
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 87
- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 29
- -1 sulfonate cyclic quaternary ammonium salt Chemical class 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000005518 polymer electrolyte Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 239000011244 liquid electrolyte Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 229910017048 AsF6 Inorganic materials 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000004419 alkynylene group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229910005143 FSO2 Inorganic materials 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 36
- 230000009471 action Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 239000007784 solid electrolyte Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 49
- 229910001416 lithium ion Inorganic materials 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910001305 LiMPO4 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018905 NaN(FSO2)2 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004804 winding 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by 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
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Secondary Cells (AREA)
Abstract
The application provides an electrolyte and an electrochemical energy storage device. The electrolyte includes an electrolyte salt and an additive. The additive comprises sulfonate cyclic quaternary ammonium salt and fluoroether compound. The combined action of the positive electrode and the negative electrode can enable a layer of compact, uniform and stable passive film to be formed on the surfaces of the positive electrode and the negative electrode of the electrochemical energy storage device, especially a low-impedance and compact solid electrolyte interface film can be formed on the surface of the negative electrode, so that continuous oxidation and reduction reactions between the electrolyte and the positive electrode and between the electrolyte and the negative electrode can be avoided, the interface impedance of the positive electrode and the negative electrode can be reduced, and the storage and gas generation of the electrochemical energy storage device in the use process can be reduced, so that the electrochemical energy storage device has better high-temperature storage performance.
Description
Technical Field
The application relates to the field of energy storage devices, in particular to electrolyte and an electrochemical energy storage device.
Background
With the increasing exhaustion of fossil energy and the increasing pressure of environmental pollution, the automobile industry urgently needs a novel energy source to provide drive for the fossil energy source, and the lithium ion battery is distinguished due to the characteristics of high energy density, no memory effect, high working voltage and the like, so that the lithium ion battery is currently the preferred scheme of a power supply of a new energy automobile. However, with the expansion of market demand of electronic products and the development of power and energy storage devices, people have continuously increased requirements on lithium ion batteries, and it is urgent to develop lithium ion batteries having high energy density and satisfying rapid charging and discharging. Currently, effective methods are to increase the voltage, the compaction density, and select a suitable electrolyte for the electrode active material.
Currently, the electrolyte widely used in the lithium ion battery is generally an electrolyte using lithium hexafluorophosphate as an electrolyte salt and using a mixture of cyclic carbonate and chain carbonate as an organic solvent, but the above electrolyte has many disadvantages, in particular, the high-temperature storage performance of the lithium ion battery is poor under high voltage, and the lithium ion battery faces the problem of rapid capacity decay after long-term cycling. The electrolyte is an important component of the lithium ion battery, has a significant influence on the electrochemical performance of the lithium ion battery, and the high-temperature storage performance of the lithium ion battery under high pressure can be improved to a certain extent by improving the composition of the electrolyte.
Disclosure of Invention
In view of the problems in the background art, the present application aims to provide an electrolyte and an electrochemical energy storage device, which have good high-temperature storage performance.
In order to achieve the above object, in one aspect of the present application, there is provided an electrolyte solution including an electrolyte salt and an additive. The additive comprises sulfonate cyclic quaternary ammonium salt and fluoroether compound.
In another aspect of the present application, an electrochemical energy storage device is provided that includes an electrolyte according to one aspect of the present application.
Compared with the prior art, the beneficial effects of this application do:
the electrolyte additive comprises the sulfonic ester cyclic quaternary ammonium salt and the fluoroether compound, so that a layer of compact, uniform and stable passivation film can be formed on the surface of the positive electrode and the surface of the negative electrode of the electrochemical energy storage device, especially a low-impedance and compact solid electrolyte interface film can be formed on the surface of the negative electrode, continuous oxidation and reduction reactions between the electrolyte and the positive electrode and between the electrolyte and the negative electrode can be avoided, the interface impedance of the positive electrode and the negative electrode is reduced, the storage and gas production of the electrochemical energy storage device in the use process can be reduced, and the electrochemical energy storage device has better high-temperature storage performance.
Detailed Description
The electrolyte and electrochemical energy storage device according to the present application are described in detail below.
First, an electrolytic solution according to the first aspect of the present application is explained.
The electrolyte according to the first aspect of the present application includes an electrolyte salt and an additive. The additive comprises sulfonate cyclic quaternary ammonium salt and fluoroether compound.
In the electrolyte according to the first aspect of the present disclosure, the cyclic quaternary ammonium sulfonate salt and the fluoroether compound may form a layer of dense, uniform and stable passivation film on both the positive and negative electrode surfaces of the electrochemical energy storage device, and particularly may form a low-impedance and dense solid electrolyte interface film (SEI film) on the negative electrode surface, thereby reducing the contact between the positive and negative electrodes and the electrolyte, so as to prevent the electrolyte from undergoing a continuous oxidation reaction and a reduction reaction on the positive and negative electrode surfaces, further reducing the decomposition of the electrolyte, avoiding an increase in internal resistance, and simultaneously reducing the storage of the electrochemical energy storage device during use, so that the electrochemical energy storage device has a better high-temperature storage performance. The reason is that the reduction potential of the cyclic quaternary ammonium sulfonate is about 1.5V, and when the voltage reaches 1.5V, the cyclic quaternary ammonium sulfonate can directionally migrate to the negative electrode, and a dense solid electrolyte interface film with good ion conductivity and composed of metal alkyl sulfonate is preferentially formed on the negative electrode, so that the reaction between the electrolyte and the negative electrode can be prevented, and the high-temperature storage performance of the electrochemical energy storage device is improved. The fluoroether compound can form a film on the positive electrode, and the oxidation potential of the fluoroether compound is higher, so that the storage gas generation of the electrochemical energy storage device can be reduced, the high-temperature storage performance of the electrochemical energy storage device is further improved, but the kinetic performance of the electrochemical energy storage device is poor due to the high content of the fluoroether compound. Therefore, under the combined action of the cyclic quaternary ammonium sulfonate and the fluoroether compound, the electrochemical energy storage device has better high-temperature storage performance.
In the electrolyte according to the first aspect of the present application, the electrolyte is a liquid electrolyte, a solid polymer electrolyte, or a gel polymer electrolyte. Since the liquid electrolyte has a similar action mechanism to that of the solid polymer electrolyte and the gel polymer electrolyte, the liquid electrolyte is merely exemplified in the present application.
In the electrolyte according to the first aspect of the present application, the cyclic quaternary ammonium sulfonate salt is selected from one or more compounds represented by formula 1; in formula 1, R11One selected from the group consisting of-CN, substituted or unsubstituted C1-12 alkyl, substituted or unsubstituted C2-12 alkenyl, substituted or unsubstituted C2-12 alkynyl, substituted or unsubstituted C1-12 alkoxy, and substituted or unsubstituted C1-12 acyloxy; r12One selected from the group consisting of substituted or unsubstituted C1-12 alkylene, substituted or unsubstituted C2-12 alkenylene, substituted or unsubstituted C2-12 alkynylene, and substituted or unsubstituted C1-12 alkyleneacyl; r13One selected from substituted or unsubstituted C1-12 alkyl, substituted or unsubstituted C2-12 alkenyl, substituted or unsubstituted C2-12 alkynyl, substituted or unsubstituted C1-12 alkoxy, substituted or unsubstituted C1-12 acyloxy, substituted or unsubstituted C6-22 aryl and substituted or unsubstituted C5-22 heteroaryl; r14Selected from substituted or unsubstituted C1-3 alkylene; the substituent is selected from one or more of-CN and halogen atom.
In the formula 1, the first and second groups,
it is meant an anion, and it is meant,
is selected from F-、NO3 -、SO4 2-、PF6 -、PF4 -、AsF6 -、
In the electrolyte according to the first aspect of the present application, in formula 1, preferably, R11One selected from substituted or unsubstituted C1-6 alkyl or halogenated alkyl, R12One selected from substituted or unsubstituted C1-12 alkylene, R13One selected from substituted or unsubstituted C1-6 alkyl or halogenated alkyl, R14One selected from substituted or unsubstituted C1-2 alkylene.
In the electrolyte according to the first aspect of the present application, the cationic group of the cyclic quaternary ammonium sulfonate salt may be selected from
In the electrolyte according to the first aspect of the present application, specifically, the cyclic quaternary ammonium sulfonate salt may be selected from one or more of the following compounds:
In the electrolyte according to the first aspect of the present application, the fluoroether compound is one or more selected from compounds represented by formula 2; in formula 2, R21、R22Each independently selected from one of C1-10 fluoroalkyl and C1-10 fluoroalkoxy.
R21-O-R22Formula 2
In the electrolyte according to the first aspect of the present application, specifically, the fluoroether compound may be selected from one or more of the following compounds;
In the electrolyte according to the first aspect of the present application, the content of the cyclic quaternary ammonium sulfonate salt is too low, and the formed anode and cathode passivation films are not enough to prevent the electrolyte from further reacting, so that the performance of the electrochemical energy storage device is not significantly improved; if the content is too large, the impedance at the positive and negative electrodes increases, which deteriorates the performance of the electrochemical energy storage device. Preferably, the content of the cyclic quaternary ammonium sulfonate salt is 0.05-10% of the total mass of the electrolyte. More preferably, the content of the cyclic quaternary ammonium sulfonate salt is 0.1 to 5 percent of the total mass of the electrolyte.
In the electrolyte according to the first aspect of the present application, the content of the fluoroether compound is too small, and the performance of the electrochemical energy storage device is not significantly improved; if the content is too large, the dynamic performance of the electrochemical energy storage device may be deteriorated due to the increase in the viscosity of the electrolyte. Preferably, the content of the fluoroether compound is 0.1 to 8 percent of the total mass of the electrolyte. More preferably, the content of the fluoroether compound is 1 to 5% of the total mass of the electrolyte.
In the electrolyte according to the first aspect of the present application, the concentration of the electrolyte salt is not particularly limited, and may be selected according to actual needs. Specifically, the content of the electrolyte salt is 6% to 25% of the total mass of the electrolyte solution. Preferably, the content of the electrolyte salt is 6% to 20% of the total mass of the electrolyte solution. Further preferably, the content of the electrolyte salt is 10% to 15% of the total mass of the electrolytic solution.
In the electrolytic solution according to the first aspect of the present application, the electrolyte salt in the electrolytic solution may be selected from a lithium salt or a sodium salt.
In the electrolyte according to the first aspect of the present application, the type of the lithium salt is not particularly limited, and may be selected according to actual needs. Preferably, the lithium salt includes at least LiPF6. The lithium salt may further include LiBF4、LiClO4、LiAsF6、LiSbF6、LiBOB、LiDFOB、LiN(SO2F)2、LiTFSI、LiPO2F2、LiTFOP、LiN(SO2RF)2、LiN(SO2F)(SO2RF), wherein RF ═ CnF2n+1It represents a saturated perfluoroalkyl group, and n is an integer of 1 to 10.
In the electrolyte according to the first aspect of the present application, the type of the sodium salt is not particularly limited, and may be selected according to actual requirementsAnd (4) selecting the row. In particular, the sodium salt may be selected from NaPF6、NaBF4、NaClO4、NaAsF6、NaCF3SO3、NaN(CF3SO2)2、NaN(C2F5SO2)2、NaN(FSO2)2One or more of them.
In the electrolyte according to the first aspect of the present application, the electrolyte further includes an organic solvent, and the type of the organic solvent is not particularly limited and may be selected according to actual needs. Preferably, a non-aqueous organic solvent is used. The non-aqueous organic solvent may include any kind of carbonate and/or carboxylate. The carbonate may include a mixture of cyclic carbonates as well as chain carbonates. The non-aqueous organic solvent may further include a halogenated compound of a carbonate. Specifically, the organic solvent may be one or more selected from ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylethyl carbonate, methyl formate, ethyl acetate, propyl propionate, ethyl propionate, γ -butyrolactone, and tetrahydrofuran.
Next, an electrochemical energy storage device according to the second aspect of the present application will be described.
An electrochemical energy storage device according to the second aspect of the present application comprises an electrolyte according to the first aspect of the present application.
In the electrochemical energy storage device according to the second aspect of the present application, the electrochemical energy storage device further comprises a positive electrode sheet, a negative electrode sheet, a separator, a packaging case, and the like.
In the electrochemical energy storage device according to the second aspect of the present application, it should be noted that the electrochemical energy storage device may be a lithium ion battery, a sodium ion battery, a zinc ion battery, or a super capacitor. In the embodiments of the present application, only the embodiment in which the electrochemical energy storage device is a lithium ion battery is shown, but the present application is not limited thereto.
In the lithium ion battery, the positive plate comprises a positive current collector and a positive film arranged on the positive current collectorAnd (3) slicing. The positive electrode diaphragm comprises a positive electrode active material, and the positive electrode diaphragm also comprises a conductive agent and a binder. The positive active material may be selected from lithium cobaltate (LiCoO)2) Lithium nickelate (LiNiO)2) Spinel type lithium manganate (LiMn)2O4) Olivine type LiMPO4Ternary material LiaNixAyB(1-x-y)O2One or more of them. Wherein the olivine type LiMPO4In the formula, M is selected from one or more of Co, Ni, Fe, Mn and V; in the ternary material LiaNixAyB(1-x-y)O2Wherein A, B is independently selected from one of Co, Al and Mn, A and B are different, a is more than or equal to 0.95 and less than or equal to 1.2, 0<x<1，0<y<1, and x + y<1. The kind of the conductive agent and the binder is not particularly limited and may be selected according to actual requirements.
In the lithium ion battery, the negative electrode sheet comprises a negative electrode current collector and a negative electrode film sheet arranged on the negative electrode current collector. The negative electrode diaphragm comprises a negative electrode active material, and the negative electrode diaphragm also comprises a conductive agent and a binder. The negative active material can be selected from the group consisting of those having a voltage of < 2V (vs. Li/Li)+) A material capable of intercalating lithium. Specifically, the negative active material may be selected from natural graphite, artificial graphite, mesophase micro carbon spheres (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12And one or more of Li-Al alloy. The kind of the conductive agent and the binder is not particularly limited and may be selected according to actual requirements. The negative electrode sheet may also be a metallic lithium sheet.
In the lithium ion battery, the kind of the separator is not particularly limited and may be selected according to actual needs, and specifically, the separator may be selected from a polyethylene film, a polypropylene film, a polyvinylidene fluoride film, and a multi-layer composite film thereof.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. In the embodiments, only the case where the electrochemical energy storage device is a lithium ion battery is shown, but the present application is not limited thereto.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified, and the cyclic quaternary ammonium sulfonate salt used is described in CN105845981A published on 8/10 of 2016.
The lithium ion batteries of examples 1 to 12 and comparative examples 1 to 7 were prepared as follows:
(1) preparation of positive plate
The positive electrode active material lithium cobaltate (LiCoO)2) Mixing acetylene black serving as a conductive agent and polyvinylidene fluoride serving as a binder according to a mass ratio of 98:1:1, adding N-methyl pyrrolidone serving as a solvent, and stirring the mixture under the action of a vacuum stirrer until the system is stable and uniform to obtain anode slurry; uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil with the thickness of 12 mu m; and (3) airing the aluminum foil at room temperature, transferring the aluminum foil to a 120 ℃ oven for drying for 1h, and then performing cold pressing and slitting to obtain the positive plate.
(2) Preparation of negative plate
Mixing the artificial graphite serving as the negative electrode active material, sodium carboxymethyl cellulose (CMC) serving as a thickening agent and styrene butadiene rubber serving as a binder according to the mass ratio of 98:1:1, adding deionized water, and obtaining negative electrode slurry under the action of a vacuum stirrer; uniformly coating the negative electrode slurry on a negative electrode current collector copper foil with the thickness of 8 mu m; and (3) airing the copper foil at room temperature, transferring the copper foil to a 120 ℃ oven for drying for 1h, and then performing cold pressing and slitting to obtain the negative plate.
(3) Preparation of the electrolyte
At water content<In a 10ppm argon atmosphere glove box, Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), and diethyl carbonate (DEC) were mixed in a volume ratio of EC: EMC: DEC: 1:1, and then a fully dried lithium salt LiPF was added6Dissolving the electrolyte in a mixed organic solvent, adding the cyclic quaternary ammonium sulfonate and the fluoroether compound, and uniformly mixing to obtain the electrolyte. Wherein, LiPF6The content of (b) was 12.5% of the total mass of the electrolyte. Specific types of cyclic quaternary ammonium sulfonate salts and fluoroether compounds used in the electrolyteAnd the contents are shown in table 1, and in table 1, the contents of the cyclic quaternary ammonium sulfonate salt and the fluoroether compound are mass percentages calculated based on the total mass of the electrolyte.
(4) Preparation of the separator
A16 μm thick polypropylene separator (model A273 from Celgard) was used.
(5) Preparation of lithium ion battery
Stacking the positive plate, the isolating film and the negative plate in sequence to enable the isolating film to be positioned between the positive plate and the negative plate to play an isolating role, and then winding to obtain a bare cell; placing the bare cell in an outer packaging shell, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the lithium ion battery.
TABLE 1 parameters of examples 1 to 12 and comparative examples 1 to 7
Next, a test procedure of the lithium ion battery is explained.
(1) High temperature storage performance test of lithium ion secondary battery
Charging the lithium ion battery to 4.5V at a constant current of 1C at 25 ℃, then charging to a current of less than 0.05C at a constant voltage of 4.5V, and then discharging to 3.0V at a constant current of 0.5C, and testing the discharge capacity of the lithium ion battery at the moment and marking as D0; charging to 4.5V at a constant current of 1C, then charging to a current of less than 0.05C at a constant voltage of 4.5V, then storing the lithium ion battery at 60 ℃ for 30 days, and after the storage is finished, discharging to 3.0V at a constant current of 1C; and then charging to 4.5V at a constant current of 1C, then charging to a current of less than 0.05C at a constant voltage of 4.5V, and then discharging to 3.0V at a constant current of 0.5C, and testing the discharge capacity of the lithium ion battery at the moment and recording as D1. Each group was tested for 15 lithium ion batteries and the average was taken.
Capacity retention (%) of the lithium ion battery stored at 60 ℃ for 30 days is [ D1/D0] × 100%.
(2) High-temperature storage gas production test of lithium ion battery
Charging the lithium ion battery at a constant current of 0.5 ℃ to a voltage of 4.5V and then at a constant voltage of 4.5V to a current of 0.05C at 25 ℃, and testing the thickness of the lithium ion battery at the moment and marking as h 0; and then putting the lithium ion battery into a constant temperature box with the temperature of 60 ℃, storing for 180 days, taking out, testing the thickness of the lithium ion battery at the moment, and recording as h 1. Each group was tested for 15 lithium ion secondary batteries and the average was taken.
The lithium ion battery stored at 60 ℃ for 180 days has a thickness expansion rate (%) [ (h1-h0)/h0] × 100%.
TABLE 2 Performance test results of examples 1 to 12 and comparative examples 1 to 7
As can be seen from the analysis of the related data in Table 2, the lithium ion battery has better high-temperature storage performance under the combined action of the cyclic quaternary ammonium sulfonate and the fluoroether compound.
Analysis in comparative examples 1-3 shows that the cyclic quaternary ammonium sulfonate and fluoroether compound are not added in comparative example 1, so that the high-temperature storage capacity retention rate and the high-temperature storage thickness expansion rate of the lithium ion battery are poor; when the electrolyte only contains the sulfonic ester cyclic quaternary ammonium salt (comparative example 2), the high-temperature storage capacity retention rate and the high-temperature storage thickness expansion rate of the lithium ion battery can be improved to a certain extent, but the improvement amplitude of the high-temperature storage thickness expansion rate is relatively small, so that the actual use requirement is difficult to meet; when the electrolyte only contains the fluoroether compound (comparative example 3), the high-temperature storage capacity retention rate and the high-temperature storage thickness expansion rate of the lithium ion battery can also be improved to a certain extent, but the improvement range of the high-temperature storage capacity retention rate is relatively small, and the actual use requirement is still difficult to meet.
It can be seen from the analysis in examples 1 to 12 and comparative examples 4 to 7 that the cyclic quaternary ammonium sulfonate salt and the fluoroether compound are added to the electrolyte, the lithium ion battery has a high-temperature storage capacity retention rate and a low high-temperature storage thickness expansion rate, and it can be understood that the specific types and the dosage changes of the cyclic quaternary ammonium sulfonate salt and the fluoroether compound inevitably directly affect the performance of the electrolyte, thereby affecting the effect of improving the performance of the lithium ion battery.
In comparative example 4, the content of the cyclic quaternary ammonium sulfonate salt was insufficient, and the improvement of the high-temperature storage capacity retention rate of the lithium ion battery was weak. In examples 1 to 5, as the content of the cyclic quaternary ammonium sulfonate salt increases, the high-temperature storage capacity retention rate and the high-temperature storage thickness expansion rate of the lithium ion battery are significantly improved. When the content of the sulfonate cyclic quaternary ammonium salt is excessively high, for example, in comparative example 5, the high-temperature storage capacity retention rate of the lithium ion battery is deteriorated.
In comparative example 6, the content of the fluoroether compound was insufficient, and the improvement of the high-temperature storage thickness expansion ratio of the lithium ion battery was weak. In examples 6 to 9 and 3, as the content of the fluoroether compound increases, the high-temperature storage thickness expansion rate of the lithium ion battery decreases significantly without a significant deterioration tendency of the high-temperature storage capacity retention rate of the lithium ion battery. When the content of the fluoroether compound is excessively high, for example, in comparative example 7, the high-temperature storage capacity retention rate of the lithium ion battery is rather deteriorated due to the deterioration of kinetic properties.
Therefore, the low or excessive content of the cyclic quaternary ammonium sulfonate and the fluoroether compound is not beneficial to improving the performance of the lithium ion battery on the whole, but can also improve the high-temperature storage performance of the lithium ion battery to a certain extent in some use requirements which are relatively low or less.
Those skilled in the art to which the present application pertains can also make appropriate changes and modifications to the above-described embodiments, based on the disclosure of the above description. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present application should fall within the scope of the claims of the present application.
Claims (10)
1. An electrolyte, comprising:
an electrolyte salt; and
an additive;
it is characterized in that the preparation method is characterized in that,
the additive comprises sulfonate cyclic quaternary ammonium salt and a fluoroether compound;
the content of the fluoroether compound is 0.1-8% of the total mass of the electrolyte;
the cyclic quaternary ammonium sulfonate is selected from one or more compounds shown in formula 1;
In formula 1, R11One selected from the group consisting of-CN, substituted or unsubstituted C1-12 alkyl, substituted or unsubstituted C2-12 alkenyl, substituted or unsubstituted C2-12 alkynyl, substituted or unsubstituted C1-12 alkoxy, and substituted or unsubstituted C1-12 acyloxy;
R12one selected from the group consisting of substituted or unsubstituted C1-12 alkylene, substituted or unsubstituted C2-12 alkenylene, substituted or unsubstituted C2-12 alkynylene, and substituted or unsubstituted C1-12 alkyleneacyl;
R13one selected from substituted or unsubstituted C1-12 alkyl, substituted or unsubstituted C2-12 alkenyl, substituted or unsubstituted C2-12 alkynyl, substituted or unsubstituted C1-12 alkoxy, substituted or unsubstituted C1-12 acyloxy, substituted or unsubstituted C6-22 aryl and substituted or unsubstituted C5-22 heteroaryl;
R14selected from substituted or unsubstituted C1-3 alkylene;
the substituent is selected from one or more of-CN and halogen atom;
the fluorine ether compound is selected from one or more of the following compounds:
2. the electrolyte of claim 1, wherein the cationic group of the cyclic quaternary ammonium sulfonate salt is selected from the group consisting of
3. The electrolyte as claimed in claim 2, wherein the cyclic quaternary ammonium sulfonate is selected from one or more of the following compounds:
4. the electrolyte of claim 1,
the content of the cyclic quaternary ammonium sulfonate is 0.05-10% of the total mass of the electrolyte;
the content of the fluoroether compound is 1-5% of the total mass of the electrolyte.
5. The electrolyte of claim 4, wherein the cyclic quaternary ammonium sulfonate salt is present in an amount of 0.1% to 5% by weight of the total electrolyte.
6. The electrolyte of claim 1, wherein the electrolyte salt is present in an amount of 6% to 25% by weight of the total electrolyte.
7. The electrolyte of claim 6, wherein the electrolyte salt is present in an amount of 6% to 20% by weight of the total electrolyte.
8. The electrolyte of claim 7, wherein the electrolyte salt is present in an amount of 10% to 15% by weight based on the total weight of the electrolyte.
9. The electrolyte of claim 1, wherein the electrolyte is a liquid electrolyte, a solid polymer electrolyte, or a gel polymer electrolyte.
10. An electrochemical energy storage device comprising an electrolyte according to any one of claims 1 to 9.
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