CA2560605C - Overcharge protection for electrochemical cells - Google Patents
Overcharge protection for electrochemical cells Download PDFInfo
- Publication number
- CA2560605C CA2560605C CA2560605A CA2560605A CA2560605C CA 2560605 C CA2560605 C CA 2560605C CA 2560605 A CA2560605 A CA 2560605A CA 2560605 A CA2560605 A CA 2560605A CA 2560605 C CA2560605 C CA 2560605C
- Authority
- CA
- Canada
- Prior art keywords
- carbonate
- cell
- lithium
- salt
- borate
- 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.)
- Expired - Fee Related
Links
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 43
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 150000001642 boronic acid derivatives Chemical group 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 32
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 29
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 230000002441 reversible effect Effects 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- PILOAHJGFSXUAY-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropyl methyl carbonate Chemical compound COC(=O)OC(F)(F)C(F)(F)C(F)(F)F PILOAHJGFSXUAY-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- QYIOFABFKUOIBV-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxol-2-one Chemical compound CC=1OC(=O)OC=1C QYIOFABFKUOIBV-UHFFFAOYSA-N 0.000 claims description 3
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims description 3
- FWLUTJHBRZTAMP-UHFFFAOYSA-N B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+] Chemical compound B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.B([O-])([O-])F.[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+] FWLUTJHBRZTAMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910013400 LiN(SO2CF2CF3) Inorganic materials 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 claims description 3
- ZXUXGOZWYSJTGF-UHFFFAOYSA-N bis(2,2,3,3,3-pentafluoropropyl) carbonate Chemical compound FC(F)(F)C(F)(F)COC(=O)OCC(F)(F)C(F)(F)F ZXUXGOZWYSJTGF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- YTHRBPGWYGAQGO-UHFFFAOYSA-N ethyl 1,1,2,2,2-pentafluoroethyl carbonate Chemical compound CCOC(=O)OC(F)(F)C(F)(F)F YTHRBPGWYGAQGO-UHFFFAOYSA-N 0.000 claims description 3
- SACILZPKPGCHNY-UHFFFAOYSA-N ethyl 1,1,2,2,3,3,3-heptafluoropropyl carbonate Chemical compound CCOC(=O)OC(F)(F)C(F)(F)C(F)(F)F SACILZPKPGCHNY-UHFFFAOYSA-N 0.000 claims description 3
- ARUVERQDOCMNCO-UHFFFAOYSA-N ethyl 1,1,2,2,3,3,4,4,4-nonafluorobutyl carbonate Chemical compound CCOC(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F ARUVERQDOCMNCO-UHFFFAOYSA-N 0.000 claims description 3
- NIQAXIMIQJNOKY-UHFFFAOYSA-N ethyl 2,2,2-trifluoroethyl carbonate Chemical compound CCOC(=O)OCC(F)(F)F NIQAXIMIQJNOKY-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001500 lithium hexafluoroborate Inorganic materials 0.000 claims description 3
- GZJQAHYLPINVDV-UHFFFAOYSA-N methyl 1,1,2,2,2-pentafluoroethyl carbonate Chemical compound COC(=O)OC(F)(F)C(F)(F)F GZJQAHYLPINVDV-UHFFFAOYSA-N 0.000 claims description 3
- WQOUFURVFJFHIW-UHFFFAOYSA-N methyl 1,1,2,2,3,3,4,4,4-nonafluorobutyl carbonate Chemical compound COC(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F WQOUFURVFJFHIW-UHFFFAOYSA-N 0.000 claims description 3
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- TVBISCWBJBKUDP-UHFFFAOYSA-N borate Chemical class [O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] TVBISCWBJBKUDP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 2
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 claims 2
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims 2
- 229910010912 Li2B12F12 Inorganic materials 0.000 claims 1
- 229910010906 Li2B12F5H7 Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229910011096 Li2B12F9H3 Inorganic materials 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910014549 LiMn204 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LNDSOCVWNZLFJP-UHFFFAOYSA-N 1,2-dimethoxyethane;4-methyl-1,3-dioxolane Chemical compound COCCOC.CC1COCO1 LNDSOCVWNZLFJP-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000005621 boronate group Chemical class 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 239000002265 redox agent Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- H01M10/052—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
- H01M10/056—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
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to an improvement in a cell which is normally susceptible to damage from overcharging comprised of a negative electrode, a positive electrode, and an electrolyte comprised of an overcharge protection salt carried in a carrier or solvent. Representative overcharge protection salts are embraced by the formula: M a Q where M is an electrochemically stable cation selected from the group consisting of alkali metal, alkaline earth metal, tetraalkylammonium, or imidazolium groups, and Q is a borate or heteroborate cluster and a is the integer 1 or 2.
Description
TITLE OF THE INVENTION:
OVERCHARGE PROTECTION FOR
ELECTROCHEMICAL CELLS
BACKGROUND OF THE INVENTION
[0004] Primary and secondary batteries comprise one or more electrochemical cells.
Many batteries comprise lithium cells, because of lithium's large reduction potential, low molecular weight of elemental lithium, and high power density. For secondary cells, the small size and high mobility of lithium cations allow for the possibility of rapid recharging.
These advantages make lithium secondary batteries ideal for portable electronic devices, e.g., cell phones and laptop computers. Recently, larger size lithium batteries are being developed which have application for use in the hybrid electric vehicle market.
[0005] In a lithium secondary cell one of most important concerns is safety and, in particular, the safety problem posed by an overcharge situation, i.e., the application of an overvoltage to a fully charged cell. One danger of overcharging lithium cells employing metal oxide cathodes is that oxygen evolution can occur and create explosive mixtures within the cell. Another danger is that the cell can overheat and cause burns.
[0006] In the case of a lithium-based secondary cell, which is of the non-aqueous type, two methods have been developed for dealing with overcharge; one method utilizes a chemical reaction and the other method an electronic circuit. The chemical method has typically involved the addition of a redox shuttle additive also referred to as a reversible oxidation/reduction agent, which is reversibly oxidized just above the fully charged cell voltage. Then, the additive migrates across the electrolyte solution in its oxidized state to the anode where it is reduced back to its original state. Electronic circuits typically disable, sometimes permanently, the battery when activated.
[0007] The following patents are representative of lithium secondary batteries and electrochemical cells:
[0008] US 5,763,119 discloses non-aqueous lithium secondary cells having overcharge protection. In the background of the patent a technique for preventing the overcharge of the cell using a chemical reaction is suggested wherein it is recommended that a reversible redox agent be added to the electrolyte solution. Fe, Ru and Ce complexes are described as having high oxidation-reduction potential and high electrochemical stability and, therefore, use as reversible oxidation/reduction agents for 4 volt-class lithium-ion secondary cells. The solution for preventing overcharge damage in '119 involved the addition of a substituted benzene, e.g., a dimethoxy fluoro or bromo benzene as a redox shuttle in a cell comprised of a metal lithium anode, a lithium cobalt oxide cathode, L1PF6 electrolyte salt and a mixture of propylene carbonate and dimethyl carbonate.
[0009] US 4,201,839 discloses an electrochemical cell based upon alkali metal-containing anodes, solid cathodes, and electrolytes where the electrolytes are closoborane compounds carried in aprotic solvents. Closoboranes employed are of the formula Z2BXn and ZCBmXm wherein Z is an alkali metal, C is carbon, R is a radical selected from the group consisting of organic hydrogen and halogen atoms, B is boron, X is one or more substituents from the group consisting of hydrogen and the halogens, m is an integer from 5 to 11, and n is an integer from 6 to 12. Specifically disclosed examples of closoborane electrolytes employed in the electrochemical cells include lithium octabromooctaborate, lithium decachlorodecaborate, lithium dodecachlorododecaborate, and lithium iododecaborate.
[0010] US 6,346,351 discloses electrolyte systems for a rechargeable cell of high compatibility towards positive electrode structures based upon a salt and solvent . =
mixture. Lithium tetrafluoroborate and lithium hexafluorophosphate are examples of salts. Examples of solvents include diethyl carbonate, dimethoxyethane, methylformate, and so forth. In the background are disclosed known electrolytes for lithium cells, which include lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, 5 lithium tetrafluoroborate, lithium bromide, and lithium hexafluoroantimonate electrolytes incorporated in solvents.
[0011] Journal of the Electrochemical Society, 151 (9) A1429-A1435 (2004) and references therein disclose boronate, borate and borane-based Lewis acids as additives capable of solubilizing LiF and other Li salts which typically have poor solubility in non-aqueous solvent systems, thus rendering these salts lithium ion electrolytes in lithium ion cells.
[0012] The previously identified patents, patent applications and publications are hereby incorporated by reference.
BRIEF SUMMARY OF THE INVENTION
[0013] This invention solves problems associated with conventional electrolytes by providing improved overcharge protection to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte. While any suitable electrolyte can be employed an example of a suitable electrolyte comprises that disclosed in U.S. Published Patent Application Nos. US20050053841 Al and US20050064288. The present invention is useful for primary and secondary cells, especially those that may be susceptible to damage from overcharging. By "overcharge" or "overcharging" it is meant charging a cell to a potential above the normal fully charged potential of the cell, or charging a cell above 100% state of charge.
[0014] One aspect of the instant invention relates to extending the overcharge capacity of cells by using at least one additive. Without wishing to be bound by any theory or explanation it is believed that such additives minimize the effects of irreversible reactions that may occur in certain electrolyte/cells. It is also believed that effective additives are those which can minimize the amount of fluoride formed in the cell on overcharge, and those which are capable of dissolving any fluoride or other resistive salts formed at the electrode surfaces.
OVERCHARGE PROTECTION FOR
ELECTROCHEMICAL CELLS
BACKGROUND OF THE INVENTION
[0004] Primary and secondary batteries comprise one or more electrochemical cells.
Many batteries comprise lithium cells, because of lithium's large reduction potential, low molecular weight of elemental lithium, and high power density. For secondary cells, the small size and high mobility of lithium cations allow for the possibility of rapid recharging.
These advantages make lithium secondary batteries ideal for portable electronic devices, e.g., cell phones and laptop computers. Recently, larger size lithium batteries are being developed which have application for use in the hybrid electric vehicle market.
[0005] In a lithium secondary cell one of most important concerns is safety and, in particular, the safety problem posed by an overcharge situation, i.e., the application of an overvoltage to a fully charged cell. One danger of overcharging lithium cells employing metal oxide cathodes is that oxygen evolution can occur and create explosive mixtures within the cell. Another danger is that the cell can overheat and cause burns.
[0006] In the case of a lithium-based secondary cell, which is of the non-aqueous type, two methods have been developed for dealing with overcharge; one method utilizes a chemical reaction and the other method an electronic circuit. The chemical method has typically involved the addition of a redox shuttle additive also referred to as a reversible oxidation/reduction agent, which is reversibly oxidized just above the fully charged cell voltage. Then, the additive migrates across the electrolyte solution in its oxidized state to the anode where it is reduced back to its original state. Electronic circuits typically disable, sometimes permanently, the battery when activated.
[0007] The following patents are representative of lithium secondary batteries and electrochemical cells:
[0008] US 5,763,119 discloses non-aqueous lithium secondary cells having overcharge protection. In the background of the patent a technique for preventing the overcharge of the cell using a chemical reaction is suggested wherein it is recommended that a reversible redox agent be added to the electrolyte solution. Fe, Ru and Ce complexes are described as having high oxidation-reduction potential and high electrochemical stability and, therefore, use as reversible oxidation/reduction agents for 4 volt-class lithium-ion secondary cells. The solution for preventing overcharge damage in '119 involved the addition of a substituted benzene, e.g., a dimethoxy fluoro or bromo benzene as a redox shuttle in a cell comprised of a metal lithium anode, a lithium cobalt oxide cathode, L1PF6 electrolyte salt and a mixture of propylene carbonate and dimethyl carbonate.
[0009] US 4,201,839 discloses an electrochemical cell based upon alkali metal-containing anodes, solid cathodes, and electrolytes where the electrolytes are closoborane compounds carried in aprotic solvents. Closoboranes employed are of the formula Z2BXn and ZCBmXm wherein Z is an alkali metal, C is carbon, R is a radical selected from the group consisting of organic hydrogen and halogen atoms, B is boron, X is one or more substituents from the group consisting of hydrogen and the halogens, m is an integer from 5 to 11, and n is an integer from 6 to 12. Specifically disclosed examples of closoborane electrolytes employed in the electrochemical cells include lithium octabromooctaborate, lithium decachlorodecaborate, lithium dodecachlorododecaborate, and lithium iododecaborate.
[0010] US 6,346,351 discloses electrolyte systems for a rechargeable cell of high compatibility towards positive electrode structures based upon a salt and solvent . =
mixture. Lithium tetrafluoroborate and lithium hexafluorophosphate are examples of salts. Examples of solvents include diethyl carbonate, dimethoxyethane, methylformate, and so forth. In the background are disclosed known electrolytes for lithium cells, which include lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, 5 lithium tetrafluoroborate, lithium bromide, and lithium hexafluoroantimonate electrolytes incorporated in solvents.
[0011] Journal of the Electrochemical Society, 151 (9) A1429-A1435 (2004) and references therein disclose boronate, borate and borane-based Lewis acids as additives capable of solubilizing LiF and other Li salts which typically have poor solubility in non-aqueous solvent systems, thus rendering these salts lithium ion electrolytes in lithium ion cells.
[0012] The previously identified patents, patent applications and publications are hereby incorporated by reference.
BRIEF SUMMARY OF THE INVENTION
[0013] This invention solves problems associated with conventional electrolytes by providing improved overcharge protection to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte. While any suitable electrolyte can be employed an example of a suitable electrolyte comprises that disclosed in U.S. Published Patent Application Nos. US20050053841 Al and US20050064288. The present invention is useful for primary and secondary cells, especially those that may be susceptible to damage from overcharging. By "overcharge" or "overcharging" it is meant charging a cell to a potential above the normal fully charged potential of the cell, or charging a cell above 100% state of charge.
[0014] One aspect of the instant invention relates to extending the overcharge capacity of cells by using at least one additive. Without wishing to be bound by any theory or explanation it is believed that such additives minimize the effects of irreversible reactions that may occur in certain electrolyte/cells. It is also believed that effective additives are those which can minimize the amount of fluoride formed in the cell on overcharge, and those which are capable of dissolving any fluoride or other resistive salts formed at the electrode surfaces.
, = CA 02560605 2009-04-07 [0014a] In accordance with one embodiment of the present invention, there is provided an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, the electrolyte comprising at least one salt that provides overcharge protection, at least one carrier, and at least one additive, wherein the additive comprises at least one, oxalato borate; wherein the salt that provides overcharge protection comprises a salt of the formula MaQ, where M is an electrochemically stable cation, Q is a borate cluster anion or heteroborate cluster anion, and a is 1 or 2.
[0014b] In accordance with another embodiment of the present invention there is provided an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte comprising at least one aprotic organic carrier, at least one lithium oxalato borate, and at least one salt that provides overcharge protection represented by the general formula Li2B12F.H12, where x=9, 10, 11 or 12, Li21112FxCl12.x where x=6, 7, 8, 9, 10, 11 or 12, or Li21312Fx(OH)12-x where x=10 or 11.
[0014c] The electrolyte may further include at least one nonreversibly oxidizable salt, such as lithium. Preferably, the nonreversibly oxidizable salt comprises at least one member selected from the group consisting of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroborate, lithium trifluoromethylsulfonate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate lithium bromide, and lithium hexafluoroantimonate, L1B(C6I-15)4, LiN(SO2OF3)2, LiN(SO2CF2CF3) and lithium bis(chelato)borates and mixtures thereof.
[0014d] In a preferred embodiment M comprises at least one member selected from the group consisting of alkali metal, alkaline earth metal, tetraalkylammonium, and imidazolium and Q comprises at least one member selected from the group consisting of: i) a c/oso-borate anion of the formula (B8_12412)2-, where Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, ii) a c/oso-ammonioborate anion compositions of formula:
((R'R"R")NB8_12Z7-11)1-; where N is bonded to B and each of R', R", R" is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and/or a polymer, Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, and iii) a c/oso-monocarborate anion compositions of formula (R¨CB7_11Z7_11)1-, where R"" is bonded to C and selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and/or a polymer; Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl.
[0014e] Preferably, the salt that provides overcharge protection is selected from the group consisting of Li21310H0_7Z3_10 where Z is Cl, OR, L12B10Cl10, L12B10H1_3C15_9, LI2B10C15-9(0R)1-5, L12B10H2C18; Li2B10H0_7(OCH3)3, Li21310C18(OH)2, Li21310Br10, Li2B8Br8, L121312C112, and L12B12I12.
- 3a -. . , , [0014f] In another preferred embodiment the salt comprises at least one lithium fluoroborate selected from the group consisting of those compounds represented by the formulas: Li2B10FxZ10-x;
and Li2B12FxZ12-x wherein x is at least 3 for the decaborate salt and at least 5 for the dodecaborate salt, and Z
represents H, Cl, Br, or OR, where R = H, 01-8 alkyl or fluoroalkyl.
Preferably, the lithium fluoroborate has a reversible oxidation potential from 0.1 to 1 volt above the voltage of the cell. Preferably, the lithium fluoroborate salt is added in an amount from about 3 to about 70 % by weight of the total weight of the nonreversibly oxidizable salt and said salt that provides overcharge protection present in the cell.
[0014g] Preferably, the carrier comprises an aprotic organic comprising at least one member selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, fluorinated oligomers, methyl propionate, butyl propionate, ethyl propionate, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxolane, 4-methyl-dioxolane dimethoxyethane, triglyme, dimethylvinylene carbonate, vinylene carbonate, chloroethylene carbonate, tetraethyleneglycol, dimethyl ether, polyethylene glycols, sulfones, and gamma-butyrolactone.
- 3b -BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
[0015] Figure 1 is a graph of capacity retention v. cycle number for Examples 1-5, where AP-F9 represents the formula of the present invention where x is 9.
[0016] Figure 2 is a graph of voltage v. time for Example 6.
[0017] Figure 3 is a graph of voltage v. time for Example 7.
[0018] Figure 4 is a graph of voltage v. time for Example 8.
[0019] Figure 5 is a graph of capacity v. cycle number for Examples 2, 6, 7 and 8, where Ch represents charge and Dch represents discharge.
[0020] Figure 6 is a graph of capacity v. cycle for Example 8.
DETAILED DESCRIPTION OF THE INVENTION
[0021] U.S. Patent Application Publication No. US20050064288 Al discloses the ranges of borate cluster salts useful for electrochemical cells, the useful salts for lithium ion cells and the use of other electrolyte salts with the borate cluster salts to provide stable Solid Electrolyte Interface (SEI) layers in lithium ion cells.
[0022] While certain salts provide overcharge protection for extended periods of time, in some cases the redox shuttle chemistry is not completely reversible (e.g., that is the borate cluster salts do undergo slow decomposition during the overcharging process). The products of this decomposition reaction can lead to electrically and ionically resistive layers on the electrodes which in turn may lead to a significant decrease in discharge capacity of the cells on long term overcharging. In some cases, an extended overcharge could occur in one or more cells in a series of cells or pack during trickle charging (e.g., trickle charging is defined as the low rate charging of a cell pack to main full pack potential), or during multiple charges of the pack if the cell (or cells) undergoing overcharge has lower capacity than the other cells in the pack.
[0023] The instant invention provides an electrolyte which allows the borate cluster salts to provide prolonged overcharge protection without substantially contributing to capacity fade of cells (e.g., by capacity fade it is meant loss of electrochemical energy storage capability after overcharging, or on successive charging and discharging of the cell). The electrolyte solution of this invention can be non-aqueous and comprise the borate cluster salts and a lithium bis-oxalato borate (e.g., as an SEI layer forming additive). The amount of lithium bis-oxalato borate will normally range from about 0.1 to about 5 wt.% of the electrolyte.
[0024] The inventive electrolyte can also incorporate a molecular (non-salt) fluorinated tri-substituted borane acid such as tris-(perfluorophenyl) borane (e.g, as an anion receptor which appears to hinder the buildup of resistive films brought about by borate decomposition that can occur during overcharge). Other suitable tri-substituted acids can be selected from the list of borates ¨ boron containing acids in which B
is bonded to 3 oxygens, boronates ¨ boron containing acids in which the boron is bound to a mixture of 3 carbons and oxygens, and boranes - boron containing acids in which the boron is bound to 3 carbons. Other soluble, non-HF generating Lewis acids may be effective in extending the life of overcharge protection provided by the borate cluster salt. If desired, the acid can be used in an electrolyte that also contains lithium bis-oxalato borate. The amount of acid normally ranges from about 0.1 to about 5 wt.% of the electrolyte. The instant invention can increase the length of effective overcharge and hence overcharge capacity can be extended greater than 4 times.
[0025] The inventive electrolyte can be produced by combining the electrolyte ingredients in conventional equipment and using conventional methods. In a typical embodiment the electrolye formula will contain 75-99 wt. % solvent, 1- 20 wt.%
salt, 0.1 to 5 wt.% acid and 0.1 to 5 wt.% LiBOB.
[0026] The following Examples are provided to illustrate certain aspects of the inventiona and shall not limit the scope of any claims appended hereto.
Example 1 [0027] A coin type cell battery (diameter 20 mm, thickness 3.2 mm) comprised of a positive electrode, negative electrode, separator and electrolyte was prepared at room temperature. The positive electrode consists of LiMn204 (positive electrode active material) 84% by weight, carbon black (conducting agent) 4% by weight, SFG-6 graphite (conducting agent) 4% by weight, polyvinylidene fluoride (binder) 8% by weight on an aluminum foil current collector. The negative electrode consists of MCMB(anode active material) 92% by weight, polyvinylidene fluoride (binder) 8% by weight on a copper foil current collector. The separator, Celgard Tm 3501, (available from Celgard Inc.) comprises the microporous polypropylene film.
[0014b] In accordance with another embodiment of the present invention there is provided an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte comprising at least one aprotic organic carrier, at least one lithium oxalato borate, and at least one salt that provides overcharge protection represented by the general formula Li2B12F.H12, where x=9, 10, 11 or 12, Li21112FxCl12.x where x=6, 7, 8, 9, 10, 11 or 12, or Li21312Fx(OH)12-x where x=10 or 11.
[0014c] The electrolyte may further include at least one nonreversibly oxidizable salt, such as lithium. Preferably, the nonreversibly oxidizable salt comprises at least one member selected from the group consisting of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroborate, lithium trifluoromethylsulfonate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate lithium bromide, and lithium hexafluoroantimonate, L1B(C6I-15)4, LiN(SO2OF3)2, LiN(SO2CF2CF3) and lithium bis(chelato)borates and mixtures thereof.
[0014d] In a preferred embodiment M comprises at least one member selected from the group consisting of alkali metal, alkaline earth metal, tetraalkylammonium, and imidazolium and Q comprises at least one member selected from the group consisting of: i) a c/oso-borate anion of the formula (B8_12412)2-, where Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, ii) a c/oso-ammonioborate anion compositions of formula:
((R'R"R")NB8_12Z7-11)1-; where N is bonded to B and each of R', R", R" is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and/or a polymer, Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, and iii) a c/oso-monocarborate anion compositions of formula (R¨CB7_11Z7_11)1-, where R"" is bonded to C and selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and/or a polymer; Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl.
[0014e] Preferably, the salt that provides overcharge protection is selected from the group consisting of Li21310H0_7Z3_10 where Z is Cl, OR, L12B10Cl10, L12B10H1_3C15_9, LI2B10C15-9(0R)1-5, L12B10H2C18; Li2B10H0_7(OCH3)3, Li21310C18(OH)2, Li21310Br10, Li2B8Br8, L121312C112, and L12B12I12.
- 3a -. . , , [0014f] In another preferred embodiment the salt comprises at least one lithium fluoroborate selected from the group consisting of those compounds represented by the formulas: Li2B10FxZ10-x;
and Li2B12FxZ12-x wherein x is at least 3 for the decaborate salt and at least 5 for the dodecaborate salt, and Z
represents H, Cl, Br, or OR, where R = H, 01-8 alkyl or fluoroalkyl.
Preferably, the lithium fluoroborate has a reversible oxidation potential from 0.1 to 1 volt above the voltage of the cell. Preferably, the lithium fluoroborate salt is added in an amount from about 3 to about 70 % by weight of the total weight of the nonreversibly oxidizable salt and said salt that provides overcharge protection present in the cell.
[0014g] Preferably, the carrier comprises an aprotic organic comprising at least one member selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, fluorinated oligomers, methyl propionate, butyl propionate, ethyl propionate, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxolane, 4-methyl-dioxolane dimethoxyethane, triglyme, dimethylvinylene carbonate, vinylene carbonate, chloroethylene carbonate, tetraethyleneglycol, dimethyl ether, polyethylene glycols, sulfones, and gamma-butyrolactone.
- 3b -BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
[0015] Figure 1 is a graph of capacity retention v. cycle number for Examples 1-5, where AP-F9 represents the formula of the present invention where x is 9.
[0016] Figure 2 is a graph of voltage v. time for Example 6.
[0017] Figure 3 is a graph of voltage v. time for Example 7.
[0018] Figure 4 is a graph of voltage v. time for Example 8.
[0019] Figure 5 is a graph of capacity v. cycle number for Examples 2, 6, 7 and 8, where Ch represents charge and Dch represents discharge.
[0020] Figure 6 is a graph of capacity v. cycle for Example 8.
DETAILED DESCRIPTION OF THE INVENTION
[0021] U.S. Patent Application Publication No. US20050064288 Al discloses the ranges of borate cluster salts useful for electrochemical cells, the useful salts for lithium ion cells and the use of other electrolyte salts with the borate cluster salts to provide stable Solid Electrolyte Interface (SEI) layers in lithium ion cells.
[0022] While certain salts provide overcharge protection for extended periods of time, in some cases the redox shuttle chemistry is not completely reversible (e.g., that is the borate cluster salts do undergo slow decomposition during the overcharging process). The products of this decomposition reaction can lead to electrically and ionically resistive layers on the electrodes which in turn may lead to a significant decrease in discharge capacity of the cells on long term overcharging. In some cases, an extended overcharge could occur in one or more cells in a series of cells or pack during trickle charging (e.g., trickle charging is defined as the low rate charging of a cell pack to main full pack potential), or during multiple charges of the pack if the cell (or cells) undergoing overcharge has lower capacity than the other cells in the pack.
[0023] The instant invention provides an electrolyte which allows the borate cluster salts to provide prolonged overcharge protection without substantially contributing to capacity fade of cells (e.g., by capacity fade it is meant loss of electrochemical energy storage capability after overcharging, or on successive charging and discharging of the cell). The electrolyte solution of this invention can be non-aqueous and comprise the borate cluster salts and a lithium bis-oxalato borate (e.g., as an SEI layer forming additive). The amount of lithium bis-oxalato borate will normally range from about 0.1 to about 5 wt.% of the electrolyte.
[0024] The inventive electrolyte can also incorporate a molecular (non-salt) fluorinated tri-substituted borane acid such as tris-(perfluorophenyl) borane (e.g, as an anion receptor which appears to hinder the buildup of resistive films brought about by borate decomposition that can occur during overcharge). Other suitable tri-substituted acids can be selected from the list of borates ¨ boron containing acids in which B
is bonded to 3 oxygens, boronates ¨ boron containing acids in which the boron is bound to a mixture of 3 carbons and oxygens, and boranes - boron containing acids in which the boron is bound to 3 carbons. Other soluble, non-HF generating Lewis acids may be effective in extending the life of overcharge protection provided by the borate cluster salt. If desired, the acid can be used in an electrolyte that also contains lithium bis-oxalato borate. The amount of acid normally ranges from about 0.1 to about 5 wt.% of the electrolyte. The instant invention can increase the length of effective overcharge and hence overcharge capacity can be extended greater than 4 times.
[0025] The inventive electrolyte can be produced by combining the electrolyte ingredients in conventional equipment and using conventional methods. In a typical embodiment the electrolye formula will contain 75-99 wt. % solvent, 1- 20 wt.%
salt, 0.1 to 5 wt.% acid and 0.1 to 5 wt.% LiBOB.
[0026] The following Examples are provided to illustrate certain aspects of the inventiona and shall not limit the scope of any claims appended hereto.
Example 1 [0027] A coin type cell battery (diameter 20 mm, thickness 3.2 mm) comprised of a positive electrode, negative electrode, separator and electrolyte was prepared at room temperature. The positive electrode consists of LiMn204 (positive electrode active material) 84% by weight, carbon black (conducting agent) 4% by weight, SFG-6 graphite (conducting agent) 4% by weight, polyvinylidene fluoride (binder) 8% by weight on an aluminum foil current collector. The negative electrode consists of MCMB(anode active material) 92% by weight, polyvinylidene fluoride (binder) 8% by weight on a copper foil current collector. The separator, Celgard Tm 3501, (available from Celgard Inc.) comprises the microporous polypropylene film.
[0028] The electrolyte was a 0.4 M solution of Li2B12F9H3 in 3:7 by weight EC
(ethylene carbonate):DEC (diethyl carbonate). The cell was charged and discharged multiple times at a C/3-rate constant current between 3.0 and 4.2 V. The capacity retention vs cycle number is shown in Fig. la. Rapid capacity fade was observed with complete fade occurring over 80 cycles.
Example 2 [0029] A cell was fabricated and cycled as in Example 1, with the exception that 1%
vinylethylene carbonate was added to the electrolyte solution of 0.4 M
L121312F9H3 in 3:7 by weight EC:DEC to help improve formation of a solid electrolyte interface at the negative electrode. As can be seen in Fig. 1 b, capacity retention was improved over example 1; however, greater than 50 % capacity loss was observed over 80 cycles and an initial irreversible capacity loss was also observed.
Example 3 [0030] A cell was fabricated and cycled as in Example 1, with the exception that the electrolyte solution was 0.36 M L12B12F9H3 and 0.08 M LiPF6 in 3:7 by weight EC:DEC.
The LIPF6 was added to help improve formation of a solid electrolyte interface at the negative electrode. As can be seen in Fig. 1 c, capacity retention was improved over Examples 1 and 2. Capacity fade was observed on cycling.
Example 4 [0031] A cell was fabricated and cycled as in Example 1, with the exception that the electrolyte solution was 0.36 M Li2B/2F9F13 and 0.08 M lithium bis-oxalatoborate (LiBOB) in 3:7 by weight EC:DEC. The LiBOB was added (e.g., to improve formation of a solid electrolyte interface at the negative electrode without adding a source of HF
as with L1PF6 addition in Example 3). As can be seen in Fig. 1 d, no capacity loss was observed over 100 charge/discharge cycles.
Example 5 [0032] A cell was fabricated and cycled as in Example 1, with the exception that the electrolyte solution was 0.36 M L12B12F9H3, 0.04 LiBOB and 0.04 M L1PF6 in 3:7 by weight EC:DEC. As can be seen in Fig. 1 e, very slow capacity fade is observed on cycling. This result and those of Examples 3 and 4 indicate that both LiPF6 and LiBOB
are capable of forming stable SEI layers on MCMB with electrolytes containing borate cluster salt, but that LiBOB alone as an additive was better than LiPF6 alone or in combination with LiPF6. Without wishing to be bound by any theory or explanation this result may be due to the sensitivity of the LiMn204 positive electrode in the presence of traces of HF contained in LiPF6.
Example 6 Overcharge Protection with Li2B12F9H3 ¨ based electrolyte [0033] A cell was fabricated as in Example 1 with an electrolyte comprising 0.4 M
Li2B12F9H3 in 3:7 by weight EC:DEC. In each charge/discharge cycle, the cell was charged at a C/3 rate for 4 hrs followed by a constant current discharge at C/3 rate to 3.0 V. Such a charging protocol effectively overcharges the cell at to at least 33% above its full charge capacity. The cycle data presented in Figure 2 show that the cell potential is limited to ¨ 4.5 V on overcharge by the use of the Li2B12F9H3 electrolyte and that this overcharge protection lasts for ¨ 40 of the mentioned overcharge/discharge cycles. This electrolye provides a total of ¨ 260 hrs overcharge protection at this overcharging rate, after which time the cell potential is no longer limited on overcharge. Figure 5 shows the charging capacity and discharge capacity retention on overcharging indicates that this cell rapidly loses 4.2 to 3V discharge capacity and by the time the overcharge protection fails, no capacity remains in the cell.
Example 7 Overcharge Protection with Li2B12F9H3¨ based electrolyte + LIBOB additive [0034] A cell was fabricated as in Example 1 with an electrolyte comprising 0.36 M
Li2B12F9H3 and 0.08M lithium bis(oxalato)borate (LiBOB) in 3:7 by weight EC:DEC. In each charge/discharge cycle, the cell was charged at a C/3 rate for 4 hrs followed by a constant current discharge at C/3 rate to 3.0 V. Such a charging protocol effectively overcharges the cell at to at least 33% above its full charge capacity. The cycle data presented in Figure 3 show that the cell potential is limited to ¨ 4.5 V on overcharge by the use of the Li2B12F9H3 electrolyte and that this overcharge protection lasts for ¨ 100 of the mentioned overcharge/discharge cycles. This electrolye formulation provides a total of ¨ 680 hrs overcharge protection at this overcharging rate, after which time the cell =
potential is no longer limited on overcharge. Figure 5 showing the charging capacity and discharge capacity retention on overcharging indicates that this cell loses 4.2 to 3V
discharge capacity at a slower rate than the cell of example 6 and stabilizes at - 30-40%
of the full charge capacity between overcharge cycles 40 and 120. At the time the overcharge protection fails, no 4.2V to 3V discharge capacity remains in the cell.
Example 8 Overcharge Protection with L12B12F9H3- based electrolyte + LIBOB additive +
tris(pentafluorophenyl) borane additive [0035] A cell was fabricated as in Example 1 with an electrolyte comprising 0.36 M
L12B12F9H3 and 0.08M lithium bis(oxalato)borate (LiBOB) and 5 wt.%
tris(pentafluorophenyl) borane in 3:7 by weight EC:DEC. In each charge/discharge cycle, the cell was charged at a C/3 rate for 4 hrs followed by a constant current discharge at C/3 rate to 3.0 V. Such a charging protocol effectively overcharges the cell at to at least 33% above its full charge capacity. The cycle data presented in Figure 4 show that the cell potential is limited to - 4.5 V on overcharge by the use of the L12B12F9H3 electrolyte and that this overcharge protection is still effective after - 160 of the mentioned overcharge/discharge cycles. This electrolye formulation was still providing overcharge protection after 865 hrs at this overcharging rate. Figure 5 shows that 4.2 to discharge capacity retention is quite good even over the 160 overcharge cycles of this test. Figure 6 shows the affect of using 5% TPFPB
(tris(pentafluorophenyl)borane).
(ethylene carbonate):DEC (diethyl carbonate). The cell was charged and discharged multiple times at a C/3-rate constant current between 3.0 and 4.2 V. The capacity retention vs cycle number is shown in Fig. la. Rapid capacity fade was observed with complete fade occurring over 80 cycles.
Example 2 [0029] A cell was fabricated and cycled as in Example 1, with the exception that 1%
vinylethylene carbonate was added to the electrolyte solution of 0.4 M
L121312F9H3 in 3:7 by weight EC:DEC to help improve formation of a solid electrolyte interface at the negative electrode. As can be seen in Fig. 1 b, capacity retention was improved over example 1; however, greater than 50 % capacity loss was observed over 80 cycles and an initial irreversible capacity loss was also observed.
Example 3 [0030] A cell was fabricated and cycled as in Example 1, with the exception that the electrolyte solution was 0.36 M L12B12F9H3 and 0.08 M LiPF6 in 3:7 by weight EC:DEC.
The LIPF6 was added to help improve formation of a solid electrolyte interface at the negative electrode. As can be seen in Fig. 1 c, capacity retention was improved over Examples 1 and 2. Capacity fade was observed on cycling.
Example 4 [0031] A cell was fabricated and cycled as in Example 1, with the exception that the electrolyte solution was 0.36 M Li2B/2F9F13 and 0.08 M lithium bis-oxalatoborate (LiBOB) in 3:7 by weight EC:DEC. The LiBOB was added (e.g., to improve formation of a solid electrolyte interface at the negative electrode without adding a source of HF
as with L1PF6 addition in Example 3). As can be seen in Fig. 1 d, no capacity loss was observed over 100 charge/discharge cycles.
Example 5 [0032] A cell was fabricated and cycled as in Example 1, with the exception that the electrolyte solution was 0.36 M L12B12F9H3, 0.04 LiBOB and 0.04 M L1PF6 in 3:7 by weight EC:DEC. As can be seen in Fig. 1 e, very slow capacity fade is observed on cycling. This result and those of Examples 3 and 4 indicate that both LiPF6 and LiBOB
are capable of forming stable SEI layers on MCMB with electrolytes containing borate cluster salt, but that LiBOB alone as an additive was better than LiPF6 alone or in combination with LiPF6. Without wishing to be bound by any theory or explanation this result may be due to the sensitivity of the LiMn204 positive electrode in the presence of traces of HF contained in LiPF6.
Example 6 Overcharge Protection with Li2B12F9H3 ¨ based electrolyte [0033] A cell was fabricated as in Example 1 with an electrolyte comprising 0.4 M
Li2B12F9H3 in 3:7 by weight EC:DEC. In each charge/discharge cycle, the cell was charged at a C/3 rate for 4 hrs followed by a constant current discharge at C/3 rate to 3.0 V. Such a charging protocol effectively overcharges the cell at to at least 33% above its full charge capacity. The cycle data presented in Figure 2 show that the cell potential is limited to ¨ 4.5 V on overcharge by the use of the Li2B12F9H3 electrolyte and that this overcharge protection lasts for ¨ 40 of the mentioned overcharge/discharge cycles. This electrolye provides a total of ¨ 260 hrs overcharge protection at this overcharging rate, after which time the cell potential is no longer limited on overcharge. Figure 5 shows the charging capacity and discharge capacity retention on overcharging indicates that this cell rapidly loses 4.2 to 3V discharge capacity and by the time the overcharge protection fails, no capacity remains in the cell.
Example 7 Overcharge Protection with Li2B12F9H3¨ based electrolyte + LIBOB additive [0034] A cell was fabricated as in Example 1 with an electrolyte comprising 0.36 M
Li2B12F9H3 and 0.08M lithium bis(oxalato)borate (LiBOB) in 3:7 by weight EC:DEC. In each charge/discharge cycle, the cell was charged at a C/3 rate for 4 hrs followed by a constant current discharge at C/3 rate to 3.0 V. Such a charging protocol effectively overcharges the cell at to at least 33% above its full charge capacity. The cycle data presented in Figure 3 show that the cell potential is limited to ¨ 4.5 V on overcharge by the use of the Li2B12F9H3 electrolyte and that this overcharge protection lasts for ¨ 100 of the mentioned overcharge/discharge cycles. This electrolye formulation provides a total of ¨ 680 hrs overcharge protection at this overcharging rate, after which time the cell =
potential is no longer limited on overcharge. Figure 5 showing the charging capacity and discharge capacity retention on overcharging indicates that this cell loses 4.2 to 3V
discharge capacity at a slower rate than the cell of example 6 and stabilizes at - 30-40%
of the full charge capacity between overcharge cycles 40 and 120. At the time the overcharge protection fails, no 4.2V to 3V discharge capacity remains in the cell.
Example 8 Overcharge Protection with L12B12F9H3- based electrolyte + LIBOB additive +
tris(pentafluorophenyl) borane additive [0035] A cell was fabricated as in Example 1 with an electrolyte comprising 0.36 M
L12B12F9H3 and 0.08M lithium bis(oxalato)borate (LiBOB) and 5 wt.%
tris(pentafluorophenyl) borane in 3:7 by weight EC:DEC. In each charge/discharge cycle, the cell was charged at a C/3 rate for 4 hrs followed by a constant current discharge at C/3 rate to 3.0 V. Such a charging protocol effectively overcharges the cell at to at least 33% above its full charge capacity. The cycle data presented in Figure 4 show that the cell potential is limited to - 4.5 V on overcharge by the use of the L12B12F9H3 electrolyte and that this overcharge protection is still effective after - 160 of the mentioned overcharge/discharge cycles. This electrolye formulation was still providing overcharge protection after 865 hrs at this overcharging rate. Figure 5 shows that 4.2 to discharge capacity retention is quite good even over the 160 overcharge cycles of this test. Figure 6 shows the affect of using 5% TPFPB
(tris(pentafluorophenyl)borane).
Claims
1. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, said electrolyte comprising at least one salt that provides overcharge protection, at least one carrier, and at least one additive, wherein the additive comprises at least one, oxalato borate; wherein said salt that provides overcharge protection comprises a salt of the formula:
M a Q
where M is an electrochemically stable cation, Q is a borate cluster anion or heteroborate cluster anion, and a is 1 or 2.
2. The cell of claim 1, wherein said electrolyte further comprises at least one nonreversibly oxidizable salt.
3. The cell of claim 1, wherein M comprises at least one member selected from the group consisting of alkali metal, alkaline earth metal, tetraalkylammonium, and imidazolium.
4. The cell of claim 1, wherein M comprises lithium.
5. The cell of claim 1, wherein Q comprises at least one member selected from the group consisting of: i) a c/oso-borate anion of the formula (B8-124-12)2-, where Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, ii) a c/oso-ammonioborate anion compositions of formula: ((RIR"R"I)NB8.12Z7-11) 1-; where N is bonded to B and each of R', R", R" is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and a polymer, Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, and iii) a c/oso-monocarborate anion compositions of formula (R""CB7-11Z7-11)1, where R" is bonded to C and selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and a polymer; Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl.
6. The cell of claim 5, wherein Q comprises c/oso-borate anion of the formula (B8-12Z8-12)2-, where Z is F, H, Cl, Br, or (OR), where R is H, C1-8 alkyl or fluoroalkyl.
7. The cell of claim 6, wherein the subscript a is 2.
8. The cell of claim 7, wherein the salt that provides overcharge protection comprises at least one member selected from the group consisting of Li2B10110_7Z3-10 where Z is CI or (OR); L12B10C110; L12B101-11_5C15_8; Li2B10C15_9(OR)1-5; 1-I2B10H2C18;
Li2B10H0_7(OCH3)3; Li2B10C18(OH)2; L12B10Br10; L12B8Br8; Li2B12C112; and Li2B12112.
9. The cell of claim 1, wherein the borate will not substantially hydrolyze to generate HF.
10. The cell of claim 9, wherein the borate comprises a lithium bis-oxalato borate.
1 1. The cell of claim 1, wherein said borate comprises lithium bis-oxalato borate.
12. The cell of claim 1 1, wherein said cell further comprises tris(pentafluorophenyl) borane.
13. The cell of claim 2, wherein the nonreversible oxidizable salt comprises lithium.
14. The cell of claim 2, wherein said nonreversible oxidizable salt comprises at least one member selected from the group consisting of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroborate, lithium trifluoromethylsulfonate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate lithium bromide, and lithium hexafluoroantimonate, LiB(C8H8)4, LiN(SO2CF3)2, LiN(SO2CF2CF3) and lithium bis(chelato)borates and mixtures thereof.
1 5. The cell of claim 1, wherein the at least one carrier comprises an aprotic organic comprising at least one member selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, fluorinated oligomers, methyl propionate, butyl propionate, ethyl propionate, sulfolane, 1,2-10 dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxyethane, triglyme, dimethylvinylene carbonate, vinylene carbonate, chloroethylene carbonate, tetraethyleneglycol, dimethyl ether, polyethylene glycols, sulfones, and gamma-butyrolactone.
16. The cell of claim 2, wherein the salt that provides overcharge protection comprises at least one lithium fluoroborate selected from the group consisting of those compounds represented by the formulas:
and wherein x is at least 3 for the decaborate salt and at least 5 for the dodecaborate salt, and Z represents H, CI, Br, or (OR), where R = H, C1-8 alkyl or fluoroalkyl.Li2B10F x Z10-x 17. The cell of claim 16, wherein the lithium fluoroborate has a reversible oxidation potential from 0.1 to 1 volt above the voltage of the cell.
Li2B12F x Z12-x 18. The cell of claim 16, wherein the lithium fluoroborate salt is added in an amount from about 3 to about 70 % by weight of the total weight of said nonreversibly oxidizable salt and said salt that provides overcharge protection present in the cell.
19. The cell of claim 16, wherein the nonreversibly oxidizable salt comprises at least one member selected from the group consisting of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroborate, lithium trifluoromethylsulfonate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate, lithium bromide, lithium hexafluoroantimonate, LiB(C6H5)4, LiN(SO2CF3)2, LiN(SO2CF2CF3) and lithium bis(chelato)borates, and mixtures thereof.
20. The cell of claim 16, wherein the salt that provides overcharge protection comprises at least one member selected from the group consisting of 12, Li2B12F x(OH)12-x where x=10 or 11, L12B12F10(OH)2, Li2B12F5H7 and L12B10Cl10.
Li2B12F12, Li2B12F x H12-x where x=10, 11 or 12, Li2B12F x CI12, where x=6, 7, 8, 9, 10, 11 or 21. The cell of claim 16, wherein the carrier comprises at least one member selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate,11 bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, fluorinated oligomers, methyl propionate, butyl propionate, ethyl propionate, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxyethane, triglyme, dimethylvinylene carbonate, vinylene carbonate, chloroethylene carbonate, tetraethyleneglycol, dimethyl ether, polyethylene glycols, sulfones, and gamma-butyrolactone.
22. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte comprising at least one aprotic organic carrier, lithium oxalato borate, and at least one salt that provides overcharge protection represented by the general formula Li2B12F x H12-x where x=9, 10, 11 or 12, Li2B12F x Cl12-x where x=6, 7, 8, 9, 10, 11 or 12, or Li2B12F x (OH)12-x where x=10 or 11.
23. The cell of claim 18, wherein said overcharge protection has a reversible oxidation potential from 0.1 to 1 volt above the voltage of the cell to act as a redox shuttle.
24. The cell of claim 18, wherein the salt that provides overcharge protection comprises a salt represented by the general formula Li2B12F x H12-x where x=9, 10, 11 or 12.
25. The cell of claim 19, wherein the electrolyte further comprises LiPF6.
M a Q
where M is an electrochemically stable cation, Q is a borate cluster anion or heteroborate cluster anion, and a is 1 or 2.
2. The cell of claim 1, wherein said electrolyte further comprises at least one nonreversibly oxidizable salt.
3. The cell of claim 1, wherein M comprises at least one member selected from the group consisting of alkali metal, alkaline earth metal, tetraalkylammonium, and imidazolium.
4. The cell of claim 1, wherein M comprises lithium.
5. The cell of claim 1, wherein Q comprises at least one member selected from the group consisting of: i) a c/oso-borate anion of the formula (B8-124-12)2-, where Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, ii) a c/oso-ammonioborate anion compositions of formula: ((RIR"R"I)NB8.12Z7-11) 1-; where N is bonded to B and each of R', R", R" is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and a polymer, Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl, and iii) a c/oso-monocarborate anion compositions of formula (R""CB7-11Z7-11)1, where R" is bonded to C and selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and a polymer; Z is F, H, Cl, Br, or (OR), where R is H, alkyl or fluoroalkyl.
6. The cell of claim 5, wherein Q comprises c/oso-borate anion of the formula (B8-12Z8-12)2-, where Z is F, H, Cl, Br, or (OR), where R is H, C1-8 alkyl or fluoroalkyl.
7. The cell of claim 6, wherein the subscript a is 2.
8. The cell of claim 7, wherein the salt that provides overcharge protection comprises at least one member selected from the group consisting of Li2B10110_7Z3-10 where Z is CI or (OR); L12B10C110; L12B101-11_5C15_8; Li2B10C15_9(OR)1-5; 1-I2B10H2C18;
Li2B10H0_7(OCH3)3; Li2B10C18(OH)2; L12B10Br10; L12B8Br8; Li2B12C112; and Li2B12112.
9. The cell of claim 1, wherein the borate will not substantially hydrolyze to generate HF.
10. The cell of claim 9, wherein the borate comprises a lithium bis-oxalato borate.
1 1. The cell of claim 1, wherein said borate comprises lithium bis-oxalato borate.
12. The cell of claim 1 1, wherein said cell further comprises tris(pentafluorophenyl) borane.
13. The cell of claim 2, wherein the nonreversible oxidizable salt comprises lithium.
14. The cell of claim 2, wherein said nonreversible oxidizable salt comprises at least one member selected from the group consisting of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroborate, lithium trifluoromethylsulfonate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate lithium bromide, and lithium hexafluoroantimonate, LiB(C8H8)4, LiN(SO2CF3)2, LiN(SO2CF2CF3) and lithium bis(chelato)borates and mixtures thereof.
1 5. The cell of claim 1, wherein the at least one carrier comprises an aprotic organic comprising at least one member selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, fluorinated oligomers, methyl propionate, butyl propionate, ethyl propionate, sulfolane, 1,2-10 dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxyethane, triglyme, dimethylvinylene carbonate, vinylene carbonate, chloroethylene carbonate, tetraethyleneglycol, dimethyl ether, polyethylene glycols, sulfones, and gamma-butyrolactone.
16. The cell of claim 2, wherein the salt that provides overcharge protection comprises at least one lithium fluoroborate selected from the group consisting of those compounds represented by the formulas:
and wherein x is at least 3 for the decaborate salt and at least 5 for the dodecaborate salt, and Z represents H, CI, Br, or (OR), where R = H, C1-8 alkyl or fluoroalkyl.Li2B10F x Z10-x 17. The cell of claim 16, wherein the lithium fluoroborate has a reversible oxidation potential from 0.1 to 1 volt above the voltage of the cell.
Li2B12F x Z12-x 18. The cell of claim 16, wherein the lithium fluoroborate salt is added in an amount from about 3 to about 70 % by weight of the total weight of said nonreversibly oxidizable salt and said salt that provides overcharge protection present in the cell.
19. The cell of claim 16, wherein the nonreversibly oxidizable salt comprises at least one member selected from the group consisting of lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluoroborate, lithium trifluoromethylsulfonate, lithium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)borate, lithium bromide, lithium hexafluoroantimonate, LiB(C6H5)4, LiN(SO2CF3)2, LiN(SO2CF2CF3) and lithium bis(chelato)borates, and mixtures thereof.
20. The cell of claim 16, wherein the salt that provides overcharge protection comprises at least one member selected from the group consisting of 12, Li2B12F x(OH)12-x where x=10 or 11, L12B12F10(OH)2, Li2B12F5H7 and L12B10Cl10.
Li2B12F12, Li2B12F x H12-x where x=10, 11 or 12, Li2B12F x CI12, where x=6, 7, 8, 9, 10, 11 or 21. The cell of claim 16, wherein the carrier comprises at least one member selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate,11 bis(trifluoroethyl) carbonate, bis(pentafluoropropyl) carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, fluorinated oligomers, methyl propionate, butyl propionate, ethyl propionate, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxyethane, triglyme, dimethylvinylene carbonate, vinylene carbonate, chloroethylene carbonate, tetraethyleneglycol, dimethyl ether, polyethylene glycols, sulfones, and gamma-butyrolactone.
22. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte comprising at least one aprotic organic carrier, lithium oxalato borate, and at least one salt that provides overcharge protection represented by the general formula Li2B12F x H12-x where x=9, 10, 11 or 12, Li2B12F x Cl12-x where x=6, 7, 8, 9, 10, 11 or 12, or Li2B12F x (OH)12-x where x=10 or 11.
23. The cell of claim 18, wherein said overcharge protection has a reversible oxidation potential from 0.1 to 1 volt above the voltage of the cell to act as a redox shuttle.
24. The cell of claim 18, wherein the salt that provides overcharge protection comprises a salt represented by the general formula Li2B12F x H12-x where x=9, 10, 11 or 12.
25. The cell of claim 19, wherein the electrolyte further comprises LiPF6.
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US11/520,564 US20070072085A1 (en) | 2005-09-26 | 2006-09-14 | Overcharge protection for electrochemical cells |
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Families Citing this family (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8980453B2 (en) | 2008-04-30 | 2015-03-17 | Medtronic, Inc. | Formation process for lithium-ion batteries |
US9065145B2 (en) * | 2004-10-29 | 2015-06-23 | Medtronic, Inc. | Lithium-ion battery |
EP2239804A3 (en) * | 2004-10-29 | 2012-03-28 | Medtronic, Inc. | Method of charging lithium-ion battery |
US7641992B2 (en) * | 2004-10-29 | 2010-01-05 | Medtronic, Inc. | Medical device having lithium-ion battery |
US8105714B2 (en) * | 2004-10-29 | 2012-01-31 | Medtronic, Inc. | Lithium-ion battery |
US9077022B2 (en) | 2004-10-29 | 2015-07-07 | Medtronic, Inc. | Lithium-ion battery |
US7682745B2 (en) * | 2004-10-29 | 2010-03-23 | Medtronic, Inc. | Medical device having lithium-ion battery |
CN101048898B (en) | 2004-10-29 | 2012-02-01 | 麦德托尼克公司 | Lithium-ion battery and medical device |
US7582387B2 (en) * | 2004-10-29 | 2009-09-01 | Medtronic, Inc. | Lithium-ion battery |
US7927742B2 (en) * | 2004-10-29 | 2011-04-19 | Medtronic, Inc. | Negative-limited lithium-ion battery |
US7807299B2 (en) * | 2004-10-29 | 2010-10-05 | Medtronic, Inc. | Lithium-ion battery |
US7563541B2 (en) * | 2004-10-29 | 2009-07-21 | Medtronic, Inc. | Lithium-ion battery |
US20080044728A1 (en) * | 2004-10-29 | 2008-02-21 | Medtronic, Inc. | Lithium-ion battery |
US7662509B2 (en) * | 2004-10-29 | 2010-02-16 | Medtronic, Inc. | Lithium-ion battery |
US20060216612A1 (en) * | 2005-01-11 | 2006-09-28 | Krishnakumar Jambunathan | Electrolytes, cells and methods of forming passivation layers |
US20080026297A1 (en) | 2005-01-11 | 2008-01-31 | Air Products And Chemicals, Inc. | Electrolytes, cells and methods of forming passivaton layers |
KR101101001B1 (en) | 2005-01-19 | 2011-12-29 | 아리조나 보드 오브 리전트스, 아리조나주의 아리조나 주립대 대행법인 | Electric current-producing device having sulfone-based electrolyte |
KR101347671B1 (en) * | 2005-06-07 | 2014-01-03 | 히다치 막셀 가부시키가이샤 | A secondary battery with nonaqueous electrolyte |
JP5034537B2 (en) * | 2007-02-13 | 2012-09-26 | ソニー株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
WO2009042958A1 (en) * | 2007-09-28 | 2009-04-02 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Non-aqueous electrolyte solution for rechargeable lithium batteries |
US9755269B2 (en) * | 2007-11-30 | 2017-09-05 | Air Products And Chemicals, Inc. | Dodecaborate salt radical anion compositions and methods for making and using such compositions |
US8187746B2 (en) * | 2008-05-16 | 2012-05-29 | Uchicago Argonne, Llc | Surface modification agents for lithium batteries |
JP5300468B2 (en) * | 2008-12-26 | 2013-09-25 | 昭和電工株式会社 | Non-aqueous electrolyte |
US8968940B2 (en) | 2010-05-25 | 2015-03-03 | Uchicago Argonne, Llc | Redox shuttles for high voltage cathodes |
KR101831458B1 (en) | 2010-05-25 | 2018-04-04 | 유시카고 아곤, 엘엘씨 | Polyether-functionalized redox shuttle additives for lithium ion batteries |
US8877390B2 (en) | 2010-05-25 | 2014-11-04 | Uchicago Argonne, Llc | Redox shuttles for lithium ion batteries |
TWI497792B (en) * | 2011-02-01 | 2015-08-21 | Taiwan Hopax Chems Mfg Co Ltd | Electrolyte for electrochemical device and the electrochemical device thereof |
US20130330635A1 (en) * | 2011-02-28 | 2013-12-12 | Showa Denko K.K. | Nonaqueous electrolytic solution for secondary battery and nonaqueous electrolytic solution secondary battery |
US8703329B2 (en) | 2011-03-25 | 2014-04-22 | Enerdel, Inc. | Redox shuttle for high voltage lithium battery |
KR20140009521A (en) * | 2011-04-27 | 2014-01-22 | 쇼와 덴코 가부시키가이샤 | Non-aqueous electrolyte solution for secondary cell, and non-aqueous electrolyte secondary cell |
WO2012147566A1 (en) * | 2011-04-28 | 2012-11-01 | 昭和電工株式会社 | Non-aqueous electrolyte solution for secondary cell, and non-aqueous electrolyte secondary cell |
KR101223628B1 (en) * | 2011-05-13 | 2013-01-17 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
US9287580B2 (en) | 2011-07-27 | 2016-03-15 | Medtronic, Inc. | Battery with auxiliary electrode |
US20130149560A1 (en) | 2011-12-09 | 2013-06-13 | Medtronic, Inc. | Auxiliary electrode for lithium-ion battery |
US9203112B2 (en) | 2012-04-26 | 2015-12-01 | Uchicago Argonne, Llc | Redox shuttles having an aromatic ring fused to a 1,1,4,4-tetrasubstituted cyclohexane ring |
JP2014112524A (en) * | 2012-11-12 | 2014-06-19 | Ricoh Co Ltd | Nonaqueous electrolyte electricity storage element |
WO2014090877A1 (en) | 2012-12-12 | 2014-06-19 | Rockwood Lithium GmbH | (hetero)aromatic iso(thio)cyanates as redox shuttle additives for electrochemical cells |
KR101535865B1 (en) * | 2013-09-17 | 2015-07-14 | 파낙스 이텍(주) | electrolyte for secondary battery containing boron-based lithium salt and a secondary battery containing the same |
WO2015179665A1 (en) * | 2014-05-22 | 2015-11-26 | Rhodia Operations | Polymer compositions, polymer films, and electronic devices containing such films |
CN107004896B (en) * | 2014-12-19 | 2019-05-14 | Nec 能源元器件株式会社 | Lithium ion secondary battery |
US11450883B2 (en) | 2020-06-30 | 2022-09-20 | Toyota Motor Engineering & Manufacturing North America, Inc. | Enhanced solid closo-borane electrolytes for batteries |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4020240A (en) * | 1975-09-03 | 1977-04-26 | P. R. Mallory & Co., Inc. | Electrochemical cell with clovoborate salt in electrolyte and method of operation and composition of matter |
US4071664A (en) * | 1977-04-01 | 1978-01-31 | P. R. Mallory & Co. Inc. | Electrolyte salt additive |
US4201839A (en) * | 1978-11-01 | 1980-05-06 | Exxon Research And Engineering Co. | Cell containing an alkali metal anode, a solid cathode, and a closoborane and/or closocarborane electrolyte |
US4331743A (en) * | 1980-09-02 | 1982-05-25 | Duracell International Inc. | Method for increasing recycling life of non-aqueous cells |
JP2884746B2 (en) * | 1990-09-03 | 1999-04-19 | 松下電器産業株式会社 | Non-aqueous electrolyte secondary battery |
JP3493873B2 (en) * | 1995-04-28 | 2004-02-03 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
US5849432A (en) * | 1995-11-03 | 1998-12-15 | Arizona Board Of Regents | Wide electrochemical window solvents for use in electrochemical devices and electrolyte solutions incorporating such solvents |
AU4451597A (en) * | 1996-09-30 | 1998-04-24 | Danionics A/S | An electrolyte system, a method for the preparation thereof, the use thereof and a battery containing the electrolyte system |
US6022643A (en) * | 1997-12-08 | 2000-02-08 | Brookhaven Science Associates | Boron compounds as anion binding agents for nonaqueous battery electrolytes |
CA2412818A1 (en) * | 2000-06-16 | 2001-12-20 | Charles A. Angell | Conductive polymeric compositions for lithium batteries |
JP4762411B2 (en) * | 2000-06-26 | 2011-08-31 | パナソニック株式会社 | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the same |
DE10111410C1 (en) * | 2001-03-08 | 2002-07-25 | Chemetall Gmbh | Lithium bis(oxalato)borate electrolyte, used in electrochemical storage system or electrochromic formulation, e.g. window, contains ternary solvent system |
US7172834B1 (en) * | 2002-07-29 | 2007-02-06 | The United States Of America As Represented By The Secretary Of The Army | Additive for enhancing the performance of electrochemical cells |
JP2004265785A (en) * | 2003-03-03 | 2004-09-24 | Nippon Shokubai Co Ltd | Ion electrolyte material |
JP2004265786A (en) * | 2003-03-03 | 2004-09-24 | Nippon Shokubai Co Ltd | Ion electrolyte material |
US7311993B2 (en) * | 2003-09-04 | 2007-12-25 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
CA2479589C (en) * | 2003-09-04 | 2011-05-24 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
KR20060042201A (en) * | 2004-02-27 | 2006-05-12 | 산요덴키가부시키가이샤 | Lithium secondary battery |
JP2005243504A (en) * | 2004-02-27 | 2005-09-08 | Sanyo Electric Co Ltd | Lithium secondary battery |
JP2005259592A (en) * | 2004-03-12 | 2005-09-22 | Sanyo Electric Co Ltd | Nonaqueous electrolytic solution for secondary battery, and nonaqueous electrolytic solution secondary battery |
US7785740B2 (en) * | 2004-04-09 | 2010-08-31 | Air Products And Chemicals, Inc. | Overcharge protection for electrochemical cells |
JP4572602B2 (en) * | 2004-06-30 | 2010-11-04 | パナソニック株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery and their production method |
US7465517B2 (en) * | 2004-08-23 | 2008-12-16 | Air Products And Chemicals, Inc. | High purity lithium polyhalogenated boron cluster salts useful in lithium batteries |
US20060216612A1 (en) * | 2005-01-11 | 2006-09-28 | Krishnakumar Jambunathan | Electrolytes, cells and methods of forming passivation layers |
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2006
- 2006-09-14 US US11/520,564 patent/US20070072085A1/en not_active Abandoned
- 2006-09-21 CA CA2560605A patent/CA2560605C/en not_active Expired - Fee Related
- 2006-09-22 EP EP20060019887 patent/EP1768210B1/en not_active Not-in-force
- 2006-09-26 TW TW095135639A patent/TWI374564B/en not_active IP Right Cessation
- 2006-09-26 KR KR1020060093372A patent/KR100817695B1/en not_active IP Right Cessation
- 2006-09-26 JP JP2006260741A patent/JP2007128865A/en not_active Withdrawn
- 2006-09-26 CN CN2006101495100A patent/CN1953264B/en not_active Expired - Fee Related
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JP2007128865A (en) | 2007-05-24 |
CN1953264B (en) | 2011-02-09 |
KR20070034967A (en) | 2007-03-29 |
JP2011204691A (en) | 2011-10-13 |
TW200713666A (en) | 2007-04-01 |
EP1768210B1 (en) | 2015-04-29 |
TWI374564B (en) | 2012-10-11 |
US20070072085A1 (en) | 2007-03-29 |
EP1768210A1 (en) | 2007-03-28 |
CA2560605A1 (en) | 2007-03-26 |
CN1953264A (en) | 2007-04-25 |
JP5457400B2 (en) | 2014-04-02 |
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