EP1417726A2 - Electrolytes polymeres et leur utilisation dans des cellules galvaniques - Google Patents
Electrolytes polymeres et leur utilisation dans des cellules galvaniquesInfo
- Publication number
- EP1417726A2 EP1417726A2 EP02760270A EP02760270A EP1417726A2 EP 1417726 A2 EP1417726 A2 EP 1417726A2 EP 02760270 A EP02760270 A EP 02760270A EP 02760270 A EP02760270 A EP 02760270A EP 1417726 A2 EP1417726 A2 EP 1417726A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbonate
- lithium
- component
- methyl
- mixture according
- 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.)
- Withdrawn
Links
- 239000005518 polymer electrolyte Substances 0.000 title description 16
- 239000000203 mixture Substances 0.000 claims abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- -1 batteries Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims description 30
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229910005965 SO 2 Inorganic materials 0.000 claims description 10
- 229920001519 homopolymer Polymers 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000005412 pyrazyl group Chemical group 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 8
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 7
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000005840 aryl radicals Chemical class 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 150000005677 organic carbonates Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 3
- 150000003857 carboxamides Chemical class 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000005684 open-chain carbonates Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 2
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000002895 organic esters Chemical class 0.000 claims description 2
- ORTFAQDWJHRMNX-UHFFFAOYSA-M oxidooxomethyl Chemical compound [O-][C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-M 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- GJWQPURHWKTFFJ-UHFFFAOYSA-N 2-methylpenta-2,3,4-trienoic acid Chemical compound OC(=O)C(C)=C=C=C GJWQPURHWKTFFJ-UHFFFAOYSA-N 0.000 claims 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 description 12
- 150000002367 halogens Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000011245 gel electrolyte Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229920001523 phosphate polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- CMQUGOHGJUTDGZ-UHFFFAOYSA-N 3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propanoic acid Chemical compound OC(=O)C(O)(C(F)(F)F)C(F)(F)F CMQUGOHGJUTDGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910012424 LiSO 3 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- UQWLFOMXECTXNQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F UQWLFOMXECTXNQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LRJNNJLCNGFADW-UHFFFAOYSA-N diethyl carbonate;1,3-dioxolan-2-one Chemical compound O=C1OCCO1.CCOC(=O)OCC LRJNNJLCNGFADW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to mixtures of borate or phosphate salts and polymers and their use in electrolytes, batteries, capacitors, supercapacitors and galvanic cells.
- Battery cells based on liquid electrolytes generally have relatively good ionic conductivities, but tend to leak, which then leads to the release of liquids that are potentially dangerous to humans and the environment. The production of such battery cells is also limited with regard to the possible sizes and shapes of these cells.
- Polymer electrolytes are usually based on an optionally crosslinked polymer and a conductive salt.
- conventional polymer electrolytes often show only low ionic conductivities, which do not meet the high demands placed on modern batteries.
- Gel or hybrid electrolytes are understood to mean electrolyte systems which, in addition to an optionally crosslinked polymer and a conducting salt, contain a solvent.
- the crosslinking of these polymers is often carried out at relatively high temperatures in the presence of the conductive salts.
- the corresponding conductive salts must therefore have a relatively high thermal solution
- REPLACEMENT BLA ⁇ (RULE 26) Have stability, since otherwise there is a risk of their decomposition and thus a reduction in the ionic conductivity of the resulting gel electrolyte.
- LiPF 6 Due to the low thermal stability, LiPF 6 , which has the greatest commercial distribution as a salt in liquid electrolytes, is not suitable for use in polymer or gel electrolytes. In addition, LiPF ⁇ is extremely sensitive to hydrolysis. Hydrofluoric acid HF can quickly develop in contact with moist air or with residual water from the solvents. In addition to its toxic properties, HF has a very negative effect on the cycle behavior and thus on the life and performance of the electrochemical cells.
- the aluminum usually used as a cathodic current arrester is not sufficiently passivated by imides (LA Dominey, Current State of Art on Lithium Battery Electrolyte in G. Pistoia (ed.) Lithium Batteries; New Materials, Development and Perspectives, Amsterdam, Elsevier, 1994 and literature cited therein).
- imides LA Dominey, Current State of Art on Lithium Battery Electrolyte in G. Pistoia (ed.) Lithium Batteries; New Materials, Development and Perspectives, Amsterdam, Elsevier, 1994 and literature cited therein.
- methanides can only be produced and purified with great effort.
- the electrochemical properties such as oxidation stability and passivation of aluminum depend very much on the purity of the methanide.
- EP 698 301 and WO 98/07729 disclose lithium spiroborates with aromatic ligands and their use as conductive salts in galvanic cells. The use of these salts as conductive salts in polymer electrolytes is not described.
- lithium bis (oxalato) borate and lithium tris (oxalato) phosphate describe two salts and their use as conductive salts.
- Polymer electrolytes based on these salts are also not disclosed here.
- the object of the invention was to provide electrolytes which do not have the disadvantages of the prior art. The task was therefore to provide electrolytes which, in addition to good ionic conductivity, also have high thermal stability.
- Another object of the present invention was to extend or improve the life and performance of batteries, capacitors, supercapacitors and galvanic cells.
- R 4 , R 5 , R 6 are the same, different or in pairs different, optionally directly connected to one another by a single or double bond and each have the individually or together
- aromatic or a heteroaromatic ring preferably phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, pyrazyl or pyrimidyl,
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 partially or completely with further groups, preferably with F, Cl, Br,
- C n F (2n + 1-x) H x can be substituted with 1 ⁇ n ⁇ 6 and 1 ⁇ x ⁇ 2n + 1.
- a mixture in the sense of the present invention comprises pure mixtures of components a) and b), mixtures in which the salt of component a) is included in the polymer of component b) and mixtures in which between the salt of component a) and the polymer of component b) chemical and / or physical bonds exist.
- the mixture according to the invention can contain component a) in an amount of 3 to 99% by weight and component b) in an amount of 97 to 1% by weight.
- the mixture can particularly preferably contain component a) in an amount of 10 to 99% by weight and component b) in an amount of 90 to 1% by weight.
- the weight ratios given above each relate to the sum of components a) and b).
- the mixtures according to the invention preferably each contain a salt of the general formula (I) or (II) as component a) and a polymer of component b). In this way, particularly good reproducibility of the electrochemical properties can be achieved.
- the mixtures according to the invention can also each contain two or more salts of the general formulas (I) and (II) as component a) and / or two or more polymers of component b).
- salts of the general formulas (I) or (II) in a mixture with further lithium salts known to the person skilled in the art in the mixtures according to the invention. They can be used in proportions between 1 and 99% in combination with other conductive salts which are used in electrochemical cells.
- conductive salts selected from the group LiPF 6 , LiBF 4 , LiCIO 4 , LiAsF 6 , LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 3 , LiN (SO 2 C 2 F 5 ) 2 , LiB (OC 2 ) 2 or Li [F ⁇ P (CnF 2n + ⁇ ) 6-x] with 1 ⁇ x ⁇ 5 and 1 ⁇ n ⁇ 8 and their mixtures.
- the mixtures according to the invention contain spiroborate or spirophosphate salts as salts of the general formulas (I) or (II).
- mixtures particularly preferably contain salts of the general formulas (I) or (II), the anions of which are selected from the following group:
- the mixture according to the invention preferably contains a homopolymer or copolymer of unsaturated nitriles, preferably acrylonitrile, vinylidenes, preferably vinylidene difluoride, methacrylates, preferably methyl methacrylate, cyclic ethers, preferably tetrahydrofuran, alkylene oxides, preferably ethylene oxide, siloxane, phosphazene, alkoxysilanes or organically modified keramics , distributed under the Brand names ORMOCERE®, or a mixture of at least two of the above-mentioned homopolymers and / or copolymers.
- unsaturated nitriles preferably acrylonitrile, vinylidenes, preferably vinylidene difluoride, methacrylates, preferably methyl methacrylate, cyclic ethers, preferably tetrahydrofuran, alkylene oxides, preferably ethylene oxide, siloxane, phosphazen
- Component b) is particularly preferably a homopolymer or copolymer of vinylidene difluoride, acrylonitrile, methyl (meth) acrylate, tetrahydrofuran, very particularly preferably a homopolymer or copolymer of vinylidene difluoride.
- These homopolymers and copolymers of vinylidene difluoride are e.g. marketed under the names Kynar® and Kynarflex® by Atofina Chemicals, Inc. and under the name Solef® by Solvay.
- polymers used according to the invention can be at least partially crosslinked.
- Crosslinking can be carried out using known crosslinking agents by customary methods known to those skilled in the art.
- the mixture according to the invention can additionally contain a solvent or a solvent mixture of two or more solvents.
- Preferred solvents are organic carbonates, organic esters, organic ethers, organic amides, sulfur-containing solvents, aprotic solvents or at least partially fluorinated derivatives of the abovementioned solvents or mixtures of at least two of these solvents and / or fluorinated derivatives of these solvents.
- Ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, vinylene carbonate or methyl propyl carbonate are preferably used as organic carbonates, and methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate or ⁇ -organic ether sulfate is preferably used as the organic ester Diethyl ether, dimethoxyethane or diethoxyethane, as organic amides preferably dimethylformamide or dimethylacetamide, as sulfur-containing solvent preferably dimethyl sulfoxide, dimethyl sulfite, diethyl sulfite or propane sultone and as aprotic solvent preferably acetonitrile, acrylonitrile or acetone.
- the invention further relates to a process for the preparation of lithium salts of the general formula (I) in electrochemically pure quality (> 99%), in which lithium hydroxide or lithium carbonate with boric acid or boron trioxide and the corresponding ligand of the salt of the general formula (I) is implemented by a process known to the person skilled in the art, wherein according to the invention only solvents are used which have a high electrochemical voltage window, such as organic carbonates.
- E rec ⁇ ⁇ 1.5 V against Li / Li + and E ox > 4.5 V against Li / Li + applies to a high electrochemical voltage window .
- Only open-chain carbonates are preferably used as the solvent, in particular dimethyl carbonate, diethyl carbonate and / or ethyl methyl carbonate.
- the invention further relates to lithium salts of the general formula (I) in electrochemically pure quality (> 99%). These can be obtained by reacting lithium hydroxide or lithium carbonate with boric acid or boron trioxide and the corresponding ligand of the salt of the general formula (I), using only solvents which have a high electrochemical voltage window.
- the invention also relates to the lithium salts defined in claims 17 and 18.
- Another object of the invention is the use of at least one mixture according to the invention in electrolytes, primary and secondary batteries, capacitors, supercapacitors and galvanic cells.
- the invention further relates to electrolytes, primary batteries, secondary batteries, capacitors, supercapacitors and galvanic cells which contain at least one mixture according to the invention and, if appropriate, further lithium salts and / or additives.
- These other lithium salts and additives are known to the person skilled in the art, for example from Doron Aurbach, Nonaqueous Electrochemistry, Marc Dekker Inc., New York 1999; D. Linden, Handbook of Batteries, Second Edition, McGraw-Hill Inc., New York 1995 and G. Mamantov and Al Popov, Chemistry of Nonaqueous Solutions, Current Progress, VCH Verlagstician, Weinheim 1994. They are hereby introduced as a reference and are therefore considered part of the disclosure.
- Organic isocyanates (DE 199 44 603) can be included to reduce the water content.
- N (CF 3 ) 2 may be included, with Kt N, P, As, Sb, S, Se AN, P, P (O), O, S, S (O), SO 2 , As, As (O), Sb, Sb (O)
- R 1 , R 2 , R 3 are the same or different
- Kt may be included in cyclic or heterocyclic ring, and the groups attached to Kt may be the same or different.
- mixtures according to the invention can also be contained in electrolytes which
- Lithium complex salts of the formula (DE 199 32 317)
- R 1 , R 2 are the same or different, optionally connected directly to one another by a single or double formation, in each case individually or together, the meaning of an aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which is unsubstituted or one to six times alkyl
- alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br) may be substituted, or in each case individually or together the meaning of an aromatic heterocyclic ring from the group pyridyl, pyrazyl or pyrimidyl, the can be unsubstituted or mono- to tetrasubstituted by alkyl (Ci to C 6 ), alkoxy groups (d to C 6 ) or halogen (F, Cl, Br), or in each case individually or jointly the meaning of an aromatic ring from the group hydroxylbenzoecarboxyl, hydroxylnaphthalenecarboxyl, hydroxylbenzenesulfonyl and hydroxylnaphthalenesulfonyl, which is unsubstituted or one to four times by alkyl (Ci to C 6 ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl .
- Br may have, R 3 to R 6 each individually or in pairs, optionally directly linked to one another by a single or double bond, have the following meanings: 1. Alkyl (Ci to C ⁇ ), alkyloxy (Ci to C 6 ) or halogen (F, Cl, Br)
- Phenyl, naphthyl, anthracenyl or phenanthrenyl which may be unsubstituted or monosubstituted or substituted six times by alkyl (Ci to CQ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br), pyridyl, pyrazyl or pyrimidyl, the unsubstituted or mono- to tetrasubstituted by alkyl (Ci to C 6 ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br).
- E is a Lewis acid selected from the group BR 1 R 2 R 3 , AIR 1 R 2 R 3 , PR 1 R 2 R 3 R 4 R 5 , AsR 1 R 2 R 3 R 4 R 5 , VR 1 R 2 R 3 R 4 R 5 with
- R 1 to R 5 are the same or different, optionally connected directly to one another by a single or double formation, in each case individually or together, the meaning of a halogen (F, Cl, Br), an alkyl or alkoxy radical (Ci to C 8 ), the can be partially or completely substituted by F, Cl, Br, an optionally linked via oxygen aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which is unsubstituted or one to six times by alkyl (Ci to C 8 ) or F, Cl , Br can be substituted, an optionally linked via oxygen aromatic heterocyclic ring from the group pyridyl, pyrazyl or Pyrimidyl, which may be unsubstituted or mono- to tetrasubstituted by alkyl (Ci to Cs) or F, Cl, Br and may have Z OR 6 , NR 6 R 7 , CR 6 R 7 R 8 , OSO
- R 6 to R 8 are the same or different, optionally connected directly to one another by a single or double bond, each individually or together has the meaning of a hydrogen or the meaning of R 1 to R 5 .
- borate salts (DE 199 59 722) of the general formula
- M is a metal ion or tetraalkylammonium ion x, y 1, 2, 3, 4, 5 or 6 R 1 to R 4, the same or different, optionally linked by a single or double bond alkoxy or carboxy radicals (C ⁇ -C 8 ).
- Additives such as silane compounds of the general formula (DE 100 276 26) SiR 1 R 2 R 3 R 4 can also be present, where R 1 to R 4 H
- R 1 to R 4 are the same or different with the meaning of an aromatic ring from the group phenyl, naphthyl which is unsubstituted or one or more times by F, C y F 2 y + ⁇ - z H z or OC y F 2y + ⁇ - z H z , OC (O) C y F 2y + ⁇ - z H z , OS ⁇ 2 CyF 2y + ⁇ - z H z , N (CnF 2 n + ⁇ - z H z ) 2 , or with the meaning of a heterocyclic aromatic ring from the group phenyl, naphthyl which is unsubstituted or one or more times by F, C y F 2 y + ⁇ - z H z or OC y F 2y + ⁇ - z H z , OC (O) C y F 2y + ⁇ - z H z , OS ⁇ 2 CyF 2y + ⁇ -
- mixtures according to the invention can also be used in electrolytes which contain lithium fluoroalkyl phosphates of the following formula (DE 100 089 55)
- Ligands (CHbF c (CF 3 ) d) may be the same or different.
- Salt is cleaned and isolated according to the usual methods.
- mixtures according to the invention can also be used in electrolytes, the salts of the formula (DE 100 16801)
- the compounds are represented by the conversion of phosphorus (V) -
- K + A ' can be contained in the electrolyte, in which K + is a cation selected from the group
- R 1 to R 5 are identical or different, optionally connected directly to one another by a single or double bond and each, individually or together, has the following meaning: - H,
- C n F (2n + ⁇ -x) H x can be substituted with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13 and
- a ⁇ an anion selected from the group [B (OR 1 ) n (OR 2 ) m (OR 3 ) 0 (OR 4 ) P r with 0 ⁇ n, m, o, p ⁇ 4 and m + n + o + p 4
- R 1 to R 4 are different or in pairs the same, optionally connected directly to one another by a single or double formation, in each case individually or together, the meaning of an aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which is unsubstituted or one or more times can be substituted by C n F ( 2n + ⁇ -x) H x with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13 or halogen (F, Cl, Br), the meaning of an aromatic heterocyclic ring from the group pyridyl, pyrazyl or pyrimidyl which is unsubstituted or one or more times by C n F ( 2 ⁇ + ⁇ -x) H x with 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13 or halogen or halogen (F, Cl, Br) can be substituted, or have the meaning of an alkyl radical (Ci to C 8 ) which is partially or
- N (C n F (2n + 1-x) H x ) 2, O (C n F (2n + 1-x) H x ), S ⁇ 2 (C n F (2n + 1-x) H x ), C n F (2n + 1-x) H x can be substituted by 1 ⁇ n ⁇ 6 and 0 ⁇ x ⁇ 13, or OR 1 to OR 4 individually or together have the meaning of an aromatic or aliphatic carboxyl, dicarboxyl, Oxysulfonyl or oxycarboxyl radicals' which are partially or completely replaced by further groups, preferably F, Cl, N (C n F (2n + ⁇ -x) H x ) 2 , 0 (C n F (2 n + ⁇ -x) H x ), S0 2 (C n F ( 2 n + ⁇ -x) H x ), C n F ( 2 n + ⁇ -x) H x can be substituted with 1 ⁇ n ⁇ 6 and 0 ⁇ x
- Ionic liquids K + A " (DE 100 279 95) with K + as above and A " also define an anion selected from the group
- the mixtures according to the invention can be used in electrolytes for electrochemical cells which contain anode material consisting of coated metal cores selected from the group Sb, Bi, Cd, In, Pb, Ga and tin or their alloys (DE 100 16 024).
- the process for producing this anode material is characterized in that a) a suspension or a sol of the metal or alloy core is produced in urotropin, b) the suspension is emulsified with hydrocarbons with C 5 -C 12, c) the emulsion on the metal or alloy cores and d) the metal hydroxides or metal oxides are converted into the corresponding oxide by tempering the system.
- the mixtures according to the invention can also be used in electrolytes for electrochemical cells, with cathodes made of common lithium intercalation and insertion compounds, but also with cathode materials consisting of lithium mixed oxide particles which are coated with one or more metal oxides (DE 199 22 522) by suspending the particles in an organic solvent, adding a solution of a hydrolyzable metal compound and a hydrolysis solution to the suspension and then filtering off the coated particles, drying them and optionally calcining them.
- cathodes made of common lithium intercalation and insertion compounds
- cathode materials consisting of lithium mixed oxide particles which are coated with one or more metal oxides (DE 199 22 522) by suspending the particles in an organic solvent, adding a solution of a hydrolyzable metal compound and a hydrolysis solution to the suspension and then filtering off the coated particles, drying them and optionally calcining them.
- They can also consist of lithium mixed oxide particles which are coated with one or more polymers (DE 19946 066) obtained by
- the mixtures according to the invention can likewise be used in systems with cathodes which consist of lithium mixed oxide particles which are coated one or more times with alkali metal compounds and metal oxides (DE 100 14 884).
- the process for producing these materials is characterized in that the particles are suspended in an organic solvent, an alkali metal salt compound suspended in an organic solvent is added, metal oxides dissolved in an organic solvent are added, the suspension is mixed with a hydrolysis solution and then the coated Particles are filtered off, dried and calcined.
- the mixtures according to the invention can likewise be used in systems which contain anode materials with doped tin oxide (DE 100 257 61).
- This anode material is produced by a) adding urea to a tin chloride solution, b) adding urotropin and a suitable doping compound to the solution, c) emulsifying the sol thus obtained in petroleum ether, d) washing the gel obtained and suctioning off the solvent such as e) the gel is dried and tempered.
- the mixtures according to the invention can also be used in systems which contain anode materials with reduced tin oxide (DE 100 257 62).
- This anode material is produced by a) adding urea to a tin chloride solution, b) adding urotropin to the solution, c) emulsifying the sol thus obtained in petroleum ether, d) washing the gel obtained and suctioning off the solvent, e ) the gel is dried and tempered and f) the SnO 2 obtained is exposed to a reducing gas stream in a fumigable furnace.
- the mixtures according to the invention have the advantage that they show no or almost no signs of thermal decomposition over a very wide temperature range.
- mixtures according to the invention have high thermal, chemical and electrochemical stability. This applies in particular to mixtures which contain salts of bisoxalatoborate, bismalonatoborate or bis [bis (trifluoromethyl) hydroxyacetato] borate.
- Lithium tris (oxalato) phosphate is synthesized according to DE 199 33 898.
- the lithium tris (oxalato) phosphate polymer / gel electrolyte is produced analogously to the second stage from example 1.
- Step 1
- the lithium bis [bis (trifluoromethyl) hydroxyacetato] borate polymer / gel electrolyte is prepared analogously to the second stage from Example 1.
- Step 1
- Lithium tris [bis (trifluoromethyl) hydroxyacetato] phosphate is synthesized analogously to lithium tris (oxalato) phosphate according to DE 199 33 898, with the difference that bis (trifluoromethyl) hydroxyacetic acid is used as the ligand instead of oxalic acid.
- the lithium tris [bis (trifluoromethyl) hydroxyacetato] phosphate polymer / gel electrolyte is produced analogously to the second stage from example 1.
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Abstract
L'invention concerne des mélanges de sels de borate ou de sels de phosphate, notamment de sels de spiroborate ou de sels de spirophosphate, et de polymères, ainsi que leur utilisation dans des électrolytes, des batteries, des condensateurs, des supercondensateurs et des cellules galvaniques.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10139409 | 2001-08-17 | ||
DE10139409A DE10139409A1 (de) | 2001-08-17 | 2001-08-17 | Polymerelektrolyte und deren Verwendung in galvanischen Zellen |
PCT/EP2002/008287 WO2003017409A2 (fr) | 2001-08-17 | 2002-07-25 | Electrolytes polymeres et leur utilisation dans des cellules galvaniques |
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EP1417726A2 true EP1417726A2 (fr) | 2004-05-12 |
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EP02760270A Withdrawn EP1417726A2 (fr) | 2001-08-17 | 2002-07-25 | Electrolytes polymeres et leur utilisation dans des cellules galvaniques |
Country Status (9)
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---|---|
US (1) | US20040209124A1 (fr) |
EP (1) | EP1417726A2 (fr) |
JP (1) | JP2005500432A (fr) |
KR (1) | KR20040030140A (fr) |
CN (1) | CN1606815A (fr) |
AU (1) | AU2002325902A1 (fr) |
CA (1) | CA2457633A1 (fr) |
DE (1) | DE10139409A1 (fr) |
WO (1) | WO2003017409A2 (fr) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4186115B2 (ja) * | 2003-06-11 | 2008-11-26 | ソニー株式会社 | リチウムイオン二次電池 |
JP2005005117A (ja) * | 2003-06-11 | 2005-01-06 | Sony Corp | 電池 |
JP4701595B2 (ja) * | 2003-09-03 | 2011-06-15 | ソニー株式会社 | リチウムイオン二次電池 |
JP2006196250A (ja) * | 2005-01-12 | 2006-07-27 | Sanyo Electric Co Ltd | リチウム二次電池 |
DE102004014629A1 (de) * | 2004-03-19 | 2005-10-06 | Varta Microbattery Gmbh | Galvanisches Element |
JP4346565B2 (ja) | 2004-03-30 | 2009-10-21 | 株式会社東芝 | 非水電解質二次電池 |
KR101373093B1 (ko) * | 2005-07-29 | 2014-03-12 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지 |
DE102007000698A1 (de) * | 2006-09-07 | 2008-03-27 | Chemetall Gmbh | Verwendung von Boratsalzen |
EP2097424A1 (fr) * | 2006-11-17 | 2009-09-09 | Chemetall GmbH | Composés de coordination du groupe du bore |
JP5315674B2 (ja) * | 2007-11-19 | 2013-10-16 | セントラル硝子株式会社 | 非水電池用電解液及びこれを用いた非水電池 |
JP5791522B2 (ja) * | 2009-02-18 | 2015-10-07 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツングChemetall GmbH | アノード材料としてリチウム金属又はリチウム金属含有合金及びビス(オキサラト)ホウ酸リチウムと少なくとも1種の別のリチウム錯塩とを有する電解質を有するガルバニ電池 |
KR101309161B1 (ko) * | 2009-11-17 | 2013-09-17 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 고분자 조성물, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 |
KR101829210B1 (ko) * | 2010-04-01 | 2018-03-29 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | 염 개질된 정전기 소산성 폴리머 |
JP2013051210A (ja) * | 2012-11-07 | 2013-03-14 | Sanyo Electric Co Ltd | リチウム二次電池 |
JP6542209B2 (ja) * | 2013-07-19 | 2019-07-10 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | リチウムイオン電池用電解質における電解質添加剤としての反応性リチウムアルコキシボレートの使用 |
CN103951689A (zh) * | 2014-05-16 | 2014-07-30 | 北京化学试剂研究所 | 液态双草酸硼酸锂的制备方法 |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
CN109134522A (zh) * | 2017-06-16 | 2019-01-04 | 中国科学院青岛生物能源与过程研究所 | 双羟基螯合氟代烷氧基硼酸盐及其制备方法和应用 |
DE102018202929A1 (de) * | 2018-02-27 | 2019-08-29 | Robert Bosch Gmbh | Hybridsuperkondensator und Verfahren zur Herstellung eines Hybridsuperkondensators |
CN111430796B (zh) * | 2020-04-02 | 2022-06-28 | 东莞市杉杉电池材料有限公司 | 一种锂离子电池电解液及含有该电解液的锂离子电池 |
CN112072170B (zh) * | 2020-07-23 | 2021-09-21 | 深圳技术大学 | 一种聚铝/硼酸盐固态电解质和一种电池 |
CN111934006B (zh) * | 2020-07-23 | 2021-09-21 | 深圳技术大学 | 固有微孔聚铝/硼酸盐固态电解质和电池 |
GB2626595A (en) * | 2023-01-27 | 2024-07-31 | Sumitomo Chemical Co | Compound |
Family Cites Families (11)
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US5273840A (en) * | 1990-08-01 | 1993-12-28 | Covalent Associates Incorporated | Methide salts, formulations, electrolytes and batteries formed therefrom |
DE4316104A1 (de) * | 1993-05-13 | 1994-11-17 | Manfred Wuehr | Elektrolyt zur Anwendung in einer galvanischen Zelle |
DE4317032A1 (de) * | 1993-05-21 | 1994-11-24 | Varta Batterie | Wiederaufladbare galvanische Lithiumzelle |
DE19633027A1 (de) * | 1996-08-16 | 1998-02-19 | Merck Patent Gmbh | Verfahren zur Herstellung von neuen Lithium-Borat-Komplexen |
DE19733948A1 (de) * | 1997-08-06 | 1999-02-11 | Merck Patent Gmbh | Verfahren zur Herstellung von Perfluoralkan-1-sulfonyl(perfluoralkylsulfonyl) imid-N-sulfonyl enthaltende Methanide, Imide und Sulfonate, und Perfluoralkan-1-N-(sulfonylbis(perfluoralkylsulfonyl)methaniden) |
DE19829030C1 (de) * | 1998-06-30 | 1999-10-07 | Metallgesellschaft Ag | Lithium-bisoxalatoborat, Verfahren zu dessen Herstellung und dessen Verwendung |
DE19933898A1 (de) * | 1999-07-22 | 2001-02-01 | Chemetall Gmbh | Tris(oxalato)phosphate, Verfahren zu deren Herstellung und deren Verwendung |
JP3498905B2 (ja) * | 1999-08-02 | 2004-02-23 | セントラル硝子株式会社 | 電気化学ディバイス用電解質 |
JP3824465B2 (ja) * | 1999-08-02 | 2006-09-20 | セントラル硝子株式会社 | イオン性錯体の合成法 |
DE19951804A1 (de) * | 1999-10-28 | 2001-05-03 | Merck Patent Gmbh | Komplexsalze zur Anwendung in elektrochemischen Zellen |
CN1182617C (zh) * | 2000-05-08 | 2004-12-29 | 森陶硝子株式会社 | 电解质、包含电解质的离子导体和包括这种离子导体的电化学装置 |
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2001
- 2001-08-17 DE DE10139409A patent/DE10139409A1/de not_active Withdrawn
-
2002
- 2002-07-25 KR KR10-2004-7002325A patent/KR20040030140A/ko not_active Application Discontinuation
- 2002-07-25 WO PCT/EP2002/008287 patent/WO2003017409A2/fr not_active Application Discontinuation
- 2002-07-25 US US10/487,020 patent/US20040209124A1/en not_active Abandoned
- 2002-07-25 EP EP02760270A patent/EP1417726A2/fr not_active Withdrawn
- 2002-07-25 CA CA002457633A patent/CA2457633A1/fr not_active Abandoned
- 2002-07-25 AU AU2002325902A patent/AU2002325902A1/en not_active Abandoned
- 2002-07-25 CN CNA028160835A patent/CN1606815A/zh active Pending
- 2002-07-25 JP JP2003522206A patent/JP2005500432A/ja active Pending
Non-Patent Citations (1)
Title |
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See references of WO03017409A2 * |
Also Published As
Publication number | Publication date |
---|---|
KR20040030140A (ko) | 2004-04-08 |
CN1606815A (zh) | 2005-04-13 |
JP2005500432A (ja) | 2005-01-06 |
WO2003017409A3 (fr) | 2004-01-22 |
US20040209124A1 (en) | 2004-10-21 |
DE10139409A1 (de) | 2003-02-27 |
WO2003017409A2 (fr) | 2003-02-27 |
CA2457633A1 (fr) | 2003-02-27 |
AU2002325902A1 (en) | 2003-03-03 |
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