CA2314740C - Electrolyte for electrochemical device - Google Patents
Electrolyte for electrochemical device Download PDFInfo
- Publication number
- CA2314740C CA2314740C CA002314740A CA2314740A CA2314740C CA 2314740 C CA2314740 C CA 2314740C CA 002314740 A CA002314740 A CA 002314740A CA 2314740 A CA2314740 A CA 2314740A CA 2314740 C CA2314740 C CA 2314740C
- Authority
- CA
- Canada
- Prior art keywords
- group
- electrolyte
- ion
- alkyl group
- halogenated
- 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
- 239000003792 electrolyte Substances 0.000 title claims abstract description 79
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 21
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims abstract 2
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims description 21
- 239000010416 ion conductor Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000010 aprotic solvent Substances 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 5
- 229910052695 Americium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052685 Curium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052766 Lawrencium Inorganic materials 0.000 claims description 4
- 229910052764 Mendelevium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052781 Neptunium Inorganic materials 0.000 claims description 4
- 229910052778 Plutonium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052774 Proactinium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052776 Thorium Inorganic materials 0.000 claims description 4
- 229910052770 Uranium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052713 technetium Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims 3
- 229910052775 Thulium Inorganic materials 0.000 claims 3
- 229910052804 chromium Inorganic materials 0.000 claims 3
- 229910052703 rhodium Inorganic materials 0.000 claims 2
- 229910052686 Californium Inorganic materials 0.000 claims 1
- 239000008896 Opium Substances 0.000 claims 1
- 229960001027 opium Drugs 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 12
- 125000003118 aryl group Chemical group 0.000 abstract description 11
- 150000004010 onium ions Chemical class 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 26
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 22
- 239000008151 electrolyte solution Substances 0.000 description 22
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 19
- 238000007599 discharging Methods 0.000 description 19
- -1 LiAsFs Inorganic materials 0.000 description 16
- 238000007600 charging Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 150000001450 anions Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 101150058243 Lipf gene Proteins 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910021382 natural graphite Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 229910013462 LiC104 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010936 titanium Substances 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
- BVKGUTLIPHZYCX-UHFFFAOYSA-N 3,3,3-trifluoro-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)C(F)(F)F BVKGUTLIPHZYCX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- NOHJBOWARMTILE-UHFFFAOYSA-N 4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butanoic acid Chemical compound OC(=O)CC(O)(C(F)(F)F)C(F)(F)F NOHJBOWARMTILE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011259 LiCoOz Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07F5/025—Boronic and borinic acid compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
The invention relates to an electrolyte for an electrochemical device. This electrolyte includes an ionic metal complex represented by the general formula (1):
wherein M is an element of groups 3-15 of the periodic table A a+
represents a metal ion, onium ion or proton X1 represents O or S;
each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-Cz20 aryl group or C6-C20 halogenated aryl group R4 represents a halogen, C1-C10 alkyl group, C1-C10halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7;
X2 represents O, S or NR5R6; each of R5 and R6 represents H or a C1-C10 alkyl group and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group. The electrolyte has high heat resistance and hydrolysis resistance as compared with conventional electrolytes.
wherein M is an element of groups 3-15 of the periodic table A a+
represents a metal ion, onium ion or proton X1 represents O or S;
each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-Cz20 aryl group or C6-C20 halogenated aryl group R4 represents a halogen, C1-C10 alkyl group, C1-C10halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7;
X2 represents O, S or NR5R6; each of R5 and R6 represents H or a C1-C10 alkyl group and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group. The electrolyte has high heat resistance and hydrolysis resistance as compared with conventional electrolytes.
Description
ELECTROLYTE FOR ELECTROCHEMICAL DEVICE
BACKGROUND OF THE INVENTION
The present invention relates to an electrolyte including an ionic metal complex having a novel chemical structure, an ionic conductor including the electrolyte, and electrochemical devices including the electrolyte, such as lithium cells, lithium ion cells, electrical double-layer capacitors.
Accompanying the evolution of portable equipment in recent years, there has been active development of electrochemical devices utilizing electrochemical phenomena, such as cells for use as their power supplies and capacitors. In addition, electrochromic devices (ECD), in which a color change occurs due to an electrochemical reaction, are examples of electrochemical devices for uses other than power supplies.
These electrochemical devices are typically composed of a pair of electrodes and an ionic conductor filled between them.
The ionic conductor contains a salt (AB) as an electrolyte, which is dissolved in a solvent, polymer or mixture thereof such that the salt is dissociated into cations (A+) and anions (B'), resulting in ionic conduction. In order to obtain the required level of ion conductivity for the device, it is necessary to dissolve a sufficient amount of this electrolyte in solvent or polymer. In actuality, there are many cases in which a solvent other than water is used, such as organic solvents and polymers. Electrolytes having sufficient solubility in such organic solvents and polymers are presently limited to only a few types. For example, electrolytes having sufficient solubility for use in lithium cells are only LiC104, LiPFs, LiBF4, LiAsFs, LiN(CFsS02)2 and LiCFsSOs. Although the cation type of the electrolyte is frequently limited by the device as is the case with the lithium ion of lithium cells, any anion can be used for the electrolyte provided it satisfies the condition of having high solubility.
Amidst the considerable diversity of the application range of these devices, efforts are made to seek out the optimum electrolyte for each application. Under the present circumstances, however, optimization efforts have reached their limit due to the limited types of available anions. In addition, existing electrolytes have various problems, thereby creating the need for'an electrolyte having a novel anion portion. More specifically, since C104 ion of LiC104 is explosive and AsFs ion of LiAsFs is toxic, they cannot be used for reasons of safety. Since LiN(C~sSO~)a and LiCFsSOs corrode the aluminum collector inside the cell when a potential is 1 o applied, their use presents difficulties. Even the only practical electrolyte of LiPFs ends up decomposing at temperatures of 70°C
and above, having problems including heat resistance and hydrolysis resistance.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a useful novel electrolyte, a novel ion conductor.containing the electrolyte, and a novel electrochemical device containing the ion conductor.
According to the present invention, there is provided an electrolyte for an electrochemical device. This electrolyte 20 comprises an ionic metal complex represented by the general formula (1):
z ~I~
A~~~, C~-4)»M \~R~)~
O
wherein M is transition metal from a selected the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Sc, Ti, V, Mo, Tc, Ru,Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, 30 Dy, Ho, Er,Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; Aa+
represents a metal ion, onium ion or proton;
a represents a number from 1 to 3: b represents a number from 1 to 3: p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; Xl represents 0 or S; each of R1 and R2 independently represents H, a halogen, a C1-Cl0 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-Clp alkylene group, C1-C1S
halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, C1-C10 alkyl group, Cl-C10 halogenated alkyl group, C6-C2p aryl group, C6-C2p halogenated aryl group or X2R~; X2 represents 0, S or NR5R6; each of R5 and R6 represents H or a C1-C10 alkyl group; and R~ represents a C1-Cl0 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
According to the present invention, there is provided an ion conductor for an electrochemical device.
This ion conductor comprises the electrolyte: and a member selected from the group consisting of a nonaqueous solvent that is an aprotic solvent, a polymer that is an aprotic polymer and a mixture thereof, said member dissolving therein said electrolyte.
According to the present invention, there is provided an electrochemical device comprising:
(a~ first and second electrodes; and (b) an ion conductor receiving therein said first and second electrodes, said ion conductor comprising:
BACKGROUND OF THE INVENTION
The present invention relates to an electrolyte including an ionic metal complex having a novel chemical structure, an ionic conductor including the electrolyte, and electrochemical devices including the electrolyte, such as lithium cells, lithium ion cells, electrical double-layer capacitors.
Accompanying the evolution of portable equipment in recent years, there has been active development of electrochemical devices utilizing electrochemical phenomena, such as cells for use as their power supplies and capacitors. In addition, electrochromic devices (ECD), in which a color change occurs due to an electrochemical reaction, are examples of electrochemical devices for uses other than power supplies.
These electrochemical devices are typically composed of a pair of electrodes and an ionic conductor filled between them.
The ionic conductor contains a salt (AB) as an electrolyte, which is dissolved in a solvent, polymer or mixture thereof such that the salt is dissociated into cations (A+) and anions (B'), resulting in ionic conduction. In order to obtain the required level of ion conductivity for the device, it is necessary to dissolve a sufficient amount of this electrolyte in solvent or polymer. In actuality, there are many cases in which a solvent other than water is used, such as organic solvents and polymers. Electrolytes having sufficient solubility in such organic solvents and polymers are presently limited to only a few types. For example, electrolytes having sufficient solubility for use in lithium cells are only LiC104, LiPFs, LiBF4, LiAsFs, LiN(CFsS02)2 and LiCFsSOs. Although the cation type of the electrolyte is frequently limited by the device as is the case with the lithium ion of lithium cells, any anion can be used for the electrolyte provided it satisfies the condition of having high solubility.
Amidst the considerable diversity of the application range of these devices, efforts are made to seek out the optimum electrolyte for each application. Under the present circumstances, however, optimization efforts have reached their limit due to the limited types of available anions. In addition, existing electrolytes have various problems, thereby creating the need for'an electrolyte having a novel anion portion. More specifically, since C104 ion of LiC104 is explosive and AsFs ion of LiAsFs is toxic, they cannot be used for reasons of safety. Since LiN(C~sSO~)a and LiCFsSOs corrode the aluminum collector inside the cell when a potential is 1 o applied, their use presents difficulties. Even the only practical electrolyte of LiPFs ends up decomposing at temperatures of 70°C
and above, having problems including heat resistance and hydrolysis resistance.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a useful novel electrolyte, a novel ion conductor.containing the electrolyte, and a novel electrochemical device containing the ion conductor.
According to the present invention, there is provided an electrolyte for an electrochemical device. This electrolyte 20 comprises an ionic metal complex represented by the general formula (1):
z ~I~
A~~~, C~-4)»M \~R~)~
O
wherein M is transition metal from a selected the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Sc, Ti, V, Mo, Tc, Ru,Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, 30 Dy, Ho, Er,Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; Aa+
represents a metal ion, onium ion or proton;
a represents a number from 1 to 3: b represents a number from 1 to 3: p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; Xl represents 0 or S; each of R1 and R2 independently represents H, a halogen, a C1-Cl0 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-Clp alkylene group, C1-C1S
halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, C1-C10 alkyl group, Cl-C10 halogenated alkyl group, C6-C2p aryl group, C6-C2p halogenated aryl group or X2R~; X2 represents 0, S or NR5R6; each of R5 and R6 represents H or a C1-C10 alkyl group; and R~ represents a C1-Cl0 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
According to the present invention, there is provided an ion conductor for an electrochemical device.
This ion conductor comprises the electrolyte: and a member selected from the group consisting of a nonaqueous solvent that is an aprotic solvent, a polymer that is an aprotic polymer and a mixture thereof, said member dissolving therein said electrolyte.
According to the present invention, there is provided an electrochemical device comprising:
(a~ first and second electrodes; and (b) an ion conductor receiving therein said first and second electrodes, said ion conductor comprising:
(1) an electrolyte according to the present invention; and (2) a member selected from the group consisting of a nonaqueous solvent that is an aprotic solvent, a polymer that is an aprotic polymer and a mixture thereof, said member dissolving therein said electrolyte.
According to the present invention, there is also provided an electrolyte for an electrochemical device, said electrolyte comprising an ionic metal complex represented by the following formula:
~'3~ ~ ~F3 ..
~i+ r3C ~ B ~ ~~~3 i \
O O O .U
An electrolyte according to the present invention has high heat resistance and hydrolysis resistance as compared with conventional electrolytes. Thus, the electrolyte can advantageously be used for electrochemical devices such as 2 0 lithium cell, lithium ion cell and electrical double-layer capacitor.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention, the alkyl groups, halogenated alkyl groups, aryl groups and halogenated aryl groups, which are contained in the ionic metal complex and the raw materials for synthesizing the same, may be branched and/or may have other functional groups such as hydroxyl groups and ether bonds.
The followings are specific nine examples of the ionic metal 3a complex represented by the general formula (1) of the present invention.
F3c cF3 - o cF3 Li+ F3 C O~B O C r3 Li+
0 0 0 o F ' ~~~ ,cF3 - ~,'3C CF3 _ CF
Li+ r3C ~O' ~O CF3 .+ r3C °. ;O_ CI~'3 F O~ B p L
' O O O
~i c'cF3 0 0 lt3C O O CF3 F cF3 _.
F v ~~ cF3 Li ~B~ Li F~P\
O O O ~ F O O
F3 . cF3 F3c cF3 _ _ F3C ~ CF3 Li+ \ O O \ + F3 C N~ ~~ C 1~ 3 / . ~ L / Li O B O
O U
O
F3c F3c \ cF3 0.x.0 CF3 (Li~2 O~Si.O
O O
Or FC-Here, although lithium ion is indicated as an example of Aa+
of the general formula (1), examples of other cations that can be used other than lithium ion include sodium ion, potassium ion, magnesium ion, calcium ion, barium ion, cesium ion, silver ion, zinc ion, copper ion, cobalt ion, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion, yttrium ion, lanthanoid ion, actinoid ion, tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium ion, triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, proton, tetraethylphosphonium ion, tetramethylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, and triethylsulfonium ion. In the case of considering the application of the ionic metal complex for electrochemical devices and the like, lithium ion, tetraalkylammonium ion and proton are preferable.
As shown in the general formula (1), the valency (valence) of the Aa+ cation is preferably from 1 to 3. If the valency is larger than 3, the problem occurs in which it becomes difficult to dissolve the ionic metal complex in solvent due to the increase in crystal lattice energy. Consequently, in the case of requiring solubility of the ionic metal complex, a valency of 1 is preferable. As shown in the general formula (1), the valency (b-) of the anion is similarly preferably from 1 to 3, and a valency of 1 is particularly preferable.
The constant p expresses the ratio of the valency of the anion to the valency of the cation, namely b/a.
In the general formula (1), M at the center of the ionic metal complex of the present invention is selected from elements of groups 3-15 of the periodic table. It is preferably Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb, and more preferably Al, B or P. Although it is possible to use various elements for the M other than these preferable examples, synthesis is relatively easy in the case of using Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb. In addition to ease of synthesis, the ionic metal complex has excellent properties in terms of low toxicity, stability and production cost in the case of using Al, B or P.
In the general formula (1), the organic or inorganic portion bonded to M is referred tows the ligand. As mentioned above, Xl in the general formula (1) represents 0 or S and is bonded to M through its hetero atom (0 or s ) . Although the bonding of an atom other than O or s is not impossible, the synthesis becomes extremely bothersome. The ionic metal complex represented by the general formula (1) is characterized by these ligands forming a chelate structure with M since there is bonding with M by a carboxyl group (-COO-) other than Xl within the same ligand. As a result of this chlelation, the heat resistance, chemical stability and hydroly sis resistance of the ionic metal complex are improved. Although constant q in this ligand is either 0 or l, in the case of 0 in particular, since the chelate ring becomes a five-member ring, chelating effects are demonstrated most prominently, making this preferable due to the resulting increase instability. In addition; since the negative charge of the central M is dissipated by electron attracting effects of the carboxyl groups) resulting in an increase in electrical stability of the anion, ion dissociation becomes extremely easy resulting in corresponding increases of the ionic metal complex in solvent solubility, ion conductivity, catalyst activity and so forth. In addition, the other properties of heat resistance, chemical stability and hydrolysis resistance are also improved.
In the general formula (1), each of Rl and R2 is independently selected from H, halogen, CnCio alkyl groups and C1-Cio halogenated alkyl groups. At least one of either Rl and RZ is preferably a fluorinated alkyl group, and more preferably, at least one of RI and R~ is a trifluoromethyl group. Due to the presence of an electron-attracting halogen and/or a halogenated alkyl group for R1 and R'', the negative charge of the central M is dissipated.
According to the present invention, there is also provided an electrolyte for an electrochemical device, said electrolyte comprising an ionic metal complex represented by the following formula:
~'3~ ~ ~F3 ..
~i+ r3C ~ B ~ ~~~3 i \
O O O .U
An electrolyte according to the present invention has high heat resistance and hydrolysis resistance as compared with conventional electrolytes. Thus, the electrolyte can advantageously be used for electrochemical devices such as 2 0 lithium cell, lithium ion cell and electrical double-layer capacitor.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention, the alkyl groups, halogenated alkyl groups, aryl groups and halogenated aryl groups, which are contained in the ionic metal complex and the raw materials for synthesizing the same, may be branched and/or may have other functional groups such as hydroxyl groups and ether bonds.
The followings are specific nine examples of the ionic metal 3a complex represented by the general formula (1) of the present invention.
F3c cF3 - o cF3 Li+ F3 C O~B O C r3 Li+
0 0 0 o F ' ~~~ ,cF3 - ~,'3C CF3 _ CF
Li+ r3C ~O' ~O CF3 .+ r3C °. ;O_ CI~'3 F O~ B p L
' O O O
~i c'cF3 0 0 lt3C O O CF3 F cF3 _.
F v ~~ cF3 Li ~B~ Li F~P\
O O O ~ F O O
F3 . cF3 F3c cF3 _ _ F3C ~ CF3 Li+ \ O O \ + F3 C N~ ~~ C 1~ 3 / . ~ L / Li O B O
O U
O
F3c F3c \ cF3 0.x.0 CF3 (Li~2 O~Si.O
O O
Or FC-Here, although lithium ion is indicated as an example of Aa+
of the general formula (1), examples of other cations that can be used other than lithium ion include sodium ion, potassium ion, magnesium ion, calcium ion, barium ion, cesium ion, silver ion, zinc ion, copper ion, cobalt ion, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion, yttrium ion, lanthanoid ion, actinoid ion, tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium ion, triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, proton, tetraethylphosphonium ion, tetramethylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, and triethylsulfonium ion. In the case of considering the application of the ionic metal complex for electrochemical devices and the like, lithium ion, tetraalkylammonium ion and proton are preferable.
As shown in the general formula (1), the valency (valence) of the Aa+ cation is preferably from 1 to 3. If the valency is larger than 3, the problem occurs in which it becomes difficult to dissolve the ionic metal complex in solvent due to the increase in crystal lattice energy. Consequently, in the case of requiring solubility of the ionic metal complex, a valency of 1 is preferable. As shown in the general formula (1), the valency (b-) of the anion is similarly preferably from 1 to 3, and a valency of 1 is particularly preferable.
The constant p expresses the ratio of the valency of the anion to the valency of the cation, namely b/a.
In the general formula (1), M at the center of the ionic metal complex of the present invention is selected from elements of groups 3-15 of the periodic table. It is preferably Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb, and more preferably Al, B or P. Although it is possible to use various elements for the M other than these preferable examples, synthesis is relatively easy in the case of using Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb. In addition to ease of synthesis, the ionic metal complex has excellent properties in terms of low toxicity, stability and production cost in the case of using Al, B or P.
In the general formula (1), the organic or inorganic portion bonded to M is referred tows the ligand. As mentioned above, Xl in the general formula (1) represents 0 or S and is bonded to M through its hetero atom (0 or s ) . Although the bonding of an atom other than O or s is not impossible, the synthesis becomes extremely bothersome. The ionic metal complex represented by the general formula (1) is characterized by these ligands forming a chelate structure with M since there is bonding with M by a carboxyl group (-COO-) other than Xl within the same ligand. As a result of this chlelation, the heat resistance, chemical stability and hydroly sis resistance of the ionic metal complex are improved. Although constant q in this ligand is either 0 or l, in the case of 0 in particular, since the chelate ring becomes a five-member ring, chelating effects are demonstrated most prominently, making this preferable due to the resulting increase instability. In addition; since the negative charge of the central M is dissipated by electron attracting effects of the carboxyl groups) resulting in an increase in electrical stability of the anion, ion dissociation becomes extremely easy resulting in corresponding increases of the ionic metal complex in solvent solubility, ion conductivity, catalyst activity and so forth. In addition, the other properties of heat resistance, chemical stability and hydrolysis resistance are also improved.
In the general formula (1), each of Rl and R2 is independently selected from H, halogen, CnCio alkyl groups and C1-Cio halogenated alkyl groups. At least one of either Rl and RZ is preferably a fluorinated alkyl group, and more preferably, at least one of RI and R~ is a trifluoromethyl group. Due to the presence of an electron-attracting halogen and/or a halogenated alkyl group for R1 and R'', the negative charge of the central M is dissipated.
This results in an increase of the anion of the general formula (1) in electrical stability. With this, the ion dissociation becomes extremely easy resulting in an increase of the ionic metal complex in solvent solubility, ion conductivity, catalyst activity and so forth.
In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also improved: The case in which the halogen is fluorine in particular has significant advantageous effects, while the case of a trifluoromethyl group has the greatest advantageous effect.
In the general formula (1), R3 is selected from C1-Clo alkylene groups, C1-Clo halogenated alkylene groups, ,C~-C2o aryl groups and C~-C2o halogenated aryl groups. 8315 preferably one which forms a 5 to 10-membered ring when a chelate ring is formed with the central M. The case of a ring having more than 10 members is not preferable, since chelating advantageous effects are reduced.
In addition, in the case R3 has a portion of hydroxyl group or carboxyl group, it is possible to form a bond between the central M
and this portion.
In the general formula (1), R4 is selected from halogens, C1-Clo alkyl groups, C1-Cio halogenated alkyl groups, Cs C2o aryl groups, C~Czo halogenated aryl groups and X'R~. Of these, fluorine is preferable. X2 represents 0, S or NR~R~ and bonds to M through one of these heteroatoms (0, S and N). Although the bonding of an atom other than 0, S or N is not impossible, the 2~ synthesis becomes extremely bothersome. Each of R~ and R6 is selected from H and Ci-Cio alkyl groups. Each of Rj and R~
differs from other groups (e.g., Rl and R2) in that the former is not required to be an electron attracting group. In the case of introducing an electron attracting group as R~ or R~, the electron density on N of NR~R~ decreases, thereby preventing coordination on the central M. R~ is selected from CuC~o alkyl groups, CnClo halogenated alkyl groups, C6 Cao aryl groups and C6 Coo halogenated aryl groups. Of these, a Ci-Cio fluorinated alkyl groups is preferable. Due to the presence of an electron-attracting halogenated alkyl group as R7, the negative charge of the central M is dissipated. Since this increases the electrical stability of the anion of the general formula (1), ion dissociation becomes extremely easy resulting in an increase of the ionic metal complex in solvent solubility, ion conductivity and catalyst activity. In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also improved.
The case in which the halogenated alkyl group as R7 is a fluorinated alkyl group in particular results in even greater advantageous effects.
In the general formula (1), the values of the constants m and n relating to the number of the above-mentioned ligands depend on the type of the central M. In fact, m is preferably from 1 to 3, while n is preferably from 0 to 4.
The anion of the ionic metal complex represented by the general formula (1) is stabilized by having therein a halogenated alkyl group with strong electron attraction, and particularly a trifluoromethyl group (CF3 group) and carbonyl group (C=O group), thereby facilitating dissociation of the ionic metal complex into the anion and canon. This is extremely important in the case of using as the electrolyte of an electrochemical device. Although there are an almost infinite number of salts referred to as electrolytes, the majority dissolve and dissociate in water, and thereby are ion conductive. Many of such salts do not even dissolve in organic solvents and so forth other than water. Such aqueous solutions are used as an electrolytic solution of electrochemical devices. However, due to the low decomposition potential of water as a solvent and its susceptibility to oxidation and reduction, there are many restrictions on its use. For example, in a lithium cell and so forth, since the potential difference between the electrodes of the device is 3 V or more, water ends up being electrolyzed into hydrogen and oxygen.
In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also improved: The case in which the halogen is fluorine in particular has significant advantageous effects, while the case of a trifluoromethyl group has the greatest advantageous effect.
In the general formula (1), R3 is selected from C1-Clo alkylene groups, C1-Clo halogenated alkylene groups, ,C~-C2o aryl groups and C~-C2o halogenated aryl groups. 8315 preferably one which forms a 5 to 10-membered ring when a chelate ring is formed with the central M. The case of a ring having more than 10 members is not preferable, since chelating advantageous effects are reduced.
In addition, in the case R3 has a portion of hydroxyl group or carboxyl group, it is possible to form a bond between the central M
and this portion.
In the general formula (1), R4 is selected from halogens, C1-Clo alkyl groups, C1-Cio halogenated alkyl groups, Cs C2o aryl groups, C~Czo halogenated aryl groups and X'R~. Of these, fluorine is preferable. X2 represents 0, S or NR~R~ and bonds to M through one of these heteroatoms (0, S and N). Although the bonding of an atom other than 0, S or N is not impossible, the 2~ synthesis becomes extremely bothersome. Each of R~ and R6 is selected from H and Ci-Cio alkyl groups. Each of Rj and R~
differs from other groups (e.g., Rl and R2) in that the former is not required to be an electron attracting group. In the case of introducing an electron attracting group as R~ or R~, the electron density on N of NR~R~ decreases, thereby preventing coordination on the central M. R~ is selected from CuC~o alkyl groups, CnClo halogenated alkyl groups, C6 Cao aryl groups and C6 Coo halogenated aryl groups. Of these, a Ci-Cio fluorinated alkyl groups is preferable. Due to the presence of an electron-attracting halogenated alkyl group as R7, the negative charge of the central M is dissipated. Since this increases the electrical stability of the anion of the general formula (1), ion dissociation becomes extremely easy resulting in an increase of the ionic metal complex in solvent solubility, ion conductivity and catalyst activity. In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also improved.
The case in which the halogenated alkyl group as R7 is a fluorinated alkyl group in particular results in even greater advantageous effects.
In the general formula (1), the values of the constants m and n relating to the number of the above-mentioned ligands depend on the type of the central M. In fact, m is preferably from 1 to 3, while n is preferably from 0 to 4.
The anion of the ionic metal complex represented by the general formula (1) is stabilized by having therein a halogenated alkyl group with strong electron attraction, and particularly a trifluoromethyl group (CF3 group) and carbonyl group (C=O group), thereby facilitating dissociation of the ionic metal complex into the anion and canon. This is extremely important in the case of using as the electrolyte of an electrochemical device. Although there are an almost infinite number of salts referred to as electrolytes, the majority dissolve and dissociate in water, and thereby are ion conductive. Many of such salts do not even dissolve in organic solvents and so forth other than water. Such aqueous solutions are used as an electrolytic solution of electrochemical devices. However, due to the low decomposition potential of water as a solvent and its susceptibility to oxidation and reduction, there are many restrictions on its use. For example, in a lithium cell and so forth, since the potential difference between the electrodes of the device is 3 V or more, water ends up being electrolyzed into hydrogen and oxygen.
There are many organic solvents and polymers that are insusceptible to oxidation and reduction as compared with water due to their structures. Therefore, they are used in devices requiring higher voltages such as lithium cells and electrical double-layer capacitors.
In comparison with conventional electrolytes, the electrolyte of the present invention is extremely soluble in organic solvent and dissociates more easily due to the above-mentioned effects of CFs groups and C=O groups and a large size of the anion of the ionic metal complex. Consequently, an electrolytic solution containing an electrolyte of the ionic metal complex dissolved in an organic solvent can be used as a superior ion conductor of electrochemical devices such as lithium cells. Complexes of organic substances and metals are typically susceptible to hydrolysis and there are many that are chemically unstable.
Since the electrolyte of the present invention, however, has a chelate structure, it is extremely stable and resistant to hydrolysis and so forth. In addition, that having fluorine within the chemical structure represented by the general formula (1) is particularly preferable since it further increases chemical stability such as oxidation resistance due to the effect of the fluorine.
Optimization of the chemical structure of the general formula (1) makes it possible to obtain an electrolyte that dissolves in organic solvents in which conventional electrolytes do not dissolve, examples of which include toluene, hexane and fluorine-containing organic solvents such as fluorohydrocarbons.
Although the electrolyte of the present invention is used as the electrolyte of electrochemical devices such as lithium cells (cells), lithium ion cells (cells) and electrical double-layer capacitors, examples of its other applications include catalysts of organic synthesis reactions, polymerization catalysts and co-catalysts (auxiliary catalysts) of olefin polymerization.
There are no particular restrictions on the process for synthesizing the electrolyte of the present invention. For example, an ionic metal complex (electrolyte) having the following formula can be synthesized by reacting LiB(OCHs)4 with a stoichiometric amount of HOC(CFs)2COOH.
F3C CF3 ' I
L,i+ r3C ~~ ~O Cr3 B~
O O O O
In the case of preparing an electrochemical device using an electrolyte of the present invention, its basic structural elements are ion conductor, negative electrode, positive electrode, collector, separator, container and the like.
A mixture of electrolyte and non-aqueous solvent or polymer is used as the ion conductor. If a non-aqueous solvent is used, the resulting ion conductor is typically referred to as an electrolytic solution, while if a polymer is used, it is typically referred to as a polymer solid electrolyte. Non-aqueous solvent may also be contained as plasticizer in polymer solid electrolytes. It is possible to use one type or a mixture of two or more types of an electrolyte of the present invention. In the case of mixing, it is necessary that one type be an electrolyte of the present invention, while examples of other electrolytes that can be used include lithium salts such as LiC104, LiPFs, LiBF4, LiCFsSOs, LiN(CFsS02)2 and LiSbFs.
There are no particular restrictions on the non-aqueous solvent provided it is an aprotic solvent that is able to dissolve an electrolyte of the present invention, and examples of this non-aqueous solvent that can be used include carbonates, esters, ethers, lactones, nitriles, amides and sulfones. In addition, the solvent can either be used alone or in the form of a mixture of two or more types of solvent. Specific examples of the solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, nitromethane, N,N-dimethylformamide, dimethylsulfoxide, sulfolane and y-butyrolactone.
There are no particular restrictions on the polymer to be mixed with the electrolyte of the invention provided it is an aprotic polymer that can dissolve the electrolyte. Examples of such polymer include polymers having polyethylene oxide on their main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers and polyacrylonitrile. In the case of adding plasticizer to these polymers, the above-mentioned aprotic non-aqueous solvent can be used. The concentration of the electrolyte of the present invention in these ion conductors is preferably 0.1 mol/dm3 or more up to the saturated concentration, and more preferably from 0.5 mol/dm3 to 1.5 mol/dm3. If the concentration is lower than 0.1 mol/dm3, ion conductivity may become too low.
There are no particular restrictions on the negative electrode material for preparing an electrochemical device. In the case of lithium cell, lithium metal (metallic lithium) or an alloy of lithium and another metal can be used. In the case of a lithium ion cell, it is possible to use an intercalation compound containing lithium atoms in a matrix of another material, such as carbon, natural graphite or metal oxide. This carbon can be obtained by baking polymer, organic substance, pitch or the like. In the case of electrical double-layer capacitor, it is possible to use activated carbon, porous metal oxide, porous metal, conductive polymer and so forth.
There are no particular restrictions on the positive electrode material. In the case of lithium cell or lithium ion cell, lithium-containing oxides such as LiCoOz, LiNi02, LiMnO~ and LiMn20~~ oxides such as Ti02> Vz05 and MoOs~ sulfides such as TiSa and FeS~ and electrically conductive polymers such as polyacetylene, polyparaphenylene, polyani.line or polypyrrole can be used. In the case of electrical double-layer capacitor, activated carbon, porous metal oxide, porous metal, electrically conductive polymer and so forth can be used.
The following nonlimitative examples are illustrative of the present invention.
In a glove box having an atmosphere of a dew point of -50°C, 20.2 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)2COOH) were dissolved in 20 mI of dimethyl carbonate. Next, 6.8 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution: under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 20.0 g of a white solid as a product. This product was identified by NMR
spectrum and elementary analysis as being LiB(OC(CFs)zC00)2 having the following formula.
~ F3C CF3 '"
Li+ F3C ~~B O C
w O O. O O
The NMR spectral data of the product is shown below.
1~F-NMR (hexafluorobenzene standard, solvent: CDsCN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) mB-NMR (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) Next,. the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = I:I) to prepare an electrolytic solution having an electrolyte concentration of I molldm~ followed by measurement of ion conductivity with an alternating current bipolar-type cell. As a result, the ion conductivity was 7.0 mS/cm.
The above-mentioned electrolyte was placed in a container made of fluororesin. When stored for 1 month at 100°C as a heat resistance test, there was no discoloration or other deterioration of the electrolytic solution. In addition, when water was added to this electrolytic solution, it was found by NMR that the electrolytic solution had not been subjected to hydrolysis at all.
A corrosion test of an aluminum collector was performed using the above-mentioned electrolytic solution. A beaker type cell was used for the test cell, using aluminum for the working electrode, and lithium metal (metallic lithium) for the counter electrode and reference electrode. When the working electrode was held at 5 V (Li/Li+), there was no flow of current whatsoever.
Following testing, although the surface of the working electrode was observed by SEM, there were no changes observed in comparison with that before testing.
A charging and discharging test of an actual cell was performed using the above-mentioned electrolytic solution. The test cell was prepared in the manner described below. The positive electrode was prepared by mixing 5 parts by weight of polyvinylidene fluoride (PVDF) as a binder and 5 parts by weight of acetylene black as a conductor with 90 parts by weight of an LiCo02 powder followed by the addition of N,N-dimethylformamide to form a paste. This paste was applied to an aluminum foil and allowed to dry to obtain the test positive electrode. Lithium metal was used for the negative electrode. A
glass fiber filter as a separator was impregnated with the electrolytic solution, thereby assembling the cell.
Next, a constant current charging and dischar grog test was conducted as described below. The current density was 0.35 mA/cm'' for both charging and discharging, while charging was performed until 4.2 V and discharging until 3.0 V (vs. Li/Li+). As a result, the initial discharge capacity was 125 mAh/g. Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 88°/ of the initial capacity.
In a glove box having an atmosphere of a dew point of -50°C, 10Øg of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)~COOH) were dissolved in 20 ml of dimethyl carbonate. Next, a lithium methoxide/methanol solution containing~3.6 g of lithium methoxide (LiOCHs) was slowly added to this solution. The dimethyl carbonate and methanol were removed under a reduced pressure condition of 60°C and 1 torr, thereby obtaining LiOC(CFs)~COOLi as a product. After dissolving this compound in acetonitrile, 4.4 g of LiBF4 were added to this solution, followed by heating to 60°C and allowing to react for 10 hours. After filtering the LiF precipitate that formed during the reaction, the dimethyl carbonate was removed under a reduced pressure condition of 80°C and 1 torr, thereby obtaining L2.5 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiBFz(OC(CFs)2C00) having the following formula.
~~3 ~1.~ Fv$ fl CF3 F O
The N1~IR spectral data of the product is shown below.
19F-N11~IR (hexaf7:uorobenzene standard, solvent: CDsCN) 15.3 ppm (2F, s) 88.2 ppm (6F, s) mp,.lrn,IR (B(OCHs)s standard, solvent: CDsCN) .14.1 ppm (t, J = 4 Hz) Next, the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3 followed by measurement of ion conductivity by the alternating current bipolar-type cell. As a result, the ion conductivity was 8.2 mS/cm.
A charging and discharging test of an actual cell was conducted using the above-mentioned electrolytic solution. The test cell (half cell) was prepared in the manner described below.
parts by weight of polyvinylidene fluoride (PVDF) as a binder 10 were mixed with 90 parts by weight of natural graphite powder followed by the addition of N,N-dimethylformamide to prepare a slurry. This slurry was applied to a nickel mesh and allowed to dry for 12 hours at 150°C to prepare a test negative electrode.
Lithium metal was used for a counter electrode. A glass fiber filter as a separator was impregnated with the above-mentioned electrolytic solution, thereby assembling the half cell.
A constant current charging and discharging test was then conducted under the conditions indicated below. The current density was 0.3 mA/cm2 for both charging and discharging, while charging was performed until 0.0 V and discharging until 1.5 V (vs.
Li/Li+). As a result, the initial discharge capacity was 320 mAh/g.
Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 95% of the initial capacity.
In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of trifluorolactic acid (HOCH(CFa)COOH) were dissolved in 20 ml of dimethyl carbonate. Next, 4.9 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 10.4 g of a white solid as a product. This product was identified by NNIR spectrum and elementary analysis as being LiB(OCH(CFs)C00)~.
F3C fl\ ~~ ~F3 s ~,i+ ~B~
~J O \~
The NMR spectral data of the product is shown below.
lsF.NMR (hexafluorobenzene standard, solvent: CD3CN) 8?.12 ppm (3F, d, J = 8 Hz) 8?.18 ppm (3F, d, J = 8 Hz) 87.32 ppm (3F, d, J = 8 Hz) Since the raw material, trifluorolactic acid, is a racemic modification having two types of optical isomers, three types of 1 s peaks were observed in 19F-NMR due to three combinations of (R,R), (S,S) and (R,S).
1H.NMR
4.57 ppm (1H, q, J = 8 Hz) iiB-NMR (B(OCHa)s standard, solvent: CDsCN) -8.03 ppm (s) Next, the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3 followed by measurement of ion conductivity by the alternating current bipolar.type cell. As a result, the ion conductivity was 6.3 mS/cm.
A charging and discharging test of an actual cell was conducted using the above-mentioned electrolyte. A test cell (half cell) was prepared in the manner described below. 10 parts by weight of polyvinylidene fluoride (PV-DF) as a binder were mixed with 90 parts by weight of natural graphite powder followed by the addition of N,N-dimethylformamide to prepare a slurry. This slurry was applied to a nickel mesh and allowed to dry for 12 hours at 150°C to prepare a test negative electrode. Lithium metal was used for a counter electrode. A glass fiber filter as a separator was impregnated with the above-mentioned electrolytic solution, thereby assembling the half cell.
A constant current charging and discharging test was then conducted under the conditions indicated below. The current density was 0.3 mA/em'' for both charging and discharging, while charging was performed until 0.0 V and discharging until 1.5 V (vs.
LilLi+). As a result, the initial discharge capacity was 340 m_Ahlg.
IO Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 94% of the initial capacity.
In a glove box having an atmosphere of a dew point of -50°C, 4.2 g of 4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butyric acid (HOC(CFs)2CH2COOH) were dissolved in 20 ml of dimethyl carbonate. Next, 1.3 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution:' After this addition, the solution was heated to 60°G and allowed to react for 10 hours. Dimethyl carbonate was removed ~rom the resulting reaction solution under a reduced pressure condition of 120°C and 1 torr, thereby obtaining 4.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OC(CFs)zCHaCOO)z.
F C CF3 CF~F
3 ~ 3 Lip H ~B H
H ~~ v _H
O
The N1~1R spectral data of the product is shown below.
'-~F-u~i~.~IR (hexafluorobenzene standard, solvent: CDsCN) 85.0 ppm (12F, s) 1H-i~ll~IR
2.86 ppm (2H, d, J = 16 Hz) 2.75 ppm (2H, d, J = 16 Hz) Next, the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 0.8 mol/dm3 followed by measurement of ion conductivity by the alternating current bipolar-type cell. As a result, the ion conductivity was 1.9 mS/cm.
A charging and discharging test of an actual cell was conducted using the above-mentioned electrolyte. A test cell (half cell) was prepared in the manner described below. 10 parts by weight of polyvinylidene fluoride (PVDF) as a binder were mixed with 90 parts by weight of natural graphite powder followed by the addition of N,N-dimethylformamide to prepare a slurry. This slurry was applied to a nickel mesh and allowed to dry for 12 hours at 150°C to prepare a test negative electrode. Lithium metal was used for a counter electrode. A glass fiber filter as a separator was impregnated with the above-mentioned electrolytic solution, thereby assembling the half cell.
A constant current charging and discharging test was tr~en conducted under the conditions indicated below. The current density was 0.3 mA/cm2 for both charging and discharging, while charging was performed until 0.0 V and discharging until 1.5 V (vs.
Li/Li+). As a result, the initial discharge capacity was 320 mAh/g.
Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 97% of the initial capacity.
LiPFs was dissolved in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:l) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3. Next, this electrolytic solution was placed in a fluororesin container, and, when subjected to a heat resistance test by storing for 1 month at 100°C, the electrolytic solution changed to have a yellow color.
When water was added to this electrolytic solution prior to conducting the heat resistance test, various hydrolysis products were found by NMR. Substances detected as hydrolysis products included hydrogen fluoride and phosphorus oxychloride.
LiN(CFaS02)2 was dissolved in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3. Next, a corrosion test of an aluminum separator was conducted using this electrolyte. A
beaker type cell was used for the test cell, using aluminum for the working electrode, and lithium metal for the counter electrode and 1 S reference electrode. When the working electrode was held at 5 V
(Li/Li+), current flowed and the current value increased with time.
Following testing, when the surface of the working electrode was observed by SEM, severe corrosion pits were found in the aluminum surface.
In comparison with conventional electrolytes, the electrolyte of the present invention is extremely soluble in organic solvent and dissociates more easily due to the above-mentioned effects of CFs groups and C=O groups and a large size of the anion of the ionic metal complex. Consequently, an electrolytic solution containing an electrolyte of the ionic metal complex dissolved in an organic solvent can be used as a superior ion conductor of electrochemical devices such as lithium cells. Complexes of organic substances and metals are typically susceptible to hydrolysis and there are many that are chemically unstable.
Since the electrolyte of the present invention, however, has a chelate structure, it is extremely stable and resistant to hydrolysis and so forth. In addition, that having fluorine within the chemical structure represented by the general formula (1) is particularly preferable since it further increases chemical stability such as oxidation resistance due to the effect of the fluorine.
Optimization of the chemical structure of the general formula (1) makes it possible to obtain an electrolyte that dissolves in organic solvents in which conventional electrolytes do not dissolve, examples of which include toluene, hexane and fluorine-containing organic solvents such as fluorohydrocarbons.
Although the electrolyte of the present invention is used as the electrolyte of electrochemical devices such as lithium cells (cells), lithium ion cells (cells) and electrical double-layer capacitors, examples of its other applications include catalysts of organic synthesis reactions, polymerization catalysts and co-catalysts (auxiliary catalysts) of olefin polymerization.
There are no particular restrictions on the process for synthesizing the electrolyte of the present invention. For example, an ionic metal complex (electrolyte) having the following formula can be synthesized by reacting LiB(OCHs)4 with a stoichiometric amount of HOC(CFs)2COOH.
F3C CF3 ' I
L,i+ r3C ~~ ~O Cr3 B~
O O O O
In the case of preparing an electrochemical device using an electrolyte of the present invention, its basic structural elements are ion conductor, negative electrode, positive electrode, collector, separator, container and the like.
A mixture of electrolyte and non-aqueous solvent or polymer is used as the ion conductor. If a non-aqueous solvent is used, the resulting ion conductor is typically referred to as an electrolytic solution, while if a polymer is used, it is typically referred to as a polymer solid electrolyte. Non-aqueous solvent may also be contained as plasticizer in polymer solid electrolytes. It is possible to use one type or a mixture of two or more types of an electrolyte of the present invention. In the case of mixing, it is necessary that one type be an electrolyte of the present invention, while examples of other electrolytes that can be used include lithium salts such as LiC104, LiPFs, LiBF4, LiCFsSOs, LiN(CFsS02)2 and LiSbFs.
There are no particular restrictions on the non-aqueous solvent provided it is an aprotic solvent that is able to dissolve an electrolyte of the present invention, and examples of this non-aqueous solvent that can be used include carbonates, esters, ethers, lactones, nitriles, amides and sulfones. In addition, the solvent can either be used alone or in the form of a mixture of two or more types of solvent. Specific examples of the solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, nitromethane, N,N-dimethylformamide, dimethylsulfoxide, sulfolane and y-butyrolactone.
There are no particular restrictions on the polymer to be mixed with the electrolyte of the invention provided it is an aprotic polymer that can dissolve the electrolyte. Examples of such polymer include polymers having polyethylene oxide on their main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers and polyacrylonitrile. In the case of adding plasticizer to these polymers, the above-mentioned aprotic non-aqueous solvent can be used. The concentration of the electrolyte of the present invention in these ion conductors is preferably 0.1 mol/dm3 or more up to the saturated concentration, and more preferably from 0.5 mol/dm3 to 1.5 mol/dm3. If the concentration is lower than 0.1 mol/dm3, ion conductivity may become too low.
There are no particular restrictions on the negative electrode material for preparing an electrochemical device. In the case of lithium cell, lithium metal (metallic lithium) or an alloy of lithium and another metal can be used. In the case of a lithium ion cell, it is possible to use an intercalation compound containing lithium atoms in a matrix of another material, such as carbon, natural graphite or metal oxide. This carbon can be obtained by baking polymer, organic substance, pitch or the like. In the case of electrical double-layer capacitor, it is possible to use activated carbon, porous metal oxide, porous metal, conductive polymer and so forth.
There are no particular restrictions on the positive electrode material. In the case of lithium cell or lithium ion cell, lithium-containing oxides such as LiCoOz, LiNi02, LiMnO~ and LiMn20~~ oxides such as Ti02> Vz05 and MoOs~ sulfides such as TiSa and FeS~ and electrically conductive polymers such as polyacetylene, polyparaphenylene, polyani.line or polypyrrole can be used. In the case of electrical double-layer capacitor, activated carbon, porous metal oxide, porous metal, electrically conductive polymer and so forth can be used.
The following nonlimitative examples are illustrative of the present invention.
In a glove box having an atmosphere of a dew point of -50°C, 20.2 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)2COOH) were dissolved in 20 mI of dimethyl carbonate. Next, 6.8 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution: under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 20.0 g of a white solid as a product. This product was identified by NMR
spectrum and elementary analysis as being LiB(OC(CFs)zC00)2 having the following formula.
~ F3C CF3 '"
Li+ F3C ~~B O C
w O O. O O
The NMR spectral data of the product is shown below.
1~F-NMR (hexafluorobenzene standard, solvent: CDsCN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) mB-NMR (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) Next,. the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = I:I) to prepare an electrolytic solution having an electrolyte concentration of I molldm~ followed by measurement of ion conductivity with an alternating current bipolar-type cell. As a result, the ion conductivity was 7.0 mS/cm.
The above-mentioned electrolyte was placed in a container made of fluororesin. When stored for 1 month at 100°C as a heat resistance test, there was no discoloration or other deterioration of the electrolytic solution. In addition, when water was added to this electrolytic solution, it was found by NMR that the electrolytic solution had not been subjected to hydrolysis at all.
A corrosion test of an aluminum collector was performed using the above-mentioned electrolytic solution. A beaker type cell was used for the test cell, using aluminum for the working electrode, and lithium metal (metallic lithium) for the counter electrode and reference electrode. When the working electrode was held at 5 V (Li/Li+), there was no flow of current whatsoever.
Following testing, although the surface of the working electrode was observed by SEM, there were no changes observed in comparison with that before testing.
A charging and discharging test of an actual cell was performed using the above-mentioned electrolytic solution. The test cell was prepared in the manner described below. The positive electrode was prepared by mixing 5 parts by weight of polyvinylidene fluoride (PVDF) as a binder and 5 parts by weight of acetylene black as a conductor with 90 parts by weight of an LiCo02 powder followed by the addition of N,N-dimethylformamide to form a paste. This paste was applied to an aluminum foil and allowed to dry to obtain the test positive electrode. Lithium metal was used for the negative electrode. A
glass fiber filter as a separator was impregnated with the electrolytic solution, thereby assembling the cell.
Next, a constant current charging and dischar grog test was conducted as described below. The current density was 0.35 mA/cm'' for both charging and discharging, while charging was performed until 4.2 V and discharging until 3.0 V (vs. Li/Li+). As a result, the initial discharge capacity was 125 mAh/g. Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 88°/ of the initial capacity.
In a glove box having an atmosphere of a dew point of -50°C, 10Øg of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)~COOH) were dissolved in 20 ml of dimethyl carbonate. Next, a lithium methoxide/methanol solution containing~3.6 g of lithium methoxide (LiOCHs) was slowly added to this solution. The dimethyl carbonate and methanol were removed under a reduced pressure condition of 60°C and 1 torr, thereby obtaining LiOC(CFs)~COOLi as a product. After dissolving this compound in acetonitrile, 4.4 g of LiBF4 were added to this solution, followed by heating to 60°C and allowing to react for 10 hours. After filtering the LiF precipitate that formed during the reaction, the dimethyl carbonate was removed under a reduced pressure condition of 80°C and 1 torr, thereby obtaining L2.5 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiBFz(OC(CFs)2C00) having the following formula.
~~3 ~1.~ Fv$ fl CF3 F O
The N1~IR spectral data of the product is shown below.
19F-N11~IR (hexaf7:uorobenzene standard, solvent: CDsCN) 15.3 ppm (2F, s) 88.2 ppm (6F, s) mp,.lrn,IR (B(OCHs)s standard, solvent: CDsCN) .14.1 ppm (t, J = 4 Hz) Next, the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3 followed by measurement of ion conductivity by the alternating current bipolar-type cell. As a result, the ion conductivity was 8.2 mS/cm.
A charging and discharging test of an actual cell was conducted using the above-mentioned electrolytic solution. The test cell (half cell) was prepared in the manner described below.
parts by weight of polyvinylidene fluoride (PVDF) as a binder 10 were mixed with 90 parts by weight of natural graphite powder followed by the addition of N,N-dimethylformamide to prepare a slurry. This slurry was applied to a nickel mesh and allowed to dry for 12 hours at 150°C to prepare a test negative electrode.
Lithium metal was used for a counter electrode. A glass fiber filter as a separator was impregnated with the above-mentioned electrolytic solution, thereby assembling the half cell.
A constant current charging and discharging test was then conducted under the conditions indicated below. The current density was 0.3 mA/cm2 for both charging and discharging, while charging was performed until 0.0 V and discharging until 1.5 V (vs.
Li/Li+). As a result, the initial discharge capacity was 320 mAh/g.
Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 95% of the initial capacity.
In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of trifluorolactic acid (HOCH(CFa)COOH) were dissolved in 20 ml of dimethyl carbonate. Next, 4.9 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 10.4 g of a white solid as a product. This product was identified by NNIR spectrum and elementary analysis as being LiB(OCH(CFs)C00)~.
F3C fl\ ~~ ~F3 s ~,i+ ~B~
~J O \~
The NMR spectral data of the product is shown below.
lsF.NMR (hexafluorobenzene standard, solvent: CD3CN) 8?.12 ppm (3F, d, J = 8 Hz) 8?.18 ppm (3F, d, J = 8 Hz) 87.32 ppm (3F, d, J = 8 Hz) Since the raw material, trifluorolactic acid, is a racemic modification having two types of optical isomers, three types of 1 s peaks were observed in 19F-NMR due to three combinations of (R,R), (S,S) and (R,S).
1H.NMR
4.57 ppm (1H, q, J = 8 Hz) iiB-NMR (B(OCHa)s standard, solvent: CDsCN) -8.03 ppm (s) Next, the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3 followed by measurement of ion conductivity by the alternating current bipolar.type cell. As a result, the ion conductivity was 6.3 mS/cm.
A charging and discharging test of an actual cell was conducted using the above-mentioned electrolyte. A test cell (half cell) was prepared in the manner described below. 10 parts by weight of polyvinylidene fluoride (PV-DF) as a binder were mixed with 90 parts by weight of natural graphite powder followed by the addition of N,N-dimethylformamide to prepare a slurry. This slurry was applied to a nickel mesh and allowed to dry for 12 hours at 150°C to prepare a test negative electrode. Lithium metal was used for a counter electrode. A glass fiber filter as a separator was impregnated with the above-mentioned electrolytic solution, thereby assembling the half cell.
A constant current charging and discharging test was then conducted under the conditions indicated below. The current density was 0.3 mA/em'' for both charging and discharging, while charging was performed until 0.0 V and discharging until 1.5 V (vs.
LilLi+). As a result, the initial discharge capacity was 340 m_Ahlg.
IO Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 94% of the initial capacity.
In a glove box having an atmosphere of a dew point of -50°C, 4.2 g of 4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butyric acid (HOC(CFs)2CH2COOH) were dissolved in 20 ml of dimethyl carbonate. Next, 1.3 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution:' After this addition, the solution was heated to 60°G and allowed to react for 10 hours. Dimethyl carbonate was removed ~rom the resulting reaction solution under a reduced pressure condition of 120°C and 1 torr, thereby obtaining 4.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OC(CFs)zCHaCOO)z.
F C CF3 CF~F
3 ~ 3 Lip H ~B H
H ~~ v _H
O
The N1~1R spectral data of the product is shown below.
'-~F-u~i~.~IR (hexafluorobenzene standard, solvent: CDsCN) 85.0 ppm (12F, s) 1H-i~ll~IR
2.86 ppm (2H, d, J = 16 Hz) 2.75 ppm (2H, d, J = 16 Hz) Next, the obtained compound was dissolved in a mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 0.8 mol/dm3 followed by measurement of ion conductivity by the alternating current bipolar-type cell. As a result, the ion conductivity was 1.9 mS/cm.
A charging and discharging test of an actual cell was conducted using the above-mentioned electrolyte. A test cell (half cell) was prepared in the manner described below. 10 parts by weight of polyvinylidene fluoride (PVDF) as a binder were mixed with 90 parts by weight of natural graphite powder followed by the addition of N,N-dimethylformamide to prepare a slurry. This slurry was applied to a nickel mesh and allowed to dry for 12 hours at 150°C to prepare a test negative electrode. Lithium metal was used for a counter electrode. A glass fiber filter as a separator was impregnated with the above-mentioned electrolytic solution, thereby assembling the half cell.
A constant current charging and discharging test was tr~en conducted under the conditions indicated below. The current density was 0.3 mA/cm2 for both charging and discharging, while charging was performed until 0.0 V and discharging until 1.5 V (vs.
Li/Li+). As a result, the initial discharge capacity was 320 mAh/g.
Although charging and discharging were repeated 20 times, results were obtained in which the capacity of the 20th cycle was 97% of the initial capacity.
LiPFs was dissolved in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:l) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3. Next, this electrolytic solution was placed in a fluororesin container, and, when subjected to a heat resistance test by storing for 1 month at 100°C, the electrolytic solution changed to have a yellow color.
When water was added to this electrolytic solution prior to conducting the heat resistance test, various hydrolysis products were found by NMR. Substances detected as hydrolysis products included hydrogen fluoride and phosphorus oxychloride.
LiN(CFaS02)2 was dissolved in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC = 1:1) to prepare an electrolytic solution having an electrolyte concentration of 1 mol/dm3. Next, a corrosion test of an aluminum separator was conducted using this electrolyte. A
beaker type cell was used for the test cell, using aluminum for the working electrode, and lithium metal for the counter electrode and 1 S reference electrode. When the working electrode was held at 5 V
(Li/Li+), current flowed and the current value increased with time.
Following testing, when the surface of the working electrode was observed by SEM, severe corrosion pits were found in the aluminum surface.
Claims (16)
1. An electrolyte for an electrochemical device, said electrolyte comprising an ionic metal complex represented by the general formula (1):
wherein M is a transition metal selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, opium ion or proton;
a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl groups R4 represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
wherein M is a transition metal selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, opium ion or proton;
a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl groups R4 represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
2. An electrolyte according to claim 1, wherein said M is an element selected from the group consisting of A1, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf and Sb.
3. An electrolyte according to claim 2, wherein said M is an element selected from the group consisting of A1, B and P.
4. An electrolyte according to claim 1, wherein said A a+
is a lithium ion, quaternary ammonium ion or proton.
is a lithium ion, quaternary ammonium ion or proton.
5. An electrolyte according to claim 1, wherein at least one of said R1 and said R2 is a fluorinated alkyl group.
6. An electrolyte according to claim 5, wherein said fluorinated alkyl group is a trifluoromethyl group.
7. An electrolyte according to claim 1, wherein said R3 is such that a chelate ring containing said M in the general formula (1) is a closed loop of bonded atoms of 5-in number.
8. An electrolyte according to claim 1, wherein said R7 is a C1-C10 fluorinated alkyl group.
9. An electrolyte according to claim 1, wherein said M of the general formula (1) is a transition metal selected from the group consisting Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Ac, Th, Pa, U, Np, Pu, Am, Cm, B k, Cf, Es, Fm, Md, No, and Lr.
10. An electrolyte according to claim 1, wherein said M of the general formula (1) is a transition metal selected from the group consisting Sc, Ti, V, Cr, Mn, Cu, Y, Zr, Nb, Mo, Tc, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Au, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr.
11. An ion conductor for an electrochemical device, said ion conductor comprising:
an electrolyte according to claim 1; and a member selected from the group consisting of a nonaqueous solvent that is an aprotic solvent, a polymer that is an aprotic polymer and a mixture thereof, said member dissolving therein said electrolyte.
an electrolyte according to claim 1; and a member selected from the group consisting of a nonaqueous solvent that is an aprotic solvent, a polymer that is an aprotic polymer and a mixture thereof, said member dissolving therein said electrolyte.
12. An ion conductor according to claim 11, which has a concentration of said electrolyte within a range of from 0.1 mol/dm3 to a saturated concentration.
13. An ion conductor according to claim 12, wherein said concentration is within a range of from 0.5 mol/dm3 to 1.5 mol/dm3.
14. An electrochemical device comprising:
(a) first and second electrodes; and (b) an ion conductor receiving therein said first and second electrodes, said ion conductor comprising:
(1) an electrolyte according to claim 1; and (2) a member selected from the group consisting of a nonaqueous solvent that is an aprotic solvent, a polymer that is an aprotic polymer and a mixture thereof, said member dissolving therein said electrolyte.
(a) first and second electrodes; and (b) an ion conductor receiving therein said first and second electrodes, said ion conductor comprising:
(1) an electrolyte according to claim 1; and (2) a member selected from the group consisting of a nonaqueous solvent that is an aprotic solvent, a polymer that is an aprotic polymer and a mixture thereof, said member dissolving therein said electrolyte.
15. An electrochemical device according to claim 14, which is a cell or an electrical double-layer capacitor.
16. An electrochemical device according to claim 15, wherein said cell is a lithium cell or a lithium ion cell.
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| CN119092807A (en) * | 2024-08-27 | 2024-12-06 | 浙江山高新能源有限公司 | A method for preparing all-solid-state lithium metal battery composite electrolyte using PVB additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3539614A (en) * | 1966-02-07 | 1970-11-10 | Sprague Electric Co | Quaternary ammonium diorganoboron compounds |
| GB2143228A (en) * | 1983-07-13 | 1985-02-06 | Standard Telephones Cables Ltd | Electrolytes |
| DE4316104A1 (en) * | 1993-05-13 | 1994-11-17 | Manfred Wuehr | Electrolyte for use in a galvanic cell |
| JP2000173343A (en) * | 1998-12-02 | 2000-06-23 | Japan Carlit Co Ltd:The | Ion conductive polymer electrolyte |
| JP3824465B2 (en) * | 1999-08-02 | 2006-09-20 | セントラル硝子株式会社 | Synthesis of ionic complexes |
-
2000
- 2000-03-13 JP JP2000069202A patent/JP3498905B2/en not_active Expired - Fee Related
- 2000-07-17 TW TW089114252A patent/TW471193B/en not_active IP Right Cessation
- 2000-07-19 DE DE60044964T patent/DE60044964D1/en not_active Expired - Lifetime
- 2000-07-19 EP EP00115579A patent/EP1075036B1/en not_active Expired - Lifetime
- 2000-07-25 US US09/625,353 patent/US6485868B1/en not_active Expired - Lifetime
- 2000-07-31 CA CA002314740A patent/CA2314740C/en not_active Expired - Fee Related
- 2000-08-01 KR KR1020000044552A patent/KR100361273B1/en not_active Expired - Fee Related
- 2000-08-02 CN CNB001224670A patent/CN1173429C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1173429C (en) | 2004-10-27 |
| JP2001110450A (en) | 2001-04-20 |
| EP1075036A2 (en) | 2001-02-07 |
| CN1282989A (en) | 2001-02-07 |
| EP1075036B1 (en) | 2010-09-15 |
| JP3498905B2 (en) | 2004-02-23 |
| CA2314740A1 (en) | 2001-02-02 |
| EP1075036A3 (en) | 2005-08-24 |
| TW471193B (en) | 2002-01-01 |
| DE60044964D1 (en) | 2010-10-28 |
| KR100361273B1 (en) | 2002-11-18 |
| US6485868B1 (en) | 2002-11-26 |
| KR20010067049A (en) | 2001-07-12 |
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