CN107394271B - 金属离子电池及其制备方法 - Google Patents
金属离子电池及其制备方法 Download PDFInfo
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- CN107394271B CN107394271B CN201710345622.1A CN201710345622A CN107394271B CN 107394271 B CN107394271 B CN 107394271B CN 201710345622 A CN201710345622 A CN 201710345622A CN 107394271 B CN107394271 B CN 107394271B
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- Prior art keywords
- halide
- metal
- ion battery
- metal ion
- anode
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- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 aluminum halide Chemical class 0.000 claims abstract description 121
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 67
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 65
- 150000005309 metal halides Chemical class 0.000 claims abstract description 65
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- 239000002608 ionic liquid Substances 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 65
- 239000011149 active material Substances 0.000 claims description 49
- 229910002804 graphite Inorganic materials 0.000 claims description 44
- 239000010439 graphite Substances 0.000 claims description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 34
- 230000002687 intercalation Effects 0.000 claims description 34
- 238000009830 intercalation Methods 0.000 claims description 34
- 230000026030 halogenation Effects 0.000 claims description 30
- 238000005658 halogenation reaction Methods 0.000 claims description 30
- 239000004411 aluminium Substances 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 22
- 238000005660 chlorination reaction Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000011135 tin Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229960004266 acetylcholine chloride Drugs 0.000 claims description 2
- JUGOREOARAHOCO-UHFFFAOYSA-M acetylcholine chloride Chemical compound [Cl-].CC(=O)OCC[N+](C)(C)C JUGOREOARAHOCO-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- SCQCUWMFZHLVCO-UHFFFAOYSA-N N1N=CC=C1.[F] Chemical class N1N=CC=C1.[F] SCQCUWMFZHLVCO-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 210000000232 gallbladder Anatomy 0.000 claims 1
- 238000002955 isolation Methods 0.000 abstract description 19
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 95
- 239000000460 chlorine Substances 0.000 description 20
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
- 229920000049 Carbon (fiber) Polymers 0.000 description 12
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 12
- 239000004917 carbon fiber Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 10
- 239000011565 manganese chloride Substances 0.000 description 10
- 239000011592 zinc chloride Substances 0.000 description 10
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 9
- 239000002985 plastic film Substances 0.000 description 9
- 229920006255 plastic film Polymers 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- 239000005030 aluminium foil Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 5
- 235000002867 manganese chloride Nutrition 0.000 description 5
- 229940099607 manganese chloride Drugs 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KEDNSMBVYXSBFC-UHFFFAOYSA-N 6-bromo-2-chloroquinoline-4-carbonyl chloride Chemical compound C1=C(Br)C=C2C(C(=O)Cl)=CC(Cl)=NC2=C1 KEDNSMBVYXSBFC-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- IQMOJMVNWCBXPB-UHFFFAOYSA-N [H]C([H])C([H])([H])[Cl]Cl Chemical compound [H]C([H])C([H])([H])[Cl]Cl IQMOJMVNWCBXPB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001349 alkyl fluorides Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- UZDWIWGMKWZEPE-UHFFFAOYSA-K chromium(iii) bromide Chemical compound [Cr+3].[Br-].[Br-].[Br-] UZDWIWGMKWZEPE-UHFFFAOYSA-K 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940016409 methylsulfonylmethane Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LNDHQUDDOUZKQV-UHFFFAOYSA-J molybdenum tetrafluoride Chemical compound F[Mo](F)(F)F LNDHQUDDOUZKQV-UHFFFAOYSA-J 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- YPFBRNLUIFQCQL-UHFFFAOYSA-K tribromomolybdenum Chemical compound Br[Mo](Br)Br YPFBRNLUIFQCQL-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 229940105965 yttrium bromide Drugs 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
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Abstract
本发明提供一种金属离子电池及其制备方法。该金属离子电池包含:一正极;一隔离层;一负极,其中该负极以隔离层与该正极相隔;以及,一电解质,设置于该正极与该负极之间,其中该电解质包含离子液体、卤化铝、及金属卤化物,其中该金属卤化物包含卤化银、卤化铜、卤化钴、卤化铁、卤化锌、卤化铟、卤化镉、卤化镍、卤化锡、卤化铬、卤化镧、卤化钇、卤化钛、卤化锰、卤化钼、或上述的组合。本发明的金属离子电池可增加金属离子电池放电电压平台数及总发电量。
Description
技术领域
本发明关于一种储能元件及其制备方法,更特别关于一种金属离子电池及其制备方法。
背景技术
铝在地球上蕴藏量非常丰富,以铝作为材料的电子装置具有较低的成本。在储能元件的应用方面,铝在电化学充放电的过程中电子转移数目可达到三,因此可提供较高的能量储存容量。再者,由于铝具有低可燃性及电子氧化还原性质,大幅提升金属离子电池在使用上的安全性。
然而,传统金属离子电池,面临低电池放电电压、无放电电压平台(dischargevoltage plateaus)的电容行为、及低电池容量等问题。因此,业界需要一种新的金属离子电池以解决上述问题。
发明内容
本发明的目的在于提供一种能够基本上克服现有技术存在的种种问题的金属离子电池,及其制备方法。
根据本发明实施例,本发明提供一种储能元件,例如为金属离子电池。该金属离子电池包含:一正极;一隔离层;一负极,其中该负极以隔离层与该正极相隔;以及一电解质,设置于该正极与该负极之间,其中该电解质包含离子液体、卤化铝、及金属卤化物,其中金属卤化物包含卤化银、卤化铜、卤化钴、卤化铁、卤化锌、卤化铟、卤化镉、卤化镍、卤化锡、卤化铬、卤化镧、卤化钇、卤化钛、卤化锰、卤化钼、或上述的组合。
根据本发明实施例,本发明提供一种金属离子电池的制备方法。该方法包含:提供一正极及一负极;提供一隔离层以分隔该正极及该负极;以及,提供一电解质,使该电解质配置于该正极及该负极之间,其中该电解质包含离子液体、卤化铝、及金属卤化物,其中该金属卤化物包含卤化银、卤化铜、卤化钴、卤化铁、卤化锌、卤化铟、卤化镉、卤化镍、卤化锡、卤化铬、卤化镧、卤化钇、卤化钛、卤化锰、卤化钼、或上述的组合。
与现有技术相比,本发明的金属离子电池的优点在于增加了金属离子电池放电电压平台数及总发电量。
附图说明
图1是本发明一实施例所述金属离子电池的示意图;以及
图2-12是显示本发明实施例及比较例所述金属离子电池在其充放电过程中,电压与时间的关系;
其中,符号说明:
10 正极; 11 集电层;
12 负极; 13 活性材料;
14 隔离层; 20 电解质;
100 金属离子电池。
具体实施方式
以下针对本发明的金属离子电池作详细说明。应了解的是,以下的叙述提供许多不同的实施例或例子,用以实施本发明的不同样态。以下所述特定的元件及排列方式仅为简单描述本发明。当然,这些仅用以举例而非本发明的限定。此外,在不同实施例中可能使用重复的标号或标示。这些重复仅为了简单清楚地叙述本发明,不代表所讨论的不同实施例及/或结构之间具有任何关连性。且在图式中,实施例的形状、数量、或是厚度可扩大,并以简化或是方便标示。再者,图式中各元件的部分将以分别描述说明之,值得注意的是,图中未绘示或描述的元件,为所属技术领域中具有通常知识者所知的形式,此外,特定的实施例仅为揭示本发明使用的特定方式,其并非用以限定本发明。
本发明提供一种金属离子电池。根据本发明实施例,该金属离子电池的电解质包含可作为刘易斯酸的金属卤化物及卤化铝。因此,在金属离子电池充放电时,该金属卤化物可形成离子尺寸不同于卤化铝酸根的卤化金属酸根,使离子液体系统在插层(intercalation)与去插层(deintercalation)反应的过程中维持可逆。此外,根据本发明某些实施例,例如:该卤化金属酸根可与氯化铝酸根相同具有四面体形(tetrahedralstructure)但具有比氯化铝酸根具有更小的离子尺寸、或为三角型构形(trigonalstructure),因此可更易于与活性材料(例如:石墨)进行插层反应,或进一步协助卤化铝酸根与活性材料进行插层反应,增加金属离子电池放电电压平台数及总发电量。
请参照图1,其为本发明一实施例所述金属离子电池100的示意图,该金属离子电池100可包含一正极10、一负极12、及一隔离层14,其中该隔离层14可设置于该正极10及该负极12之间,以使得该负极以该隔离层14与该正极相隔,避免该正极10与该负极12直接接触。该金属离子电池100包含一电解质20设置于该金属离子电池100内,并位于该正极与该负极之间,使得电解质20与该正极10及负极12接触。该金属离子电池100可为充电式的二次电池,但本发明亦涵盖一次电池。
根据本发明实施例,该正极10可包含一集电层11及一活性材料13设置于该集电层11之上。根据本发明实施例,该正极10亦可由该集电层11及活性材料13所构成。根据本发明实施例,该集电层11可为导电性碳基材,例如碳布、碳毡、或碳纸。举例来说,该导电性碳基材可具有片电阻介于约1mΩ·cm2至6mΩ·cm2之间、以及含碳量大于65wt%。该活性材料13包括层状活性材料或该层状活性材料的团聚物。根据本发明实施例,该活性材料13可为插层碳材,例如:石墨(包含天然石墨、人工石墨、中间相碳微球、热解石墨、发泡石墨、鳞片石墨、或膨胀石墨)、石墨烯、纳米碳管或上述材料的组合。根据本发明实施例,该活性材料13可为层状双氢氧化物(layered double hydroxide)、层状氧化物、层状硫族化合物(layered chalcogenide)或上述材料的组合。该活性材料13可具有一孔隙度介于约0.05至0.95之间,例如介于约0.3至0.9之间。此外,根据本发明实施例,该活性材料13可直接成长于该集电层11之上(即两者之间没有任何介质),或是利用粘着剂将该活性材料13固定于该集电层11上。
根据本发明实施例,该隔离层14的材质可为玻璃纤维、聚乙烯(polyethylene、PE)、聚丙烯(Polypropylene、PP)、无纺布、木质纤维、聚醚砜树脂(Poly(ether sulfones)、PES)、陶瓷纤维等或上述的组合。
根据本发明实施例,该负极12可为一金属或其合金、一集电层、或其组合。举例来说,该负极12可由该金属或其合金所构成。此外,该负极12亦可为集电层。再者,该负极12亦可由集电层及金属或其合金(设置于该集电层)所构成。该负极可包含银、铜、铁、钴、铝、锌、铟、镉、镍、锡、铬、镧、钇、钛、锰、钼、钨、钽或包含上述金属的合金。为提升金属离子电池总发电量及避免金属离子电池在使用过程中发生自燃的状况,该负极非为碱金族(例如:Li)或碱土族的金属。该集电层可为导电性碳基材,例如碳布、碳毡、或碳纸。举例来说,该导电性碳基材可具有片电阻介于约1mΩ·cm2至6mΩ·cm2之间、以及含碳量大于65wt%。
根据本发明实施例,该电解质20可包含一离子液体、卤化铝、及金属卤化物。该金属卤化物与卤化铝的总摩尔数与该离子液体的摩尔比大于或等于约1.1、或大于或等于约1.2,例如介于1.1:1至2.1:1之间、或例如约1.1、约1.3、约1.5、或约1.8。若低于1.1,则倾向路易斯中性电解液,插层活性物质少,不利插层反应进行。若大于2.1则在室温区间不易使金属卤化物及卤化铝与离子液体形成液相互溶。该离子液体具有一熔点低于100℃,例如可为室温离子液体(room temperature ion liquid、RTIL)。举例来说,该离子液体可包含尿素(urea)、N-二甲基脲(N-methylurea)、氯化胆碱(choline chloride)、乙酰氯化胆碱(ethylchlorine chloride)、碱金族卤化物(alkali halide)、二甲基亚砜(dimethylsulfoxide)、二甲基砜(methylsulfonylmethane)、烷基咪唑鎓盐(alkylimidazoliumsalt)、烷基吡啶鎓盐(alkylpyridinium salt)、烷基氟吡唑鎓盐(alkylfluoropyrazoliumsalt)、烷基三唑鎓盐(alkyltriazolium salt)、芳烷铵盐(aralkylammonium salt)、烷基烷氧基铵盐(alkylalkoxyammonium salt)、芳烷鏻盐(aralkylphosphonium salt)、芳烷锍盐(aralkylsulfonium salt)、及其混合物。根据本发明实施例,该电解质可更包含添加剂,以提高电导率且降低粘度。
该金属卤化物包含可作为刘易斯酸的金属氟化物、金属氯化物、或金属溴化物,使电解质系统维持可逆。此外,为提升金属离子电池总发电量及避免金属离子电池在使用过程中发生自燃的状况,该金属卤化物非为碱金族卤化物或碱土族卤化物。该金属卤化物可包含卤化银(例如氟化银、氯化银、或溴化银)、卤化铜(例如氟化铜、氯化铜、或溴化铜)、卤化铁(例如氟化铁、氯化铁、或溴化铁)、卤化钴(例如氟化钴、氯化钴、或溴化钴)、卤化锌(例如氟化锌、氯化锌、或溴化锌)、卤化铟(例如氟化铟、氯化铟、或溴化铟)、卤化镉(例如氟化镉、氯化镉、或溴化镉)、卤化镍(例如氟化镍、氯化镍、或溴化镍)、卤化锡(例如氟化锡、氯化锡、或溴化锡)、卤化铬(例如氟化铬、氯化铬、或溴化铬)、卤化镧(例如氟化镧、氯化镧、或溴化镧)、卤化钇(例如氟化钇、氯化银、或溴化钇)、卤化钛(例如氟化钛、氯化钛、或溴化钛)、卤化锰(例如氟化锰、氯化锰、或溴化锰)、卤化钼(例如氟化钼、氯化钼、或溴化钼)、或上述的组合。在此,本发明所述的金属卤化物可为带不同正电价数金属的卤化物。举例来说,本发明所述的氯化铜可为CuCl、CuCl2、或其组合;氯化铁可为FeCl2、FeCl3、或其组合;氯化钴可为CoCl3、CoCl2、或其组合;氯化铬可为CrCl2、CrCl3、或其组合;氯化锌可为ZnCl2、ZnCl4、或其组合;氯化锡可为SnCl2、SnCl4、或其组合;以及,氯化锰可为MnCl2、MnCl3、或其组合。根据本发明实施例,该金属卤化物不包含卤化铝,因此在金属离子电池充放电时,该金属卤化物可形成离子尺寸不同于卤化铝酸根的卤化金属酸根。
本发明所述的电解质具有卤化铝,例如:氟化铝、氯化铝、或溴化铝,以在金属离子电池进行充放电时,使该电解质内产生不同种类的卤化金属酸根及卤化铝酸根。根据本发明某些实施例,该金属卤化物与该卤化铝的摩尔数比是1:100至1:1。若金属卤化物与该卤化铝的摩尔数比过低,则该金属卤化物插层所贡献电量不足,电池会维持原来单纯卤化铝的插层行为。若金属卤化物与该卤化铝的摩尔数比过高,则该金属卤化物不易与卤化铝于离子液体中互溶,电解液中会有沉积物析出。
由于本发明所述的金属卤化物与活性材料(例如:石墨)插层后的放电平台,小于氯化铝与活性材料(例如:石墨)之间的放电平台(约1.8V),显示本发明所述的金属卤化物在金属离子电池进行充放电时,更倾向与石墨电极进行插层反应。值得注意的是,该负极所包含的金属可与该金属卤化物的金属相同或不相同。
根据本发明某些实施例,当本发明所述的金属卤化物为卤化铜、卤化铁、卤化钴、卤化铬、卤化锌、卤化锡、或卤化锰(例如氯化铜、氯化钴、氯化铁、氯化铬、氯化锌、氯化锡、或氯化锰)时,可在金属离子电池充放电时,产生具有带正二价金属的卤化金属酸根(例如氯化金属酸根)。由于具有带正二价金属的卤化金属酸根可具有三角型构形(trigonalconfiguration),因此较具有四面体构形(tetrahedral configuration)的氯化铝酸根(AlCl4 -)更容易与活性材料(例如:石墨)进行插层反应,或进一步协助氯化铝酸根与活性材料进行插层反应,提升金属离子电池放电电压及总发电量。另一方面,根据本发明某些实施例,当本发明所述的金属卤化物为FeCl2时,可在金属离子电池充放电时,产生离子尺寸较氯化铝酸根(离子尺寸为)小的卤化金属酸根(例如:FeCl3 -,(平面三角构型离子高度为))。如此一来,该具有较小离子尺寸的金属卤化物更容易与活性材料(例如:石墨)进行插层反应,或进一步协助氯化铝酸根与活性材料进行插层反应,提升金属离子电池放电电压及总发电量。根据本发明某些实施例,由本发明所述的金属卤氯化物在金属离子电池充放电后所形成的卤化金属酸根,其离子尺寸可小于约
根据本发明实施例,本发明亦提供一种金属离子电池的制备方法,以制备上述金属离子电池。该方法,包含:提供一正极及一负极;提供一隔离层以分隔该正极及该负极;以及,提供一电解质,使该电解质配置于该正极及该负极之间,其中该电解质包含一离子液体、卤化铝及一金属卤化物,其中该金属卤化物是卤化银、卤化铜、卤化铁、卤化钴、卤化锌、卤化铟、卤化镉、卤化镍、卤化锡、卤化铬、卤化镧、卤化钇、卤化钛、卤化锰、卤化钼、或上述的组合。
根据本发明实施例,该正极材料可为利用电化学或气相法(vapor phaseintercalation)所预插层的材料。
根据本发明某些实施例,当该电解质包含离子液体、金属卤化物、及卤化铝时,该金属卤化物及卤化铝可同时加入离子液体中并进行混合得到该电解质,接着在将该电解质配置于该正极及该负极之间。
根据本发明某些实施例,当该电解质包含离子液体、金属卤化物、及卤化铝时,可先将一部份离子液体与金属卤化物混合,并配置于该正极及该负极之间。接着,在该正极及该负极间施加一电位差,使该金属卤化物与该离子液体反应形成一卤化金属酸根,且该卤化金属酸根对该正极的活性材料进行插层反应。在施加该电位差之后,在将离子液体与卤化铝混合,并配置于该正极及该负极之间。在此,由于由金属卤化物所形成的卤化金属酸根会先与活性材料进行插层反应,作为一已预插嵌金属卤化物的正极材料,可有助后续制作电池时卤化铝酸根与活性材料进行插层反应,增加金属离子电池放电电压平台数及总发电量。
根据本发明其他实施例,当该电解质包含离子液体、金属卤化物、及卤化铝时,可先将一部份离子液体与卤化铝混合,并配置于该正极及该负极之间。接着,在该正极及该负极间施加一电位差,使该卤化铝与该离子液体反应形成一卤化铝酸根,且该卤化铝酸根对该正极的活性材料进行插层反应。在施加该电位差之后,在将离子液体与金属卤化物混合,并配置于该正极及该负极之间。在此,由于由卤化铝所形成的卤化铝酸根会先与活性材料进行插层反应,作为一已预插嵌金属卤化物的正极材料,可有协助后续制作电池时卤化金属酸根与活性材料进行插层反应,提升金属离子电池放电电压及总发电量。
根据本发明实施例,预插层的正极的制备步骤包含:对该金属卤化物加热,产生一金属卤化物气体;以及,利用该金属卤化物气体对该正极进行预插嵌。
根据本发明实施例,预插层的正极的制备步骤包含:对该卤化铝加热,产生一卤化铝气体;以及,利用该卤化铝气体对该正极进行预插嵌。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂,下文特举数实施例及比较实施例,作详细说明如下:
实施例1:
提供一厚度为0.025mm的铝箔,对其进行裁切,得到铝电极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(53mg))。接着,按照铝电极(作为负极)、隔离膜(作为隔离层)、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化亚铁(FeCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及FeCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且FeCl2与AlCl3的摩尔比约为1:13),得到金属离子电池(1)。
接着,使用NEWARE电池分析仪量测实施例1所得的金属离子电池(1)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.6V,放电截止电压为0.3V),可得知其最大比容量为159mAh/g,如表1所示。图2是绘示为金属离子电池(1)在充放电过程中,电压与时间的关系图。由图2可知,金属离子电池(1)在2.0V至2.6V显现出多个充电电压平台,且在2.2V至1.0V显现出多个放电电压平台。此外,金属离子电池(1)在1000mA/g电流下进行充放电测试时,充放电循环次数可达400次以上。
再现性实验
实施例2:
提供一厚度为0.025mm的铝箔,对其进行裁切,得到铝电极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(57mg))。接着,按照铝电极(作为负极)、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化亚铁(FeCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及FeCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且FeCl2与AlCl3的摩尔比约为1:13),得到金属离子电池(2)。
接着,使用NEWARE电池分析仪量测实施例2所得的金属离子电池(2)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.6V,放电截止电压为0.2V),可得知其最大比容量为173.3mAh/g,如图3与表1所示。
实施例3:
依实施例1所述方式进行,除了将FeCl2与AlCl3的摩尔比由1:13改为1:27,并将膨胀石墨由53mg降低至42mg,得到金属离子电池(3)。
接着,使用NEWARE电池分析仪量测实施例3所得的金属离子电池(3)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.7V,放电截止电压为0.3V),可得知其最大比容量为176mAh/g,如图4与如表1所示。
实施例4:
依实施例1所述方式进行,除了将活性材质为膨胀石墨由57mg增加至63mg,并将FeCl2与AlCl3的摩尔比由1:13改为3:11,得到金属离子电池(4)。
接着,使用NEWARE电池分析仪量测实施例4所得的金属离子电池(4)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.8V,放电截止电压为0.3V),可得知其最大比容量为169mAh/g,如图5与表1所示。
比较例1:
提供一厚度为0.025mm的铝箔,对其进行裁切,得到铝电极。提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(59mg))。接着,按照铝电极(作为负极)、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3与[EMIm]Cl的比约为1.4:1,得到金属离子电池(5)。
接着,使用NEWARE电池分析仪量测比较例1所得的金属离子电池(5)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.45V,放电截止电压为1.5V),可得知其最大比容量为72.1mAh/g,如图6与表1所示。
表1
金属氯化物 | 最大比容量(mAh/g) | |
金属离子电池(1) | AlCl<sub>3</sub>/FeCl<sub>2</sub>(13:1) | 161 |
金属离子电池(2) | AlCl<sub>3</sub>/FeCl<sub>2</sub>(13:1) | 173.3 |
金属离子电池(3) | AlCl<sub>3</sub>/FeCl<sub>2</sub>(27:1) | 176 |
金属离子电池(4) | AlCl<sub>3</sub>/FeCl<sub>2</sub>(11:3) | 169 |
金属离子电池(5) | AlCl<sub>3</sub> | 72.1 |
由表1可知,与电解质仅包含氯化铝的金属离子电池(5)相比,当金属离子电池的电解质进一步包含氯化铝及氯化铁时,所得的金属离子电池的比容量可提升至2.4倍,且显现出多个充放电电压平台。
实施例5:
提供一厚度为0.025mm的铝箔,对其进行裁切,得到铝电极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(77mg))。接着,按照铝电极(作为负极)、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化锌(ZnCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及ZnCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且ZnCl2与AlCl3的摩尔比约为1:13),得到金属离子电池(6)。
接着,使用NEWARE电池分析仪量测实施例5所得的金属离子电池(6)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.7V,放电截止电压为0.2V),可得知其最大比容量为106mAh/g,如表2所示。图7是绘示为金属离子电池(6)在充放电过程中,电压与时间的关系图。由图7可知,金属离子电池(6)在1.9V至2.7V显现出多个充电电压平台,且在2.3V至0.2V显现出多个放电电压平台。
实施例6:
提供一厚度为0.025mm的铝箔,对其进行裁切,得到铝电极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(66mg))。接着,按照铝电极(作为负极)、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化铜(CuCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及CuCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且CuCl2与AlCl3的摩尔比约为1:13),得到金属离子电池(7)。
接着,使用NEWARE电池分析仪量测实施例6所得的金属离子电池(7)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.7V,放电截止电压为0.25V),可得知其最大比容量为112mAh/g,如表2所示。图8是绘示为金属离子电池(7)在充放电过程中,电压与时间的关系图。由图8可知,金属离子电池(7)在1.9V至2.7V显现出多个充电电压平台,且在2.3V至0.25V显现出多个放电电压平台。
实施例7:
提供一厚度为0.025mm的铝箔,对其进行裁切,得到铝电极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(42mg))。接着,按照铝电极(作为负极)、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化锰(MnCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及MnCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且MnCl2与AlCl3的摩尔比约为1:13),得到金属离子电池(8)。
接着,使用NEWARE电池分析仪量测实施例7所得的金属离子电池(8)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.7V,放电截止电压为0.3V),可得知其最大比容量为162mAh/g,如图9与如表2所示。
表2
金属氯化物 | 最大比容量(mAh/g) | |
金属离子电池(5) | AlCl<sub>3</sub> | 72 |
金属离子电池(6) | AlCl<sub>3</sub>/ZnCl<sub>2</sub>(13:1) | 106 |
金属离子电池(7) | AlCl<sub>3</sub>/CuCl<sub>2</sub>(13:1) | 112 |
金属离子电池(8) | AlCl<sub>3</sub>/MnCl<sub>2</sub>(13:1) | 162 |
由表2可知,与电解质仅包含氯化铝的金属离子电池(5)相比,当金属离子电池的电解质进一步包含氯化铝及氯化锌(或氯化锰、氯化铜)时,所得的金属离子电池的比容量可提升1.38倍至2.25倍,且显现出多个充放电电压平台。
实施例8:
提供一厚度为0.24mm的碳纤维纸(由台湾碳能制造及贩卖),对其进行裁切,得到负极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为天然石墨(128mg))。接着,按照负极、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化亚铁(FeCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及FeCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且FeCl2与AlCl3的摩尔比约为1:13),得到金属离子电池(9)。
接着,使用NEWARE电池分析仪量测实施例8所得的金属离子电池(9)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为2.7V,放电截止电压为0.2V),可得知其最大比容量为96mAh/g,如图10与如表3所示。
实施例9:
提供一厚度为0.1mm的不锈钢(由新日铁制造及贩卖,型号YUS190,成份主要是铁及铬),对其进行裁切,得到不锈钢电极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(62mg))。接着,按照不锈钢电极(作为负极)、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化铁(FeCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及FeCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且FeCl3与AlCl3的摩尔比约为1:13),得到金属离子电池(10)。
接着,使用NEWARE电池分析仪量测实施例9所得的金属离子电池(10)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为3.3V,放电截止电压为0.2V),可得知其最大比容量为87mAh/g,如图11与如表3所示。
实施例10:
提供一厚度为0.025mm的铜箔(友和代理,厂牌是Alfa Aesar),对其进行裁切,得到不锈钢电极。接着,提供隔离膜(玻璃滤纸(2层)、商品编号为沃特曼(Whatman)GFA)及一石墨电极(包含一活性材质配置于一集电基板上,其中该集电基板为碳纤维纸、活性材质为膨胀石墨(66mg))。接着,按照铜箔(作为负极)、隔离膜、及石墨电极(作为正极)的顺序排列,并以铝塑膜将其封装并注入电解质(氯化铝(AlCl3)/氯化铁(FeCl2)/氯化l-乙基-3-甲基咪唑鎓(1-ethyl-3-methylimidazolium chloride、[EMIm]Cl)、其中AlCl3及FeCl2的总合与[EMIm]Cl的摩尔比约为1.4:1,且FeCl2与AlCl3的摩尔比约为1:13),得到金属离子电池(11)。
接着,使用NEWARE电池分析仪量测实施例10所得的金属离子电池(11)的电池效能(量测条件为:以定电流方式进行充放电测试(1000mA/g),充电截止电压为3.3V,放电截止电压为0.3V),可得知其最大比容量为105mAh/g,如图12与表3所示。
表3
负极 | 金属氯化物 | 最大比容量(mAh/g) | |
金属离子电池(5) | 铝 | AlCl<sub>3</sub> | 72 |
金属离子电池(9) | 碳纤维纸 | AlCl<sub>3</sub>/FeCl<sub>2</sub>(13:1) | 96.1 |
金属离子电池(10) | 不锈钢 | AlCl<sub>3</sub>/FeCl<sub>2</sub>(13:1) | 87 |
金属离子电池(11) | 铜箔 | AlCl<sub>3</sub>/FeCl<sub>2</sub>(13:1) | 105 |
由表3可知,即使将电极由铝换为碳纤维纸或是不锈钢,当所使用电解质同时包含氯化铝及氯化铁时,所得的金属离子电池的比容量可提升1.38倍至1.55倍(与电解质仅为氯化铝的金属离子电池(5)相比),且显现出多个充放电电压平台。
虽然本发明已以数个实施例发明如上,然其并非用以限定本发明,任何本技术领域中具有通常知识者,在不脱离本发明的精神和范围内,当可作任意的更动与润饰,因此本发明的保护范围当视后附的申请专利范围所界定者为准。
Claims (19)
1.一种金属离子电池,包含:
正极;
隔离层;
负极,其中该负极以隔离层与该正极相隔;以及
电解质,设置于该正极与该负极之间,其中该电解质由离子液体、卤化铝、及金属卤化物组成,其中该金属卤化物不包含卤化铝且是卤化银、卤化铜、卤化铁、卤化钴、卤化锌、卤化铟、卤化镉、卤化镍、卤化锡、卤化铬、卤化镧、卤化钇、卤化钛、卤化锰、卤化钼、或上述的组合,其中该金属卤化物与卤化铝的总摩尔数与该离子液体的摩尔的比是1.1:1至2.1:1;该金属卤化物与该卤化铝的摩尔数比是1:100至1:1。
2.如权利要求1所述的金属离子电池,其中该正极由集电层及活性材料所构成。
3.如权利要求2所述的金属离子电池,其中该集电层是导电性碳基材。
4.如权利要求3所述的金属离子电池,其中该导电性碳基材是碳布、碳毡、或碳纸。
5.如权利要求2所述的金属离子电池,其中该活性材料是层状活性材料。
6.如权利要求2所述的金属离子电池,其中该活性材料是石墨、纳米碳管、石墨烯、或上述的组合。
7.如权利要求6所述的金属离子电池,其中该石墨是天然石墨、人工石墨、中间相碳微球、热解石墨、发泡石墨、鳞片石墨、膨胀石墨、或上述材料的组合。
8.如权利要求1所述的金属离子电池,其中该负极包含金属或其合金、集电层、或其组合。
9.如权利要求8所述的金属离子电池,其中该金属或其合金包含银、铜、铁、钴、铝、锌、铟、镉、镍、锡、铬、镧、钇、钛、锰、钨、钽或钼。
10.如权利要求1所述的金属离子电池,其中在该金属离子电池进行充放电后,该金属卤化物可与该离子液体形成卤化金属酸根,而该卤化铝可与该离子液体形成卤化铝酸根。
11.如权利要求10所述的金属离子电池,其中该卤化金属酸根的离子尺寸小于该卤化铝酸根的离子尺寸。
12.如权利要求1所述的金属离子电池,其中该离子液体包含尿素、N-二甲基脲、氯化胆碱、乙酰氯化胆碱、碱金族卤化物、二甲基亚砜、二甲基砜、烷基咪唑鎓盐、烷基吡啶鎓盐、烷基氟吡唑鎓盐、烷基三唑鎓盐、芳烷铵盐、烷基烷氧基铵盐、芳烷鏻盐、芳烷锍盐、或上述材料的组合。
13.一种金属离子电池的制备方法,包含:
提供正极及负极;
提供隔离层以分隔该正极及该负极;以及
提供电解质,使该电解质配置于该正极及该负极之间,其中该电解质由离子液体、卤化铝、及金属卤化物组成,其中该金属卤化物不包含卤化铝且是卤化银、卤化铜、卤化铁、卤化钴、卤化锌、卤化铟、卤化镉、卤化镍、卤化锡、卤化铬、卤化镧、卤化钇、卤化钛、卤化锰、卤化钼、或上述的组合,其中该金属卤化物与卤化铝的总摩尔数与该离子液体的摩尔的比是1.1:1至2.1:1;该金属卤化物与该卤化铝的摩尔数比是1:100至1:1。
14.如权利要求13所述的金属离子电池的制备方法,其中该正极由集电层及活性材料所构成。
15.如权利要求14所述的金属离子电池的制备方法,其中该活性材料是利用电化学或气相法所得的预插层的材料。
16.如权利要求15所述的金属离子电池的制备方法,其中该预插层的材料的制备步骤包含:
将该离子液体与该金属卤化物混合,并配置于该正极及该负极之间;
使该金属卤化物与该离子液体反应形成卤化金属酸根;以及
在该正极及该负极间施加电位差,且该卤化金属酸根对该正极进行插层反应,得到由预插层的材料组成的正极。
17.如权利要求15所述的金属离子电池的制备方法,其中该预插层的材料的制备步骤包含:
将该离子液体与该卤化铝混合,并配置于该正极及该负极之间;
使该卤化铝与该离子液体反应形成卤化铝酸根;以及
在该正极及该负极间施加电位差,且该卤化铝酸根对该正极进行插层反应,得到由预插层的材料组成的正极。
18.如权利要求15所述的金属离子电池的制备方法,其中该预插层的材料的制备步骤包含:
对该金属卤化物加热,产生金属卤化物气体;以及
利用该金属卤化物气体对该正极进行预插嵌。
19.如权利要求15所述的金属离子电池的制备方法,其中该预插层的材料的制备步骤包含:
对该卤化铝加热,产生一卤化铝气体;以及
利用该卤化铝气体对该正极进行预插嵌。
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2017
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- 2017-05-17 CN CN201710345622.1A patent/CN107394271B/zh active Active
- 2017-05-17 US US15/597,353 patent/US20170338513A1/en not_active Abandoned
- 2017-05-17 EP EP17171504.8A patent/EP3246980B1/en active Active
- 2017-05-17 KR KR1020170060863A patent/KR102011367B1/ko active IP Right Grant
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CN107394271A (zh) | 2017-11-24 |
US20170338513A1 (en) | 2017-11-23 |
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EP3246980A1 (en) | 2017-11-22 |
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JP6701122B2 (ja) | 2020-05-27 |
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