EP3526878A1 - Batterie à ions aluminium rechargeable - Google Patents
Batterie à ions aluminium rechargeableInfo
- Publication number
- EP3526878A1 EP3526878A1 EP17860452.6A EP17860452A EP3526878A1 EP 3526878 A1 EP3526878 A1 EP 3526878A1 EP 17860452 A EP17860452 A EP 17860452A EP 3526878 A1 EP3526878 A1 EP 3526878A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminum
- oxide
- group
- transition metal
- manganese
- 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.)
- Pending
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims description 316
- 239000003792 electrolyte Substances 0.000 claims abstract description 140
- 238000000034 method Methods 0.000 claims abstract description 47
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 aluminum compound Chemical class 0.000 claims description 306
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 248
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 202
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 198
- 239000000203 mixture Substances 0.000 claims description 170
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 166
- 229910052723 transition metal Inorganic materials 0.000 claims description 144
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 108
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 108
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 107
- 239000010949 copper Substances 0.000 claims description 107
- 239000010941 cobalt Substances 0.000 claims description 100
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 99
- 229910052802 copper Inorganic materials 0.000 claims description 99
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 96
- 239000010936 titanium Substances 0.000 claims description 96
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 95
- 239000011651 chromium Substances 0.000 claims description 95
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 95
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 94
- 239000010937 tungsten Substances 0.000 claims description 94
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 93
- 239000011701 zinc Substances 0.000 claims description 93
- 229910017052 cobalt Inorganic materials 0.000 claims description 92
- 229910052759 nickel Inorganic materials 0.000 claims description 92
- 229910052742 iron Inorganic materials 0.000 claims description 91
- 229910052719 titanium Inorganic materials 0.000 claims description 88
- 229910052804 chromium Inorganic materials 0.000 claims description 87
- 229910052721 tungsten Inorganic materials 0.000 claims description 86
- 229910052725 zinc Inorganic materials 0.000 claims description 85
- 150000003624 transition metals Chemical class 0.000 claims description 84
- 239000002253 acid Substances 0.000 claims description 79
- 239000011888 foil Substances 0.000 claims description 78
- 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 78
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 75
- 239000011733 molybdenum Substances 0.000 claims description 75
- 229910052720 vanadium Inorganic materials 0.000 claims description 74
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 68
- 229910052751 metal Inorganic materials 0.000 claims description 68
- 239000002184 metal Substances 0.000 claims description 68
- 229910052750 molybdenum Inorganic materials 0.000 claims description 67
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 66
- 229910052744 lithium Inorganic materials 0.000 claims description 64
- 229910002804 graphite Inorganic materials 0.000 claims description 59
- 239000010439 graphite Substances 0.000 claims description 59
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 56
- 239000004743 Polypropylene Substances 0.000 claims description 51
- 150000002500 ions Chemical class 0.000 claims description 51
- 229920001155 polypropylene Polymers 0.000 claims description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000002131 composite material Substances 0.000 claims description 41
- 239000011734 sodium Substances 0.000 claims description 38
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 37
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 36
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 36
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 239000011591 potassium Substances 0.000 claims description 36
- 239000011135 tin Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 29
- 229910052708 sodium Inorganic materials 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- 229910052700 potassium Inorganic materials 0.000 claims description 28
- 229910052718 tin Inorganic materials 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 27
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 26
- 229910021389 graphene Inorganic materials 0.000 claims description 26
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 claims description 25
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000004677 Nylon Substances 0.000 claims description 22
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- 229920001778 nylon Polymers 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 229920001410 Microfiber Polymers 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003658 microfiber Substances 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- FMGDJQPRGBQGAI-UHFFFAOYSA-K tribromoalumane hexahydrate Chemical compound O.O.O.O.O.O.[Al+3].[Br-].[Br-].[Br-] FMGDJQPRGBQGAI-UHFFFAOYSA-K 0.000 claims description 14
- TXBSWQWDLFJQMU-UHFFFAOYSA-N 4-(chloromethyl)-1,2-diethoxybenzene Chemical compound CCOC1=CC=C(CCl)C=C1OCC TXBSWQWDLFJQMU-UHFFFAOYSA-N 0.000 claims description 13
- 229910000838 Al alloy Inorganic materials 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 13
- MXJUQVJZBURDQQ-UHFFFAOYSA-K aluminum;triiodide;hexahydrate Chemical compound O.O.O.O.O.O.[Al+3].[I-].[I-].[I-] MXJUQVJZBURDQQ-UHFFFAOYSA-K 0.000 claims description 13
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910002601 GaN Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- AJGDITRVXRPLBY-UHFFFAOYSA-N aluminum indium Chemical compound [Al].[In] AJGDITRVXRPLBY-UHFFFAOYSA-N 0.000 claims description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002905 metal composite material Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 claims description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 10
- DEVXQDKRGJCZMV-UHFFFAOYSA-K Aluminum acetoacetate Chemical compound [Al+3].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O DEVXQDKRGJCZMV-UHFFFAOYSA-K 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 10
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 10
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229940009827 aluminum acetate Drugs 0.000 claims description 10
- 229940118662 aluminum carbonate Drugs 0.000 claims description 10
- HQQUTGFAWJNQIP-UHFFFAOYSA-K aluminum;diacetate;hydroxide Chemical compound CC(=O)O[Al](O)OC(C)=O HQQUTGFAWJNQIP-UHFFFAOYSA-K 0.000 claims description 10
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 10
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims description 10
- RSMSFENOAKAUJU-UHFFFAOYSA-L bis[[2-(4-chlorophenoxy)-2-methylpropanoyl]oxy]aluminum;hydrate Chemical compound O.C=1C=C(Cl)C=CC=1OC(C)(C)C(=O)O[Al]OC(=O)C(C)(C)OC1=CC=C(Cl)C=C1 RSMSFENOAKAUJU-UHFFFAOYSA-L 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 229910014235 MyOz Inorganic materials 0.000 claims description 8
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims description 8
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- KWXIRYKCFANFRC-UHFFFAOYSA-N [O--].[O--].[O--].[Al+3].[In+3] Chemical compound [O--].[O--].[O--].[Al+3].[In+3] KWXIRYKCFANFRC-UHFFFAOYSA-N 0.000 claims description 8
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 8
- 150000004820 halides Chemical group 0.000 claims description 8
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 8
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 8
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 8
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 8
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium peroxide Inorganic materials [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 8
- SKFYTVYMYJCRET-UHFFFAOYSA-J potassium;tetrafluoroalumanuide Chemical compound [F-].[F-].[F-].[F-].[Al+3].[K+] SKFYTVYMYJCRET-UHFFFAOYSA-J 0.000 claims description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten dioxide Inorganic materials O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
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- 230000002588 toxic effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000252506 Characiformes Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- BZWNOUGHXUDNCG-UHFFFAOYSA-N aluminum lithium manganese(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[Al+3].[Mn++] BZWNOUGHXUDNCG-UHFFFAOYSA-N 0.000 description 2
- 229910002111 aluminum magnesium boride Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910020828 NaAlH4 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PZBHVYWEEVVAKK-UHFFFAOYSA-N [Al+3].O[N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Al+3].O[N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PZBHVYWEEVVAKK-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- UYGPQLSLSJKHDQ-UHFFFAOYSA-H dialuminum;sulfonato sulfate Chemical compound [Al+3].[Al+3].[O-]S(=O)(=O)OS([O-])(=O)=O.[O-]S(=O)(=O)OS([O-])(=O)=O.[O-]S(=O)(=O)OS([O-])(=O)=O UYGPQLSLSJKHDQ-UHFFFAOYSA-H 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 208000008127 lead poisoning Diseases 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical class [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011738 major mineral Substances 0.000 description 1
- 235000011963 major mineral Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to rechargeable batteries using charge carriers comprising aluminum ions, and particularly batteries with reduced toxic components to minimize human health hazards and environmental damage.
- Lead acid batteries are the most widely used battery technology for grid storage owing to their low cost (about $ 100-$ 150 / kWh).
- lead acid batteries have a comparatively low gravimetric energy density (30-50 Wh/kg) and a poor cycle life, between 500 and 1000 charge / discharge cycles, based on the low depths of discharge (50-75%).
- lead acid batteries have significant safety problems associated with handling and disposal, due to the presence of sulfuric acid and toxic lead components. Reports of increased lead poisoning and acid-related injuries among workers and children exposed to unsafe handling and disposal of lead acid batteries, have raised strong concerns over large-scale implementation of lead acid batteries as storage for electricity generated from renewable energy sources.
- sodium ion batteries are estimated to reach a price of about $250 /kWh by 2020, but the volumetric energy density of sodium ion battery technology is lower than that of lead acid batteries at less than about 30 Wh/L.
- vanadium redox flow batteries offer high capacity, long discharge times and high cycle life, but have relatively low gravimetric and volumetric energy densities, and are expensive due to the high cost of vanadium and other components.
- Liquid metal batteries on the other hand are based on ion exchange between two immiscible molten salt electrolytes, but must operate at high temperatures, up to 450°C, rely on a complicated lead-antimony-lithium composite for ion exchange, and such systems have problems of flammability and toxicity.
- a rechargeable battery using an electrolyte comprising aluminum ions is disclosed, as well as methods of making the battery and methods of using the battery.
- a battery in certain embodiments, includes an anode comprising aluminum metal, an aluminum alloy or an aluminum compound, a cathode, and an electrolyte comprising a solvent and an aluminum salt, and a porous separator comprising an electrically insulating material that prevents direct contact of the anode and the cathode.
- the battery is a rechargeable battery.
- a battery in certain embodiments, includes an anode comprising aluminum, an aluminum alloy or an aluminum compound; a cathode that comprises a material selected from the group consisting of lithium manganese oxide; acid-treated lithium manganese oxide; electrochemically delithiated lithium manganese oxide; hydrothermally delithiated lithium manganese oxide; a lithium metal manganese oxide; an acid-treated lithium metal manganese oxide; a transition metal oxide; a transition metal sulfide; a transition metal nitride; a transition metal carbide; an aluminum transition metal oxide; an aluminum transition metal sulfide; an aluminum transition metal nitride; an aluminum transition metal carbide; a graphite metal composite; graphite-graphite oxide; manganese dioxide; electrolytic manganese dioxide; sulfur; a sulfur composite; phosphorus; a phosphorus composite; and graphene, wherein graphene is defined as carbon with fewer than one hundred sheets; and a porous separator comprising
- the ion comprising aluminum is selected from the group consisting of Al 3+ , Al(OH) 4 1_ , AICV " , A1H 4 1_ , AlF 6 l A1(N0 3 ) 4 1_ , A1(S0 4 ) 2 1_ , A1H 4 1_ , A1F 4 1_ , AlBr 4 1_ , All " , A1(C10 4 ) 4 1_ , A1(PF 6 ) 4 1_ , A10 2 1_ , A1(BF 4 ) 4 1_ , and mixtures thereof.
- the solvent comprises at least one compound selected from the group consisting of water, hydrogen peroxide, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, N-methyl pyrrolidone, a substituted or unsubstituted C1-C4 straight chain or branched alkyl carbonate, a substituted or unsubstituted C1-C4 straight chain or branched alkene carbonate, an ionic liquid and mixtures thereof.
- the manganese dioxide has been synthesized on a porous S1O2 template.
- the ionic liquid comprises at least one cation selected from the group consisting of a substituted or unsubstituted quaternary ammonium ion, substituted or unsubstituted imidazolium ion, a substituted or unsubstituted pyrrolidinium, a substituted or unsubstituted piperdinium, and a substituted or unsubstituted phosphonium ion, and at least one anion selected from the group consisting of a halide ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanate ion, a dicyanamide ion, a substituted or unsubstituted borate ion, a substituted or unsubstituted acetate ion, a substituted or unsubstituted imide ion, a substituted or unsubstituted
- the anode is an aluminum alloy comprising aluminum metal and at least one of manganese, magnesium, lithium, zirconium, iron, cobalt, tungsten, vanadium, nickel, copper, silicon, chromium, titanium, tin and zinc.
- the anode is aluminum metal or an aluminum alloy that has received a surface treatment to increase its hydrophilic properties.
- the surface treatment comprises the step of contacting a surface of the aluminum with an aqueous solution of an alkali metal hydroxide.
- anode is an aluminum metal foil or an aluminum alloy foil.
- the anode is an aluminum compound selected from the group consisting of an aluminum transition metal oxide (Al x M y O z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range from 0 to 8, inclusive), an aluminum transition metal sulfide (Al x M y S z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range from 0 to 8, inclusive), an aluminum transition metal nitride (Al x M y N z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper
- the anode is treated with a reagent selected from the group consisting of alkali metal hydroxides, alkali metal phosphates, alkali metal phosphides, alkali metal nitrates, alkali metal nitrides, alkali metal sulfates, alkali metal sulfides of alkali metals and mixtures thereof, wherein the alkali metal is at least one of lithium, sodium, potassium, calcium, rubidium, or cesium.
- a reagent selected from the group consisting of alkali metal hydroxides, alkali metal phosphates, alkali metal phosphides, alkali metal nitrates, alkali metal nitrides, alkali metal sulfates, alkali metal sulfides of alkali metals and mixtures thereof, wherein the alkali metal is at least one of lithium, sodium, potassium, calcium, rubidium, or cesium.
- the anode is treated with phosphoric acid, nitric acid, sulfuric acid, sulfurous acid, acetic acid, hydrochloric acid, hydrofluoric acid, hydrogen peroxide, polyvinyl alcohol, ozone, oxygen plasma etching or laser etching.
- the anode comprises aluminum coated with a metal oxide layer, aluminum coated with a metal phosphate layer, aluminum coated with a metal nitride layer, aluminum coated with a metal sulfide layer, or aluminum coated with a metal carbide layer, wherein the metal is selected from the group consisting of titanium, molybdenum, cobalt, tin, vanadium, ruthenium, palladium, copper, nickel, zinc, iron, manganese, chromium, silver, gold, platinum and mixtures thereof.
- the anode is coated with a layer of ionically conducting, insulating or electrically conductive polymer selected from the group consisting of a polyaniline, a polyacetylene, a polyphenylene vinylene, a parylene, a polypyrrole, a polythiophene, a polyphenylene sulfide, a polystyrene, a polyvinyl alcohol, a polyethylene oxide, a polymethyl methacrylate, graphite and mixtures thereof.
- Suitable coating methods are known in the art, including spin coating, drop casting, spray coating, chemical vapor deposition, and coating pastes of the polymer with doctor- blade or slot-die methods.
- the anode further comprises a redox catalyst such as platinum, a compound comprising zirconium, vanadium pentoxide, silver oxide, iron oxide, molybdenum oxide, bismuth oxide, bismuth-molybdenum oxide, iron molybdenum oxide, palladium salts, copper salts, cobalt salts, manganese salts, Prussian blue analogs such as cobalt hexacyanocobaltate or manganese hexacyanocobaltate, and mixtures thereof.
- a redox catalyst such as platinum, a compound comprising zirconium, vanadium pentoxide, silver oxide, iron oxide, molybdenum oxide, bismuth oxide, bismuth-molybdenum oxide, iron molybdenum oxide, palladium salts, copper salts, cobalt salts, manganese salts, Prussian blue analogs such as cobalt hexacyanocobaltate or manganese hexacyanocobaltate
- the solvent comprises at least one compound selected from the group consisting of water, hydrogen peroxide, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, N-methyl pyrrolidone, a substituted or unsubstituted C1-C4 straight chain or branched alkyl carbonate, a substituted or unsubstituted C1-C4 straight chain or branched alkene carbonate, an ionic liquid comprising at least one cation selected from the group consisting of a substituted or unsubstituted quaternary ammonium ion, substituted or unsubstituted imidazolium ion, a substituted or unsubstituted pyrrolidinium, a substituted or unsubstituted piperdinium, and a substituted or unsubstituted phosphonium ion, and at least one anion selected from the group consisting of a halide
- the solvent comprises at least one compound selected from the group consisting of water, hydrogen peroxide, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, N-methyl pyrrolidone, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, a fluorocarbonate, a glycol, a methyl imide, phosphinate, amine, an imidazolium acetate, an imidazolium aluminate, an imidazolium carbonate, an imidazolium cyanate, an imidazolium dicyanamide, an imidazolium halide, an imidazolium hexafiuorophosphate, an imidazolium imide, an imidazolium nitrate, an imidazolium phosphate, an imidazolium sulfate, an imidazolium sulfonate, an imidazolium halide,
- tetrafluoroborate an imidazolium tosylate, a pyrrolidinium halide, a pyrrolidinium imide, a pyrrolidinium tetrafluoroborate, a tetrabutylammonium benzoate, a tetrabutylammonium cyanate, a tetrabutylammonium halide, preferably tetrabutylammonium bromide, a tetrabutylammonium sulfonate, a tetrabutylammonium trifiuoroacetate, a phosphonium tetrafluoroborate, preferably tetrabutylphosphonium tetrafluoroborate, phosphonium, a phosphonium halide, a phosphonium sulfonate, a phosphonium tosylate and mixtures thereof.
- the aluminum salt is selected from the group consisting of aluminum bromide hexahydrate, aluminum fluoride, aluminum fluoride trihydrate, aluminum iodide, aluminum iodide hexahydrate, aluminum perchlorate, aluminum hydroxide, aluminum acetate, aluminum acetoacetate, aluminum nitrate, aluminum nitrate nonahydrate, aluminum antimonide, aluminum arsenate, aluminum bromide, aluminum sulfate, aluminum phosphate, aluminum carbonate, aluminum chloride, aluminum chlorohydrate, aluminum clofibrate, aluminum diacetate, aluminum diboride, aluminum diethyl phosphinate, aluminum formate, aluminum gallium arsenide, aluminum gallium indium phosphide, aluminum gallium nitride, aluminum gallium phosphide, aluminum indium arsenide, aluminum iodide, aluminum magnesium boride, aluminum molybdate, aluminum bromide, aluminum iodide, aluminum oxide, aluminum oxy
- the aluminum salt is selected from the group consisting of aluminum acetate, aluminum acetoacetate, aluminum antimonide, aluminum arsenate, aluminum bromide, aluminum bromide hexahydrate, aluminum carbonate, aluminum chloride, aluminum chlorohydrate, aluminum clofibrate, aluminum diacetate, aluminum diethyl phosphinate, aluminum fluoride, aluminum fluoride trihydrate, aluminum formate, aluminum gallium arsenide, aluminum gallium indium phosphide, aluminum gallium nitride, aluminum gallium phosphide, aluminum hydroxide, aluminum indium arsenide, aluminum iodide, aluminum iodide hexahydrate, aluminum molybdate, aluminum nitrate, aluminum nitrate nonahydrate, aluminum oxide, aluminum perchlorate, aluminum phosphate, aluminum silicate, aluminoxane, ammonium aluminum sulfate and mixtures thereof.
- the aluminum salt is selected from the group consisting of aluminum acetate, aluminum acetoacetate, aluminum bromide, aluminum bromide hexahydrate, aluminum carbonate, aluminum chloride, aluminum chlorohydrate, aluminum clofibrate, aluminum diacetate, aluminum diethyl phosphinate, aluminum fluoride, aluminum fluoride trihydrate, aluminum formate, aluminum hydroxide, aluminum iodide, aluminum iodide hexahydrate, aluminum molybdate, aluminum nitrate, aluminum nitrate nonahydrate, aluminum perchlorate, aluminum phosphate, aluminum silicate, aluminum sulfate, aluminum sulfide, aluminoxane, ammonium aluminum sulfate, ammonium hexafluoroaluminate and mixtures thereof
- the electrolyte further comprises lithium
- the electrolyte further comprises at least one ion selected from the group consisting of Li 1+ , CI 1" , and C3 ⁇ 4 1+ .
- the charge is carried by an ion selected from the group consisting of Li 1+ , CI 1" , and C3 ⁇ 4 1+ during the discharge of the battery.
- the electrolyte further comprises at least one compound selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide, rubidium oxide, cesium oxide, polytetrafluoroethylene, polyethylene oxide, acetonitrile butadiene styrene, styrene butadiene rubber, ethyl vinyl acetate, polyvinyl alcohol, poly(vinylidene fluoride-co-hexafluoropropylene), polymethyl methacrylate and mixtures thereof.
- the molarity of the aluminum salt ranges from 0.05 M to 5 M and the concentration of water ranges from 5 weight% to 95 weight%.
- the electrolyte is an aqueous solution of an aluminum salt selected from the group consisting of aluminum bromide hexahydrate, aluminum fluoride, aluminum fluoride trihydrate, aluminum iodide, aluminum iodide hexahydrate, aluminum perchlorate, aluminum hydroxide, aluminum acetate, aluminum acetoacetate, aluminum nitrate, aluminum nitrate nonahydrate, aluminum antimonide, aluminum arsenate, aluminum bromide, aluminum sulfate, aluminum phosphate, aluminum carbonate, aluminum chloride, aluminum chlorohydrate, aluminum clofibrate, aluminum diacetate, aluminum diboride, aluminum diethyl phosphinate, aluminum formate, aluminum gallium arsenide, aluminum gallium indium phosphide, aluminum gallium nitride, aluminum gallium phosphide, aluminum indium arsenide, aluminum iodide, aluminum magnesium boride, aluminum molybdate, aluminum bromide, aluminum
- the electrolyte is an aqueous solution of an aluminum salt is selected from the group consisting of aluminum bromide hexahydrate, aluminum fluoride, aluminum fluoride trihydrate, aluminum iodide, aluminum iodide hexahydrate, aluminum perchlorate, aluminum hydroxide, aluminum acetate, aluminum acetoacetate, aluminum nitrate, aluminum nitrate nonahydrate, aluminum antimonide, aluminum arsenate, aluminum bromide, aluminum sulfate, aluminum phosphate, aluminum carbonate, aluminum chloride, aluminum chlorohydrate, aluminum clofibrate, aluminum diacetate, aluminum diethyl phosphinate, aluminum formate, aluminum gallium arsenide, aluminum gallium indium phosphide, aluminum gallium nitride, aluminum gallium phosphide, aluminum indium arsenide, aluminum iodide, aluminum molybdate, aluminum bromide
- the electrolyte is an aqueous solution of an aluminum salt selected from the group consisting of aluminum bromide hexahydrate, aluminum fluoride, aluminum fluoride trihydrate, aluminum iodide, aluminum iodide hexahydrate, aluminum perchlorate, aluminum hydroxide, aluminum acetate, aluminum acetoacetate, aluminum nitrate, aluminum nitrate nonahydrate, aluminum bromide, aluminum sulfate, aluminum phosphate, aluminum carbonate, aluminum chloride, aluminum chlorohydrate, aluminum clofibrate, aluminum diacetate, aluminum diethyl phosphinate, aluminum formate, aluminum iodide, aluminum molybdate, aluminum bromide, aluminum iodide, aluminum silicate, aluminoxane, ammonium aluminum sulfate, and mixtures thereof.
- an aluminum salt selected from the group consisting of aluminum bromide hexahydrate, aluminum fluoride, aluminum fluoride trihydrate, aluminum iodide, aluminum
- the electrolyte further comprises at least one of
- polytetrafluoroethylene polyethylene oxide, acetonitrile butadiene styrene, styrene butadiene rubber, ethyl vinyl acetate, polyvinyl alcohol, poly(vinylidene fiuoride-co- hexafiuoropropylene), polymethyl methacrylate and mixtures thereof.
- the molarity of the aluminum salt ranges from 0.05 M to 5 M and the concentration of water ranges from 5 weight% to 95 weight%.
- the electrolyte comprises at least two ions selected from the group consisting of Al 3+ , Li 1+ , Al(OH) 4 1_ , A1C1 4 1_ , A1H 4 1_ , A1F 6 1_ , A1(N0 3 )4 1_ , A1(S0 4 )2 1_ , A1H 4 1_ , AIF4 1" , ⁇ 1 ⁇ 4 1” , AII4 1" , A1(C104)4 1_ , A1(PF 6 )4 1_ , AIO2 1" , A1(BF 4 ) 4 1” , CI 1" , and C3 ⁇ 4 1+ .
- the cathode comprises a material selected from the group consisting of lithium manganese oxide, acid-treated lithium manganese oxide, lithium metal manganese oxide (where the metal can be nickel, cobalt, aluminum, chromium, sodium, potassium, iron, copper, tin, titanium, tungsten, zinc, platinum and combinations thereof), acid-treated lithium metal manganese oxide, transition metal oxide (where the metals include, but are not limited to iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, cobalt and mixtures thereof), transition metal sulfide (where the metals include, but are not limited to iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, cobalt and mixtures thereof), transition metal nitride (where the metals could include, but are not limited to iron, vanadium, titanium,
- transition metal carbide where the metals could include, but are not limited to iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, cobalt and mixtures thereof
- aluminum transition metal oxide aluminum transition metal sulfide, aluminum transition metal nitride, aluminum transition metal carbide, graphite metal composite (where the metal can be conductive metals including but not limited to nickel, iron, copper, cobalt, chromium, aluminum, sodium, potassium, iron, copper, tin, titanium, tungsten, zinc, platinum, gold, silver), graphite-graphite oxide, manganese dioxide, electrolytic manganese dioxide, sulfur, sulfur composites (where the composites may include carbon, aluminum, lithium, iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium,
- the cathode comprises a material selected from the group consisting of a lithium metal manganese oxide, wherein the metal is selected from the group consisting of nickel, cobalt, aluminum, chromium, sodium, potassium, iron, copper, tin, titanium, tungsten, zinc, platinum and mixtures thereof; an acid-treated lithium metal manganese oxide, wherein the metal is selected from the group consisting of nickel, cobalt, aluminum, chromium, sodium, potassium, iron, copper, tin, titanium, tungsten, zinc, platinum and mixtures thereof; a transition metal oxide, wherein the transition metal is selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, cobalt and mixtures thereof; a transition metal sulfide, wherein the transition metal is selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium,
- the cathode comprises acid-treated lithium manganese oxide that has been treated using iron oxide nanoparticles in a magnetic field.
- the cathode further includes a redox catalyst such as platinum, a compound comprising zirconium, vanadium pentoxide, silver oxide, iron oxide, molybdenum oxide, bismuth oxide, bismuth-molybdenum oxide, iron molybdenum oxide, palladium salts, copper salts, cobalt salts, manganese salts, Prussian blue analogs and mixtures thereof.
- a redox catalyst such as platinum, a compound comprising zirconium, vanadium pentoxide, silver oxide, iron oxide, molybdenum oxide, bismuth oxide, bismuth-molybdenum oxide, iron molybdenum oxide, palladium salts, copper salts, cobalt salts, manganese salts, Prussian blue analogs and mixtures thereof.
- lithium manganese oxide, acid-treated lithium manganese oxide, electrochemically delithiated lithium manganese oxide, lithium metal manganese oxide, acid-treated lithium metal manganese oxide, transition metal oxide, transition metal sulfide, transition metal nitride, transition metal carbide, aluminum transition metal oxide, aluminum transition metal sulfide, aluminum transition metal nitride, aluminum transition metal carbide, graphite metal composite, graphite-graphite oxide, manganese dioxide, electrolytic manganese dioxide, sulfur composites, phosphorus composites, and graphene maybe further mixed with a metal such as copper, nickel, iron, zinc, lithium, sodium, potassium, magnesium, titanium, vanadium, chromium, molybdenum, tungsten, manganese, cobalt, indium, aluminum and lead, a semi-metal or metalloid such as boron, silicon and germanium, zeolite, polymethylmethacrylate, polyethylene oxide, polyvinyl alcohol, polyaniline
- the morphology of the metal, semi-metal, zeolite or oxide, hydroxide, sulfate, nitrate, phosphate, carbonates and halides may be in the form of hollow tubes, hollow spheres and hollow cubes.
- the metal, semi-metal, zeolite or oxide, hydroxide, sulfate, nitrate, phosphate, carbonates and halides may be crystalline, amorphous or polymorphous.
- the metal, semi-metal, zeolite, polymethylmethacrylate, polyethylene oxide, polyvinyl alcohol, polyaniline, polyvinyldifluoride, polytetrafluoroethylene, or an oxide, hydroxide, sulfate, nitrate, phosphate, carbonates and halides of the metal or metalloid may be removed through wet or dry etching or through thermal decomposition of polymers to create a porous cathode template with increased hydrophilicity.
- the cathode is further subject to a surface treatment with at least one of hydroxides, phosphates, phosphides, nitrates, nitrides, sulfates, sulfides of alkali metals where the alkali metals include at least one of lithium, sodium, potassium, calcium, rubidium, cesium, phosphoric acid, nitric acid, sulfuric acid, sulfurous acid, acetic acid, hydrochloric acid, hydrofluoric acid, hydrogen peroxide, ozone, oxygen plasma etching, electrochemical delithiation, hydrothermal delithiation, and laser etching.
- alkali metals include at least one of lithium, sodium, potassium, calcium, rubidium, cesium, phosphoric acid, nitric acid, sulfuric acid, sulfurous acid, acetic acid, hydrochloric acid, hydrofluoric acid, hydrogen peroxide, ozone, oxygen plasma etching, electrochemical delithiation, hydrothermal delithiation,
- the lithium manganese oxide has been subjected to acid treatment.
- the anode comprises aluminum metal
- the cathode comprises graphite-graphite oxide
- the aluminum salt comprises aluminum nitrate.
- the anode comprises aluminum metal
- the cathode comprises delithiated lithium manganese oxide
- the aluminum salt comprises aluminum nitrate.
- a battery in certain embodiments, includes an anode comprising aluminum, an aluminum alloy or an aluminum compound; a cathode that comprises a material selected from the group consisting of lithium manganese oxide; acid-treated lithium manganese oxide; electrochemically delithiated lithium manganese oxide; hydrothermally delithiated lithium manganese oxide; a lithium metal manganese oxide; an acid-treated lithium metal manganese oxide; a transition metal oxide; a transition metal sulfide; a transition metal nitride; a transition metal carbide; an aluminum transition metal oxide; an aluminum transition metal sulfide; an aluminum transition metal nitride; an aluminum transition metal carbide; a graphite metal composite; graphite-graphite oxide; manganese dioxide; electrolytic manganese dioxide; sulfur; a sulfur composite; phosphorus; a phosphorus composite; and graphene, wherein graphene is defined as carbon with fewer than one hundred sheets; and an electrolyte comprising
- a battery comprises an anode comprising aluminum, an aluminum alloy selected from the group comprising of aluminum and at least one of manganese, magnesium, lithium, zirconium, iron, cobalt, tungsten, vanadium, nickel, copper, silicon, chromium, titanium, tin and zinc or an aluminum compound selected from the group consisting of an aluminum transition metal oxide (Al x M y O z , where M is the transition metal including but not limited to iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, cobalt), an aluminum transition metal sulfide (Al x M y S z ), an aluminum transition metal nitride, an aluminum transition metal carbide, aluminum lithium cobalt oxide (AIL1 3 C0O2), lithium aluminum hydride (L1AIH4), sodium aluminum hydride (NaAlH/ t ), potassium aluminum fluoride (KAIF4), aluminum
- Al x M y O z
- a battery that includes an anode comprising aluminum metal; an aluminum alloy comprising aluminum and at least one selected from the group consisting of manganese, magnesium, lithium, zirconium, iron, cobalt, tungsten, vanadium, nickel, copper, silicon, chromium, titanium, tin and zinc; or an aluminum compound selected from the group consisting of an aluminum transition metal oxide
- Al x M y O z where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range from 0 to 8, inclusive
- an aluminum transition metal sulfide Al x M y S z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range from 0 to 8, inclusive
- an aluminum transition metal nitride Al x M y N z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range
- the anode and cathode are coated onto a current collector
- the collector is a metal or a conductive non-metal that includes at least one of nickel, copper, aluminum, stainless steel, vanadium, titanium, molybdenum, carbon, tin, brass, gold and palladium.
- the current collector may be further subject to surface treatment, prior to electrode coating, in order to improve adhesion.
- Such treatments include surface etching in an acidic solution, iron chloride solution or an alkali metal hydroxide solution, buffer oxide etchant, piranha solution, plasma etching, gas etching, laser etching, ion implantation.
- the anode and cathode are coated on to a porous polymer separator membrane.
- the anode and cathode are free standing, such as in the form of a foil, a sheet or a plate.
- the anode and cathode are delaminated from the current collector after coating and drying of the electrode by using at least one of a surface etchant such as alkali metal hydroxides, acids, buffer oxide etchant and piranha solution (a mixture of concentrated sulfuric acid with hydrogen peroxide, in a ratio of 3: 1 to 7: 1).
- the anode is free-standing, such as in the form of a foil, a sheet or a plate, while the cathode is coated on to a current collector.
- a system that includes at least one such rechargeable battery that is operatively connected to a controller, and wherein the controller is operatively connected to a source of electrical power and to a load.
- the controller is effective to control the charging of the battery by the source of electrical power.
- the controller is effective to control the discharging of the battery by the load.
- the source of electrical power is a solar panel or wind-powered generator.
- the load is a local electrical load or a power distribution grid.
- a method includes the steps of contacting lithium manganese oxide powder with an excess volume of an acid selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, acetic acid, hydroiodic acid, phosphoric acid and mixtures thereof to form a suspension; and filtering the suspension to recover delithiated lithium manganese oxide.
- a method also includes the step of contacting the delithiated manganese oxide with a 0.1-4 M hydroxide solution selected from the group consisting of lithium hydroxide, potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide and mixtures thereof.
- the hydroxide solution further comprises a solvent selected from the group consisting of water, ethanol, N-methyl pyrrolidone and mixtures thereof.
- a method includes the steps of the steps of combining 2-98 wt% lithium manganese oxide with 0-20 wt% (based on the total weight of the mixture) of a polymer binder selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene, styrene -butadiene rubber and mixtures thereof to form a mixture; combining the mixture with a solvent selected from the group consisting of water, ethanol, N-methyl pyrrolidone, dimethyl sulfoxide and mixtures thereof and mixing to form a slurry; casting the slurry on a substrate selected from the group consisting of aluminum, stainless steel, nickel, copper and pyrolytic graphite; drying the slurry and the substrate to form a cathode; placing the cathode in an electrochemical cell having a lithium foil electrode, a lithium ion electrolyte and a separator; and applying a voltage between the catho
- the mixture further comprises 0-20 wt% (based on the total weight of the mixture) of a thickening agent that is polysaccharide gum. In certain embodiments, the mixture further comprises 0-50 wt% (based on the total weight of the mixture) of a conductive carbon additive selected from the group consisting of activated carbon, Super-P carbon and mixtures thereof. In certain embodiments, the mixture comprises 80 wt% lithium manganese oxide, 6 wt% styrene-butadiene rubber, and further comprises 4 wt%
- a method includes the steps of combining a material selected from the group consisting of a metal oxide selected from the group consisting of lithium manganese oxide, delithiated lithium manganese oxide, manganese dioxide, titanium oxide, tin oxide, iron oxide, vanadium oxide, molybdenum oxide, cobalt oxide and mixtures thereof; an aluminum transition metal oxide (Al x M y O z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range from 0 to 8, inclusive); an aluminum transition metal sulfide (Al x M y S z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, mo
- the method the step of combining includes combining the material and the sacrificial template with a conductive additive selected from the group consisting of activated carbon, Super-P carbon and mixtures thereof to form a mixture.
- the method the step of combining includes combining the material and the sacrificial template with a polymer binder selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene, styrene -butadiene rubber and mixtures thereof to form a mixture.
- the method also includes the steps of combining the porous product with a solvent selected from the group consisting of water, methanol, ethanol, dimethyl sulfoxide, dimethyl formamide, N-methyl pyrrolidone and mixtures thereof and mixing to form a slurry; casting the slurry on a substrate selected from the group consisting of aluminum, stainless steel, nickel, copper and pyrolytic graphite; and drying the slurry and the substrate to form an electrode.
- the method also includes the step of contacting the electrode with an 1-50 wt% aqueous solution of hydrogen peroxide for 5-60 minutes at room temperature.
- a method includes the steps of combining Lii_ x Mn02 powder with at least one of deionized water, a base selected from the group consistiong of lithium hydroxide, potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide and mixtures thereof; an acid selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, sulfurous acid, acetic acid, hydrochloric acid, hydrofluoric acid, a metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, cobalt and mixtures thereof; and carbon to form a mixture; sealing the mixture in a hydrothermal pressure chamber; heating the hydrothermal pressure chamber to about 90 °C about 900 °C; treating the heated mixture for about 0.5-24 hours; and retrieving the treated mixture.
- a method includes the steps of combining iron oxide nanoparticles, delithiated manganese oxide, conductive carbon and polyvinylidene fluoride to form a mixture; adding the mixture to N-methyl pyrrolidone to form a slurry; coating the slurry onto a metal substrate; placing the slurry-coated metal substrate in a magnetic field; and allowing the slurry to dry.
- FIG. 1 A is a photograph of aluminum foil suitable for use as an anode that has been treated with a drop of an aqueous solution of lithium hydroxide
- FIG. IB is a photograph of the piece of the treated aluminum foil of FIG. 1A showing a change in the appearance of the drop of the aqueous solution of lithium hydroxide
- FIG. 1 C is a photograph of the piece of treated aluminum foil of FIG. IB showing the greyish-white appearance of the aluminum foil following the drying of the lithium hydroxide solution
- FIG. ID is a photograph of the piece of treated aluminum foil of FIG. 1 C showing the effect of placing a drop of deionized water on the treated aluminum foil indicating an increase in hydrophilicity of the treated aluminum foil
- FIG. IE is a photograph of a drop of deionized water on untreated aluminum foil for comparison to FIG. ID.
- FIG. 2 is a schematic diagram of an exploded view of a test battery 100 in a coin cell format, showing the positive case 1 10, a spring 120, a first spacer 130, the cathode 140, the separator 150, the anode 160, a second spacer 170 and the negative case 180.
- FIG. 3 is an x-ray photoelectron spectroscopy (XPS) profile of carbon sheets following a 100% depth of discharge, showing a strong peak corresponding to Al 2p transition, associated with the presence of gibbsite, Al(OH)3, crystals.
- XPS x-ray photoelectron spectroscopy
- FIG. 4A shows the voltage profile that was produced by applying current at a current density of 0.1 mA/cm 2 to a test battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte.
- FIG. 4A shows the voltage profile that was produced by applying current at a current density of 0.1 mA/cm 2 to a test battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte.
- FIG. 4B shows the voltage profile that was produced by applying current at a current density of 0.1 mA/cm 2 to a test battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising graphite-graphite oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte.
- the observed average operating voltage is significantly higher with the use of acid treated lithium manganese oxide cathodes, possibly owing to the higher activation energy for diffusion and intercalation of ions.
- Carbon is known to possess a sufficiently low activation energy for diffusion and intercalation of metal ions (the intercalation voltage of lithium ions in carbon against a lithium metal occurs at about 100 mV).
- FIG. 5A shows the battery capacity as a function of cycle index of a battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and a graphite-graphite oxide composite cathode.
- the coulombic efficiency was estimated to be close to 100%, indicating efficient and reversible charge and discharge kinetics.
- 5B shows the battery capacity as a function of cycle index of a battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and an acid treated Lii_ x Mn02 cathode.
- the reduction in capacity after over 800 charge / discharge cycles is only about 3 % of the original capacity.
- FIG. 6A shows sequential cyclic voltammetry profiles of a battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and an acid treated lithium manganese oxide cathode.
- FIG. 6A shows sequential cyclic voltammetry profiles of a battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and an acid treated lithium manganese oxide cathode.
- FIG. 6B shows sequential cyclic voltammetry profiles of a battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and a graphite-graphite oxide cathode.
- the test batteries in the coin cell format were cycled at various voltage sweep rates between 10 mV/sec and 50 mV/sec within a voltage range of 0 V and 1.5 V.
- FIG. 7A shows the results of electrochemical impedance spectroscopy (EIS) of a test cell having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , a 0.5 M aqueous aluminum nitrate electrolyte and an acid treated lithium manganese oxide cathode.
- EIS electrochemical impedance spectroscopy
- FIG. 7B shows the results of electrochemical impedance spectroscopy (EIS) of a test cell having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and a graphite-graphite oxide cathode.
- EIS electrochemical impedance spectroscopy
- FIG. 8A is a schematic representation of a prismatic cell 80.
- FIG. 8B illustrates the discharge voltage profile of a prismatic cell rated at 1 mAh.
- the cell had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , a 0.5 M aqueous aluminum nitrate electrolyte and were tested at 10 ⁇ /cm 2 .
- FIG. 9A is a schematic representation of a pouch cell 90.
- FIG. 9B illustrates the discharge profile of a pouch cell comprising 0.8 cm x 1 cm electrodes and hydrophilic polypropylene separators.
- the cell had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid- treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , a 0.5 M aqueous aluminum nitrate electrolyte and were tested at about 25 ⁇ /cm 2 .
- FIG. 9C illustrates the voltage profile of a single interface pouch cell cycled at 20 ⁇ /cm 2 where the anode comprised phosphate -treated aluminum foil, the cathode consisted of acid-delithiated manganese dioxide coated on nickel foil and the separator was a Celgard 3500 polypropylene sheet. The separator thickness was about 25 ⁇ and the average pore size was about 67 nm, and the electrolyte was 0.5 M aqueous aluminum nitrate.
- FIG. 10 is a block diagram of a system 800 that incorporates the battery 810 of the present disclosure, showing a controller 820 that is operatively connected to battery 810, a source of electrical power 830, a local electrical load 840 and an electrical power distribution grid 850.
- FIG. 1 1 compares the discharge and charging properties of two batteries differing in electrolyte composition: one battery having a 0.5 M A1(N(3 ⁇ 4) 3 (aq) electrolyte (curve 1) and another battery having a 0.5 M A1(N0 3 ) 3 and 2 M LiOH (aq) electrolyte (curve 2).
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and was tested at current densities of 10 ⁇ /cm 2 .
- FIG. 12 illustrates the effect of separator pore size on the average discharge potential produced at a given current density, where pentagons (1) represent measurements made on a battery having a polypropylene separator with 0.067 ⁇ pores, a triangle (2) represents measurements made on a battery having a mixed cellulose ester separator with 0.20 ⁇ pores, a circle (3) represents measurements made on a battery having a nylon separator with 0.45 ⁇ pores, squares (4) represent measurements made on a battery having a nylon separator with 0.80 ⁇ pores, and diamonds (5) represent measurements made on a battery having a glass microfiber separator with 1.0 ⁇ pores.
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- Polypropylene separators
- FIG. 13 illustrates the discharge of a battery having a polypropylene separator with 0.067 ⁇ pores at a current density of 10 ⁇ /cm 2 .
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- FIG. 14 illustrates the discharge of a battery having a nylon separator with 0.80 ⁇ pores at a current densities of 20 ⁇ /cm 2 (curve 1), 40 ⁇ /cm 2 (curve 2), and 40 ⁇ /cm 2 (curve 3).
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid- treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- FIG. 15 illustrates the discharge of a battery having a glass microfiber separator with 1.0 ⁇ pores at a current densities of 20 ⁇ /cm 2 (curve 1) and 40 ⁇ /cm 2 (curve 2).
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- FIG. 16 is a photograph of the free-standing, translucent solid polymer electrolyte measuring about 1 mm in thickness and about 3 cm in diameter.
- FIG. 17 illustrates the voltage profile of a battery having a solid-polymer electrolyte, showing a short duration of discharge at 50 ⁇ /cm 2 , followed by discharging at 20 ⁇ /cm 2 and charging at a current density of 20 ⁇ /cm 2 , with an inset of a photograph of solid polymer electrolytes.
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ . The surface of the cathode was further treated with 2 M LiOH prior to assembly and testing.
- the electrolyte was prepared by mixing 6.7 weight% poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), 20 weight% aluminum nitrate and 10 weight% LiOH in 73.3 weight% deionized water. The solution was then placed inside a furnace maintained at 120 °C overnight to remove the water content and obtain the resultant solid polymer electrolyte.
- PVDF-HFP poly(vinylidene fluoride-co-hexafluoropropylene)
- FIG. 18 shows a discharge profile produced by a combination of low-current and high-current pulses.
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 0.5 M aluminum nitrate (aq) electrolyte and a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ .
- the current densities were switched between 100 A/g (low-current pulse) and 500 A/g (high- current pulse), where the current is normalized with respect to the mass of the cathode.
- FIG. 19 shows discharge voltage profiles illustrating that a combination of hydroxide etching and delithiation of a Mn0 2 cathode along with incorporation of LiOH in the electrolyte can produce a two-fold increase in current densities.
- Curve 1 was obtained from a battery having a 0.1 mAh rating discharged for 8 hours at a current density of 10 ⁇ /cm 2 .
- Curve 2 was obtained from a battery having a 0.1 mAh rating discharged for 5 hours at a current density of 20 ⁇ /cm 2 .
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N0 3 )3 and 2 M LiOH (aq) electrolyte.
- FIG. 20 shows a discharging voltage profile (curve 1) and a charging voltage profile (curve 2) of a battery having a cathode comprising Mn0 2 synthesized by a combination of acid-based (nitric acid) delithiation followed by 2M LiOH treatment of the Mn02 coated cathode, where the discharge cut-off (dashed line) has been set at 1 V.
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N0 3 ) 3 (aq) electrolyte.
- FIG. 21 shows a discharging voltage profiles of batteries having different treatments of the delithiated Mn0 2 cathode.
- Curve 1 is the discharging voltage profile of a battery having a cathode comprising Mn0 2 that was delithiated using nitric acid.
- Curve 2 is the discharging voltage profile of a battery having a cathode comprising Mn0 2 that was delithiated with electrochemical delithiation.
- Curve 3 is the discharging voltage profile of a battery having a cathode comprising Mn02 that was delithiated using nitric acid, followed by treatment of the cathode with 2M LiOH.
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N0 3 )3 (aq) electrolyte.
- FIG. 22 illustrates the discharge voltage profile of a battery having a cathode with a 100 ⁇ thick layer of porous Mn0 2 cathode, a 15 ⁇ thick aluminum foil anode that had been treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a current density of about 10 ⁇ /cm 2 .
- the electrolyte was 20 weight% aluminum nitrate and 80 weight% water.
- FIG. 23 illustrates the charge voltage profile (curve 1) and the discharge voltage profile (curve 2) of a Mn0 2 cathode with a cross-sectional thickness of 100 ⁇ , assembled against a 15 ⁇ thick aluminum foil that had been treated with LiOH, with a glass micro fiber separator and a current density of about 10 ⁇ /cm 2 .
- the cathode was treated with H2O2 and the electrolyte comprised 10 weight% H2O2.
- FIG. 24 is charge-discharge voltage profile of acid-delithiated, iodine-doped manganese oxide cathode.
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, an acid- delithiated, iodine-doped manganese oxide cathode, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N0 3 )3 (aq) electrolyte. Even at about 2-times the discharge current density, the cathode displayed low charge and discharge hysteresis of 84 mV and 129 mV respectively.
- FIG. 25 is an XPS profile of an aluminum metal foil anode.
- FIG. 26 is an XPS profile of a manganese oxide cathode.
- FIG. 27 illustrates the charge and discharge cycle of a battery comprising a titanium oxide cathode, an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and 0.5 M A1(N0 3 ) 3 electrolyte.
- FIG. 28 illustrates the charge/discharge voltage profile of an aluminum ion battery having an organic electrolyte.
- FIG. 29 compares the voltage profile of an aluminum ion battery having a 0.5 M A1(N(3 ⁇ 4) 3 (aq) electrolyte (curve 1, filled triangles) to the voltage profile of an aluminum ion battery having a 0.5 M A1(N(3 ⁇ 4) 3 (aq) electrolyte containing 10% methanol (curve 2, filled circles).
- the aluminum ion battery chemistry described in this disclosure relies on simple electrode and aqueous electrolyte chemistry and is based on the movement of
- incorporación of aluminum anode and graphite or acid-treated lithium manganese oxide cathode, along with an aqueous electrolyte comprising an inexpensive aluminum salt ensures cost-competitiveness of the technology.
- Aluminum is abundantly available and is inherently safer and electrochemically more robust compared to lithium metal, facilitating the use in aqueous environments as well as ambient atmospheric conditions in a safe and reliable manner.
- the approach adopted here to incorporate hydrophilicity to aluminum- based anodes is inexpensive and highly scalable.
- Both carbon and lithium manganese oxide cathodes are easy to manufacture and are considered to be extremely safe over a wide range of operating conditions and are compatible with a wide range of aqueous, non-aqueous, ionic and solid electrolytes, lending flexibility and scalability to the battery technology.
- the use of air stable electrodes and aqueous electrolytes is expected to significantly reduce the time, cost and complexity of manufacturing of the proposed aluminum ion aqueous battery relative to other competing battery chemistries that rely on elaborate manufacturing and assembly techniques, often in humidity-controlled dry room environments.
- the preliminary performance parameters indicate excellent reliability and repeatability.
- the estimated volumetric and gravimetric energy density are about 30 Wh/L and 75 Wh/kg respectively for the aluminum-graphite system and 50 Wh/L and 150 Wh/kg respectively for the aluminum- lithium manganese oxide system, normalized with respect to the mass and volume of cathode, thereby offering significant advancements over alternate emerging battery technologies.
- aluminum and “aluminium” are used interchangeably to refer to the same element. “Aluminum” is the preferred term that is used.
- aluminum ion includes aluminum ion, Al 3+ and polyatomic aluminum anions, such as the hydroxyaluminate anion, Al(OH)4 1_ , the tetrachloroaluminate ion, AICI4 1" , the tetrahydroaluminate ion, AIH4 1" , and the hexafluoroaluminate ion, AlFe 1" , aluminum tetranitrate, A1(N03)4 1_ , aluminum disulfate, A1(S04)2 1_ , tetrahydroaluminate ion, AIH4 1" , tetrafiuoroaluminate ion, AIF4 1" , tetraboroaluminate, AIB ⁇ 1" , tetraiodidealuminate, AII4 1” , tetraperchloratealuminate, A
- delivery or “delithiated” refers to the removal of lithium from lithium manganese oxide, including removal by chemical methods, such as acid treatment, and electrochemical methods.
- the product of the delithiation of lithium manganese oxide can be expressed as Lii -I Mn0 2 , where x denotes the amount of lithium removed by the delithiation method. As the delithiation method approaches complete removal of lithium, x approaches 1, and the product is substantially Mn02. In certain embodiments, the product is substantially Mn02.
- the aluminum-ion battery storage technology is based on the movement of aluminum ions between an anode and a cathode, through an aqueous electrolyte and a separator that is permeable to the aluminum ions.
- the aluminum ions are polyatomic aluminum anions.
- the separator is a polymeric material.
- a porous, at least partially hydrophilic polymer separator provides an insulating separation layer between the anode and cathode, thereby preventing potential shorting between the two electrodes.
- the polymer separator is a polypropylene, cellulose ester or nylon separator. The porosity of the separator is adapted to facilitate the movement of the aluminum ions between the anode and cathode.
- Aluminum electrochemistry has several advantages over the other battery technologies that are available today.
- Aluminum has a theoretical energy density of 1060 Wh/kg, compared to 406 Wh/kg of lithium ions, due to the presence of three valence electrons in aluminum as compared to one valence electron in lithium.
- Aluminum is the third most abundant element (after oxygen and silicon), and the most abundant metal available in the earth's crust (8.1 weight %), compared to lithium (0.0017 weight %), sodium
- aluminum is both mechanically and electrochemically robust and can be safely operated in ambient air as well as humid environments while simultaneously facilitating a greater flexibility in the choice of electrolytes (aqueous, organic, ionic and solid) and operating conditions.
- electrochemically active elements that form hydroxides that possess sufficient ionic mobility and electrical conductivity may also be used.
- Such elements include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as calcium and magnesium, transition metals such as manganese, and post- transition metals such as tin.
- the electrolyte comprises an aqueous solution of an aluminum salt.
- a preferred solvent is deionized water.
- the aluminum salts include aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum bromide hexahydrate, aluminum fluoride, aluminum fluoride trihydrate, aluminum iodide
- Preferred aluminum salts are aluminum nitrate, aluminum bromide hexahydrate, aluminum fluoride, aluminum iodide hexahydrate, and combinations thereof.
- the aluminum salt is aluminum nitrate.
- the aluminum salt is present in an aqueous solution of about 0.05 M to about 5.0 M. In some embodiments, the aluminum salt is present in an aqueous solution of about 0.5 M to about 3.0 M. In certain embodiments, the electrolyte comprises about 0.1M to about 3.0 M sodium nitrate aqueous solution. In certain preferred
- the electrolyte comprises about 1M to about 3.0 M sodium nitrate (aqueous).
- aqueous aluminum salt electrolyte is environmentally benign, non-toxic and non-flammable and is therefore safer than organic electrolytes used in commercial lithium ion batteries and many sodium ion batteries today.
- an anode comprises aluminum metal foils.
- the aluminum metal foil has been treated to increase its hydrophilic properties.
- an anode comprises an aluminum compound selected from the group consisting of an aluminum transition metal oxide (Al x M y O z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range from 0 to 8, inclusive), an aluminum transition metal sulfide (Al x M y S z , where M is a transition metal selected from the group consisting of iron, vanadium, titanium, molybdenum, copper, nickel, zinc, tungsten, manganese, chromium, and cobalt, and x, y, and z range from 0 to 8, inclusive), an aluminum transition metal nitride (Al x M y
- an anode comprises an alloy of aluminum and at least one metal selected from the group consisting of lithium, sodium, potassium, manganese and magnesium.
- the anode comprises aluminum and at least one of manganese, magnesium, lithium, zirconium, iron, cobalt, tungsten, vanadium, nickel, copper, silicon, chromium, titanium, tin and zinc.
- the operating voltage in batteries that use carbon- based cathodes could be increased through the incorporation of high activation energy alloy anodes.
- Improvement of cathode materials can be gained by introduction of porosity and voids or modifications in the grain structure and orientation within the existing graphite or lithium manganese oxide compositions. Such improvements can provide a more efficient movement and storage of larger charged ions in the discharge reaction, thereby increasing the net capacity of the battery.
- Alternatives to aluminum anodes such as aluminum metal sulfides and aluminum metal oxides can potentially offer higher operating voltages, associated with the high activation energy of such compounds. Moreover, such alternatives also facilitate the incorporation of a mixed, hybrid-ion technology whereby the capacity contribution is available from more than one metal ion, thereby directly increasing the achievable capacities and hence, available energy densities. Such alternatives to aluminum anodes are also more stable over a wider range of operating parameters such as mechanical stresses, high / low operating temperatures and choice of electrolytes.
- Cobalt changes its oxidation state from Co 2+ to Co 4+ following the dissociation reaction and the release of one aluminum ion and three lithium ions.
- the active ions may come from the electrode comprising of aluminum alloys or aluminum-based compounds, an electrolyte comprising of one or more of aluminum salts, salts of one or more of aluminum, carbon, lithium, sodium, potassium, calcium, magnesium, manganese and other active ions such as sulfate, phosphate, nitrate, hydroxide, oxides, carbonates and halides
- an electrolyte comprising of one or more of aluminum salts, salts of one or more of aluminum, carbon, lithium, sodium, potassium, calcium, magnesium, manganese and other active ions such as sulfate, phosphate, nitrate, hydroxide, oxides, carbonates and halides
- electrolyte comprises water (solvent), methyl chloride (salt) and aluminum chloride (salt) and the anode is aluminum metal.
- Aqueous electrolytes containing a dispersion of alternate aluminum salts can effect changes in ionic mobility and operating voltages.
- Electrolytic additives such as lithium chloride and sodium sulfate are being studied to understand their effect on operating voltages.
- additional metal salts will be incorporated into the electrolyte based on the confirmation of an alternate aluminum-metal alloy anode. Studies are also underway to further improve the electrolyte performance through incorporation of electrolytic salts or hydrolysis suppressants.
- hydrolysis suppressants including but not limited to phosphoric acid, phosphorous acid, acetic acid, carboxylic acid, formic acid, formamides, halogenated hydrocarbons, silicone, sulfates, nitrates, halides and phosphates of alkali metals including lithium, sodium, potassium and calcium, bis(trifiuoromethane)sulfonamides and
- bis(fluorosulfonyl)imides of alkali metals including lithium, sodium, potassium and calcium, epoxy, mineral oils, synthetic hydrocarbon oils, esters, aromatic halides, ethers and aromatic ethers can used.
- ionic liquid electrolytes offer the ability to achieve significantly higher operating voltages (typically, > 5 V), thereby increasing the achievable energy density (defined as the product of charge storage and operating voltage).
- Solid electrolytes comprising aluminum and aluminum-metal-based salts dispersed in polymers such as polyethylene oxides will also be tested in the proposed aluminum ion battery chemistry. Solid electrolytes are low cost alternatives to ionic electrolytes that allow reasonably high operating voltages along with a marked improvement in terms of ionic mobility.
- the separator is a porous polypropylene separator or a nylon membrane separator that provides an insulating layer between the anode and cathode along and provides sufficient porosity for the efficient transport of ions between the two electrodes.
- the separator comprises a porous polymer material selected to provide the needed functionality at lesser expense, which can significantly drive down the cost of the technology.
- Cathode Materials Two cathode materials were studied in working examples: acid or electrochemically treated lithium manganese oxide and graphite-graphite oxide composite.
- a suitable cathode material should have sufficient porosity and inter-sheet voids to accommodate the insertion and intercalation of large polyatomic aluminum anions.
- the cathode material should also be at least partially hydrophilic, or treated to achieve at least partial hydrophilicity, for wettability with an aqueous electrolyte.
- cathode materials meet these criteria, but other materials, notably graphene, polyvinyl alcohol, polyacrylic acid, polymethyl methacrylate, polyvinylpyrrolidone, polyethyleminine, polyethylene glycol, polyethylene oxide, tin oxide, vanadium oxide, titanium oxide, silicon oxide, iron oxide, cobalt oxide, manganese dioxide, molybdenum sulfide, tungsten sulfide, iron phosphate, silicon, molybdenum, tin and germanium could also meet these criteria.
- Pristine graphite cathodes do not typically provide large inter-sheet voids and porosity or hydrophilicity. While oxygen plasma treated graphite could improve the hydrophilicity of the cathode material, there is an issue of whether inter-sheet voids would accommodate large polyatomic aluminum anions.
- the spinel structure of lithium manganese oxide provides hydrophilicity as well as porosity and inter-sheet voids suitable for accommodating large polyatomic aluminum anions.
- graphite - graphite oxide composites were found to be suitable cathode materials for the proposed aluminum-ion chemistry, owing to the hydrophilicity and large inter-sheet voids introduced by the oxygen atoms.
- graphene also has sufficiently large inter-sheet voids, owing to the precursor graphene oxide material, which is subsequently reduced to increase conductivity and form graphene.
- graphene is inherently hydrophobic and therefore, graphene sheets need to be exposed to oxygen plasma to introduce oxygen containing species and improve hydrophilicity.
- graphene can be mixed with hydrophilic functional groups, such as hydroxyls, carbonyls, carboxyl, aminos, phosphates and sulfhydrils, to introduce partial hydrophilicity.
- Additional alternate cathode materials capable of accommodating the diffusion and storage of large aluminum-based ions, such as tin oxide, vanadium oxide, titanium oxide, silicon oxide, iron oxide, cobalt oxide, manganese dioxide, molybdenum sulfide, tungsten sulfide, iron phosphate, silicon, molybdenum, tin and germanium, are being studied to evaluate on the cost, porosity and inter-sheet voids of the potential materials.
- Lithium manganese oxide materials can be improved by leaching lithium atoms from the lithium manganese oxide materials through treatment with acids.
- a mineral acid such as nitric acid or hydrochloride acid
- the lithium atoms are removed in the form of the corresponding lithium nitrates or lithium chlorides, thereby creating additional voids within the cathode structure.
- Suitable acids include aqueous solutions of 10%-90% nitric, hydrochloric, sulfuric, acetic, hydroiodic, hydrofluoric, or phosphoric acid.
- lithium atoms can be removed by dispersing lithium manganese oxide in an acidic medium (30% - 70% concentrated hydrochloric or nitric acids) and sonicated for 1-6 hours until a stable dispersion is obtained. In other embodiments, lithium atoms can be removed by dispersing lithium manganese oxide in an acidic medium (where the pH of the medium is maintained between 0.01 and 7.0) and sonicated for 1-24 hours until a stable dispersion is obtained If nitric acid is used the color of the lithium manganese oxide changes from black to brownish-red.
- lithium atoms can be removed by stirring the suspension of dispersing lithium manganese oxide in an acidic medium at room temperature for about 0.5 to about 6 hours, typically about two hours.
- lithium atoms can be removed by stirring the suspension of dispersing lithium manganese oxide in an acidic medium (where the pH of the medium is maintained between 0.01 and 7.0) at room temperature for about 1 to about 24 hours, typically about twelve hours.
- the suspensions were stirred for various durations from 0.5 hours to 24 hours at different temperatures from room temperature to about 80 °C.
- the resulting suspension is then filtered through a filter membrane with pore size ranging from 0.1 - 40 ⁇ , preferably with a pore size greater than 0.2 ⁇ and is repeatedly washed with deionized water or ethanol to remove trace amounts of residues, such as L1NO 3 .
- Suitable filter membrane materials such as nylon, are those that can withstand the acid used in the process.
- the filtrate is then dried in a vacuum furnace to obtain the resultant powder, Lii_ x Mn0 2 , where x denotes the amount of lithium removed by the acid treatment process. As the acid treatment approaches complete removal of lithium, x approaches 1, and the product is substantially Mn0 2 .
- lithium manganese oxide is dispersed in 30% concentrated hydrochloric acid or 67% concentrated nitric acid and sonicated for six hours until a stable dispersion is obtained. Formation of a dispersion is indicated by a change in color from black to reddish brown. The resulting suspension is then filtered through a Whatman nylon membrane filter with pore size ranging from 0.2 - 0.45 ⁇ and is repeatedly washed to remove trace amounts of the acid. The residue is then dried in a vacuum furnace at 1 10 °C to obtain the resultant powder, Lii_ x Mn02.
- acid-delithiated or electrochemically delithiated manganese oxide maybe further subjected to a hydrothermal reaction, steam exfoliation or gas-based exfoliation.
- Hydrothermal reaction involves combining Lii_ x Mn0 2 powder with one or a combination of deionized water, base (such as KOH), acid (such as H2SO4), metals (such as copper) and carbon, sealing the mixture in a hydrothermal pressure chamber and heating the chamber at temperatures ranging from 90 °C to 900 °C for 0.5 hours to 24 hours. The product is then washed several times in deionized water and ethanol to obtain the porous Lii_ x Mn0 2 .
- the product may be further subject to wet or dry etching to remove trace contaminants such as metals, oxides, sulfides, sulfates and hydroxides.
- Steam exfoliation or gas-based exfoliation (where the gas may include one or a combination of and not limited to carbon dioxide, carbon monoxide, sulfur dioxide, nitrogen dioxide) rely on a flow of steam or gas within a temperature range of 100 °C to 2000 °C and a pressure range of 1 atmospheres to 10 atmospheres to introduce structural expansion in Lii_ x Mn0 2 .
- lithium manganese oxide, acid-treated lithium manganese oxide, electrochemically delithiated lithium manganese oxide, lithium metal manganese oxide, acid-treated lithium metal manganese oxide, transition metal oxide, transition metal sulfide, transition metal nitride, transition metal carbide, aluminum transition metal oxide, aluminum transition metal sulfide, aluminum transition metal nitride, aluminum transition metal carbide, graphite metal composite, graphite-graphite oxide, manganese dioxide, electrolytic manganese dioxide, sulfur composites, phosphorus composites, and graphene can be further mixed with a metal such as copper, nickel, iron, zinc, lithium, sodium, potassium, magnesium, titanium, vanadium, chromium, molybdenum, tungsten, manganese, cobalt, indium, aluminum and lead, a semi-metal or metalloid such as boron, silicon and germanium, zeolite and oxides, phosphates, phosphides, sulfates
- Batteries were fabricated that used the aluminum based electrochemistry, including an aluminum anode and an aqueous solution of an aluminum salt as an electrolyte.
- batteries contained an aluminum anode, an acid treated lithium manganese oxide cathode and an aqueous solution of an aluminum salt as an electrolyte in a coin cell configuration.
- batteries contained an aluminum anode, a graphite-graphite oxide composite cathode and an aqueous solution of an aluminum salt as an electrolyte in a coin cell configuration.
- batteries contained an aluminum anode, a graphene cathode and an aqueous solution of an aluminum salt as an electrolyte in a coin cell configuration.
- the batteries having an aluminum anode and an acid treated lithium manganese oxide cathode chemistry provided an open circuit voltage of about 1 volt.
- the batteries having an aluminum anode and graphite-graphite oxide composite cathode provided an open circuit voltage between 600 mV and 800 mV.
- the batteries having an aluminum anode and a graphene cathode provided an open circuit voltage between 600 mV and 800 mV.
- FIG. 1A is a photograph of a piece of aluminum foil treated with a drop of 1
- FIG. IB is a photograph of the piece of the treated aluminum foil of FIG. 1A showing a change in the appearance of the drop of the aqueous solution of lithium hydroxide. After a short time the aqueous solution of lithium hydroxide was wiped away and the surface of the aluminum foil was allowed to air dry at room temperature (25 °C). Reaction times of 5- 10 seconds to 1 hour have been tested, but the reaction appears to be complete in 5- 10 seconds.
- FIG. 1 C is a photograph of the piece of treated aluminum foil of FIG. IB showing the greyish-white appearance of the aluminum foil following the drying of the lithium hydroxide solution.
- FIG. ID is a photograph of the piece of treated aluminum foil of FIG.
- FIG. IE is a photograph of a drop of deionized water on untreated aluminum foil for comparison to FIG. ID.
- an aqueous solution of about 0.01M to about 5.5M lithium hydroxide can be used.
- FIG. 2 is a schematic diagram of an exploded view of a test battery 100 in a coin cell format, showing the positive case 1 10, a spring 120, a first spacer 130, a cathode 140, a separator 150, an anode 160, a second spacer 170 and the negative case 180.
- aliquots of the electrolyte are placed between the separator 150 and the anode 160, as well between the separator 150 and the cathode 140.
- the first spacer 130, the cathode 140, the separator 150, the anode 160, and the second spacer 170 are immersed in and equilibrated with the electrolyte prior to assembly of the test battery.
- a battery grade aluminum foil is used as the anode 160.
- Battery grade foils are generally > 99% pure.
- the thickness of any battery-grade foil should be limited, since the thickness directly impacts the volumetric energy density at the system level, defined as: (Net Available Energy Density in Watt-hours / Total volume of the electrode, including the current collector).
- Thicker current collectors also reduce the maximum number of electrodes that can be stacked in a battery pack / module.
- battery-grade current collectors vary between 8 - 30 ⁇ in thickness.
- Mechanical robustness is also necessary to prevent any wear and tear during the electrode coating or cell / battery assembly process.
- the tensile strength of commercial battery-grade foils vary between 100-500 N/mm.
- Suitable battery grade aluminum foil and other materials may be obtained from MTI Corporation, Richmond, CA and Targray Technology International Inc., Laguna Niguel, CA.
- Battery grade lithium manganese oxide cathode and graphite may be obtained from MTI Corporation, Richmond, CA and Sigma Aldrich, St. Louis, MO.
- Graphene and graphite oxide may be purchased from Sigma Aldrich, St. Louis, MO, Graphene Supermarket, Calverton, NY, and ACS Material, Medford, MA.
- hydroxyaluminate (Al(OH)4 ⁇ ) ions were formed according to chemical reaction (6):
- the hydroxyaluminate ions diffuse through the pores and inter- sheet voids of the cathode material and are oxidized to give Al(OH) 3 (aluminum hydroxide).
- Al(OH) 3 aluminum hydroxide
- the presence of aluminum hydroxide on the aluminum foil anode of a completely (100%) discharged test cell has been confirmed using x-ray photoelectron spectroscopy (XPS), as shown in FIG. 3.
- XPS profile shows one major Al 2p transition at 74.3 eV, indicating the presence of gibbsite, Al(OH)3 on the anode.
- the transition at 74.3 eV has been reported to be characteristic of gibbsite by Kloprogge et al.
- the lithium ions would then flow towards the aluminum anode and possibly intercalate with aluminum, owing to the high affinity between lithium and aluminum, forming a hybrid-ion battery chemistry.
- This hypothesis could relate to an observed increase in capacity (about 40%) compared to the capacities obtained with carbon-based cathodes devoid of any lithium component.
- XPS examination of the aluminum anode in a test cell having a lithium manganese oxide cathode did not show any significant signs of lithium-based alloys at the anode site at a fully charged state.
- the aluminum-ion cells were cycled between safe voltage cut-off limits of 0 V (discharge) and 2 V (charge). However, the average operating voltage was about 1.1 V for discharge and 1.2 V for charge for the cells having an aluminum anode and an acid treated lithium manganese oxide cathode (FIG. 4A) and 0.4 V for discharge and 0.9 V for charge for the cells having an aluminum anode and a graphite-graphite oxide cathode (FIG. 4B), within the safe voltage cut-off limits.
- FIG. 4A shows the voltage profile that was produced by applying current at a current density of 0.1 niA/cm 2 to a test battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1 , a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 um, and a 0.5 M aqueous aluminum nitrate electrolyte.
- FIG. 4A shows the voltage profile that was produced by applying current at a current density of 0.1 niA/cm 2 to a test battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1 , a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 um, and a 0.5 M aqueous aluminum nitrate electrolyte.
- FIG. 4B shows the voltage profile that was produced by applying current at a current density of 0.1 niA/cm 2 to a test battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising graphite-graphite oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte.
- the observed average operating voltage is significantly higher with the use of acid treated lithium manganese oxide cathodes, possibly owing to the higher activation energy for diffusion and intercalation of ions.
- Carbon is known to possess a sufficiently low activation energy for diffusion and intercalation of metal ions (the intercalation voltage of lithium ions in carbon against a lithium metal occurs at about 100 mV).
- FIG. 4A unlike the voltage profiles observed in sodium ion batteries, enabling critical advantages such as incorporation of simpler battery management systems and installation of fewer cells in series owing to the high operating voltages, all of which can significantly drive down the cost of the technology.
- the charge / discharge rates were limited between C/l and C/12 (a rate of C/n implies charge or discharge in n hours). While cycle life testing is currently underway, both the graphite -based and lithium manganese oxide -based
- FIG. 5A shows the battery charge capacity, open triangles, and discharge capacity, open circles, as a function of the cycle index of a battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and a graphite-graphite oxide composite cathode.
- the coulombic efficiency was estimated to be close to 100% over 30
- FIG. 5B shows the battery charge capacity as a function of cycle index of a battery having an anode comprising an aluminum foil treated with LiOH as described in Example 1, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M aqueous aluminum nitrate electrolyte and an acid treated Lii_ x Mn02 cathode.
- the reduction in capacity after over 800 charge / discharge cycles is about 3 % of the original capacity.
- the acid treated lithium manganese oxide - aluminum chemistry with an aqueous electrolyte provides higher energy density (about 100- 150 Wh/kg) and volumetric energy density (about 30-60 Wh/L) than the graphite-graphite oxide - aluminum chemistry (about 50-75 Wh/kg and about 20-30 Wh/L), owing to the higher electrochemical affinity towards aluminum observed in acid treated lithium manganese oxide.
- graphite-graphite oxide cathodes are generally cheaper than lithium manganese oxide. Further modifications to the cathode chemistry may significantly boost the performance metrics of graphite-graphite oxide cathodes.
- n is the number of electrons exchanged
- F Faraday's constant
- A is the area of the electrode
- D is the diffusion coefficient
- C is the molar concentration
- t is time for diffusion and 3 ⁇ 4is the radius of the cathode particles.
- the diffusion coefficient of hydroxyaluminate ions in lithium manganese oxide and graphite-graphite oxide composite cathodes was calculated to be 1.14xl0 "7 cm 2 /sec and 3.54xl0 "8 cm 2 /sec respectively, well within the acceptable range of ion diffusion coefficients in metal-ion batteries.
- EIS electrochemical impedance spectroscopy
- the EIS profile was fitted with a Randies equivalent circuit model and the electrolytic resistance, interfacial resistance and charge transfer resistances, summarized in Table 2, below, were estimated based on the fit.
- the electrolytic resistances were estimated to be between 2-4 ⁇ , significantly lower than the typical electrolytic resistances of 10-20 ⁇ , consistent with the absence of any gas pockets within the electrolyte.
- the interfacial resistance was estimated to be 1 1 ⁇ at the lithium manganese oxide - electrolyte interface and 20 ⁇ at the graphite-graphite oxide - electrolyte interface, again consistent with the absence of any insulating gas pockets.
- the charge transfer resistance of acid treated lithium manganese oxide was estimated to be about 100 ⁇ while that of graphite-graphite oxide composite was estimated to be slightly higher at about 131 ⁇ , possibly attributed to the presence of oxygen-containing functional groups.
- Charge transfer resistance is indicative of the electron conductivity of the active electrode material and is independent of the formation of gas pockets.
- a charge-transfer resistance of 100- 150 ⁇ is generally considered to be suitable for battery storage applications.
- FIG. 8A A schematic depiction of the prismatic cell assembly is provided in FIG. 8A.
- the prismatic assembly 80 comprised a metallic or a polymer base plate 82 an insulating polymer gasket 84 and a top plate resembling the structure of the base plate, not shown for clarity.
- the components had threaded through-holes along its edges.
- nylon screws were used to seal the assembly while simultaneously preventing a shorting between the two plates while for polymer base and top plates, both nylon and metallic screws sufficed.
- a prismatic cell was assembled with an electrode area of 2 cm x 5 cm and rated at a capacity of 1 mAh. Standard polypropylene separators were used in the assembly.
- the cell comprised a single interface, although multiple interfaces can also be incorporated with the setup.
- FIG. 8B illustrates the discharge voltage profile of a prismatic cell rated at 1 mAh.
- the cell had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , a 0.5 M aqueous aluminum nitrate electrolyte and were tested at 10 ⁇ /cm 2 .
- Pouch cells were assembled by introducing the anode-separator-cathode interface in the cell assembly section of an aluminum laminate pouch cell packaging case. This was followed by connecting the electrodes to an aluminum current collector tab through mechanical contacts or ultrasonic welding. Next, three edges of the pouch cell were sealed using a heat sealer set between about 20-50 psi and 150-180 °C. A section of the pouch cell was retained at one of the edges that acted as the gas trap. The purpose of the gas trap is to contain the gas evolution during the formation cycle, after which the gas trap section can be cut and the edge resealed for subsequent cycling. Prior to sealing the fourth and final edge of the pouch cell, the electrodes-separator assembly was wetted with the electrolyte.
- FIG. 9A A schematic diagram of a pouch cell 90 is provided in FIG. 9A, showing a cell assembly section 92, a gas trap 94 and current collector terminals 96.
- a pouch cell assembled in this fashion involved electrodes between 1 cm x 0.8 cm and 1 cm x 1 cm, rated between 0.06-0.08 mAh.
- FIG. 9B illustrates the discharge profile of a pouch cell comprising 0.8 cm x 1 cm electrodes and hydrophilic polypropylene separators.
- the cell had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid- treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , a 0.5 M aqueous aluminum nitrate electrolyte and were tested at about 25 ⁇ /cm 2 .
- a pouch cell assembled in this fashion can also incorporate scalability and multiple interfaces can be packed in series / parallel configurations to achieve a pre-determined capacity and voltage rating.
- Pouch cells having one to four interfaces were assembled, sealed and tested at current densities ranging between 5 ⁇ /cm 2 and 20 ⁇ /cm 2 .
- the anode comprised phosphate-treated aluminum foil
- the cathode consisted of acid-delithiated manganese dioxide coated on nickel foil
- the separator was a Celgard 3500 polypropylene sheet.
- the separator thickness was about 25 ⁇ and the average pore size was about 67 nm, and the electrolyte was 0.5 M aqueous aluminum nitrate.
- the phosphate treatment of the aluminum anode was carried out by immersing pristine aluminum foil in a solution of about 0.1 - 1 M phosphoric acid, with the addition of about 0.1-20 weight% sodium nitrite as an oxidizing agent. The pH was maintained between 1 and 4. The reaction time was between about 1-60 minutes at 20-60 degrees Celsius.
- the pouch cells were placed between adjustable clamps prior to cycling. The cells were then charged and discharged within a voltage window of 0.75 V and 1.7 V (FIG. 9C). The cells displayed an average gravimetric capacity ranging between -40 niAh/gcathode (when tested at 20 ⁇ /cm 2 ) and -70 mAh/gcathode (when tested at 5 ⁇ /cm 2 ).
- Liquid metal batteries operate at very high temperatures and incorporate the use of toxic materials such as antimony and lead as well as flammable lithium metal, thereby posing serious safety concerns.
- FIG. 8 is a block diagram of an embodiment of a system 800 that incorporates the battery 810 of the present disclosure, showing a controller 820 that is operatively connected to battery 810, a source of electrical power 830, a local electrical load 840 and an electrical power distribution grid 850.
- the source of electrical power 830 is based on a renewable energy source, that is, a wind turbine or a solar panel.
- the controller 820 is operatively connected to the source of electrical power 830 and to the battery 810 of the present disclosure to mediate the charging of the battery 810.
- the controller 820 is operatively connected to the source of at least one local electrical loads 840 and to the battery 810 of the present disclosure to mediate the discharging of the battery 810.
- the local electrical loads 840 can include devices requiring DC electrical supply or AC electrical supply, including, without limitation, cell phone or computer battery chargers, computers, home appliances, water pumps, and refrigeration equipment.
- the controller 820 is operatively connected to a power distribution grid 850 to permit selling excess electrical power to the power distribution grid 850.
- the electrolyte 0.5 M aqueous A1(N0 3 ) 3 , was mixed with
- FIG. 1 1 compares the discharge and charging properties of two batteries differing in electrolyte composition: one battery having a 0.5 M A1(N0 3 )3 (aq) electrolyte (curve 1) and another battery having a 0.5 M A1(N0 3 )3 and 2 M LiOH (aq) electrolyte (curve 2).
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid- treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and was tested at current densities of 10 ⁇ /cm 2 .
- the results illustrated in FIG. 1 1 suggest that incorporation of a composite electrolyte can result in a reduced over-potential. Incorporation of LiOH in the electrolyte reduces the over-potential by preventing loss of active Al-ion species during transportation in the electrolyte.
- the over-potential relates to the discharge voltage hysteresis caused by the cell composition.
- curve 1 in which the electrolyte is 0.5 M (aq) A1(N0 3 )3 with no LiOH additive, the higher internal resistances cause an increase in the AV value (which is known as the over- potential), causing it to discharge at a lower voltage.
- the pore size of the separator can dictate the ion transportation kinetics.
- Standard batteries such as lithium ion batteries generally use a polypropylene separator with pore sizes less than 0.1 ⁇ , which is sufficient to permit the flow of the relatively smaller lithium ions.
- small pore sizes hinder the efficient flow of ions, resulting in an increased internal cell resistance and lower charging rate and discharging rate. Therefore, in an effort to reduce accumulation of charge and resistance build-up at the separator surface, batteries having separators with larger pore diameters were studied.
- the separators that were tested included polypropylene separators (standard,
- FIG. 12 illustrates the effect of separator pore size on the average discharge potential produced at a given current density, where pentagons (1) represent measurements made on a battery having a polypropylene separator with 0.067 ⁇ pores, a triangle (2) represents measurements made on a battery having a mixed cellulose ester separator with 0.20 ⁇ pores, a circle (3) represents measurements made on a battery having a nylon separator with 0.45 ⁇ pores, squares (4) represent measurements made on a battery having a nylon separator with 0.80 ⁇ pores, and diamonds (5) represent measurements made on a battery having a glass microfiber separator with 1.0 ⁇ pores.
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- Polypropylene separators were tested at 10 ⁇ /cm 2 and 20 ⁇ /cm 2 ; mixed cellulose ester separators (triangle) and nylon separators (circle) were tested at 20 ⁇ /cm 2 ; nylon separators (squares) were tested at 20 ⁇ /cm 2 , 40 ⁇ /cm 2 and 50 ⁇ /cm 2 ; and glass microfiber separators (diamonds) were tested at 20 ⁇ /cm 2 and 40 ⁇ /cm 2 .
- the pore size of the separators can also influence suitability of a battery for an intended application. Understandably, separators with larger pore sizes are also thicker than those with smaller pore sizes. Therefore, while the range of optimum pore sizes is rather large, a specific choice can be made based on the intended application. For example, smaller pore sizes (example, polypropylene, 0.067 ⁇ pore diameter and 25 ⁇ thick) can optimize energy density (volumetric and gravimetric) while larger pore sizes (example, glass microfiber, 1 ⁇ pore diameter and 500 ⁇ thick) can optimize rate capability and hence, improve the power density of such batteries.
- smaller pore sizes example, polypropylene, 0.067 ⁇ pore diameter and 25 ⁇ thick
- larger pore sizes example, glass microfiber, 1 ⁇ pore diameter and 500 ⁇ thick
- FIG. 13 illustrates the discharge of a battery having a polypropylene separator with 0.067 ⁇ pores at a current density of 10 ⁇ /cm 2 .
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- FIG. 14 illustrates the discharge of a battery having a nylon separator
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- FIG. 15 illustrates the discharge of a battery having a glass microfiber separator with 1.0 ⁇ pores at a current densities of 20 ⁇ /cm 2 (curve 1) and 40 ⁇ /cm 2 (curve 2).
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid- treated lithium manganese oxide, and the electrolyte was an 0.5 M aqueous aluminum nitrate solution.
- separators with larger pore sizes enabled a higher voltage of operation, even at significantly higher current densities.
- a polypropylene separator (0.067 ⁇ pore size), a nylon separator (0.8 ⁇ pore size) and a glass microfiber separator (1 ⁇ pore size) displayed an average discharge potential of 1.01 V, 1.17 V and 1.18 V respectively. See FIG. 12.
- Table 3 summarizes the average charge and discharge potential and the typical charge and discharge voltage hysteresis values for batteries constructed with various separators, compared against baseline (standard 0.067 ⁇ pore size polypropylene separator tested at a current density of about 10 ⁇ /cm 2 ).
- Table 3 shows that batteries having nylon or glass microfiber separators produced higher voltages (1.17 V - 1.18 V) compared to standard polypropylene separators (1.11 V) even at twice the current density.
- discharge and charge hysteresis voltages were found to be within sufficiently acceptable values even at four- fold higher current densities (data not shown).
- Suitable separators also include, but are not limited to, polyvinylidene fluoride, polytetrafluoroethylene, cellulose acetate, nitrocellulose, polysulfone, polyether sulfone, polyacrylonitrile, polyamide, polyimide, polyethylene, polyvinylchloride, cellulose, polyester, rubber, polyolefins, glass mat, polypropylene, mixed cellulose ester, nylon, glass microfiber, polycarbonate, polysulfones, cotton and methacrylates.
- anion exchange membranes and proton exchange membranes such as NAFION® may be used as the separator.
- Ceramic separators including, but not limited to, alumina, zirconium oxides and silicon oxides can also be used. As identified through the tests, the separators can have a pore size ranging between 0.067 ⁇ and 1.2 ⁇ . However, separators with lower or higher porosities and thicknesses can also be used for specific applications.
- a solid polymer electrolyte incorporating at least one of aluminum salts with or without at least one of hydroxides can be used in certain embodiments.
- SPEs solid polymer electrolyte
- the aluminum salt ensures efficient flow of aluminum ions through the electrolyte
- added hydroxides contribute OH " to enable the formation of Al(OH)4 1_ ions during the transportation of ions.
- Aluminum salts include but are not limited to A1(N0 3 )3, A1 2 (S0 4 )3 and A1C3 ⁇ 4 and combinations and variations thereof.
- Hydroxides include but are not limited to Al(OH) 3 , LiOH, NaOH, KOH, Ca(OH) 3 , Mg(OH) 2 and NH4OH and mixtures thereof.
- a cross-linking polymer such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF:HFP) or polymethyl methacrylate (PMMA) is mixed with aluminum nitrate in a ratio ranging between 1 : 1 and 1 : 10. The mixture is then dissolved in a solvent such as N-methyl pyrrolidone or dimethyl sulfoxide and heated at temperatures ranging from 50-200 °C under constant stirring for 2 hours in order to initiate the polymerization reaction.
- PVDF:HFP poly(vinylidene fluoride-co-hexafluoropropylene)
- PMMA polymethyl methacrylate
- the solution is observed to turn viscous, following which it is transferred to a vacuum furnace chamber where it is further heated at the above temperature range for 2-24 hours in order to remove the solvent and obtain the resultant solid polymer electrolyte.
- the produced solid polymer electrolyte comprises the aluminum salt and the cross-linking polymer in the weight ratio that was selected, typically the cross-linking polymer at 9-50 wt% and the aluminum salt at 50-91 wt%).
- the cross-linking polymer may be mixed with aluminum halides (such as AICI 3 , AIB ⁇ , AII 3 ) and l-ethyl-3-methylimidazolium chloride (EMIMCl, Sigma-Aldrich), l-ethyl-3-methylimidazolium bromide (EMIMBr, Sigma- Aldrich), or l-ethyl-3-methylimidazolium iodide (EMIMI, Sigma-Aldrich), where the ratio of the aluminum halide to the l-ethyl-3-methylimidazolium halide ranges from 1 : 1 to 5: 1 (weight: weight).
- aluminum halides such as AICI 3 , AIB ⁇ , AII 3
- EMIMCl l-ethyl-3-methylimidazolium chloride
- EMIMBr l-ethyl-3-methylimidazolium bromide
- EMIMI l-ethyl-3-methylimidazol
- the combined aluminum halide and 1- ethyl methylimidazolium halide is then mixed with the cross linking polymer such as PVDF:HFP or PMMA in a ratio of 1 : 1 to 10: 1 (weigh weight).
- the cross linking polymer such as PVDF:HFP or PMMA
- 0.1 to 1 g of the mixture per mL of solvent is combined with a solvent such as solvent can be N-methyl pyrrolidone or DMSO.
- the mixing and heating steps are similar to the process described above.
- the resultant solid polymer electrolyte will contain aluminum salt, ethyl methylimidazolium halide and the cross-linking polymer in the weight ratio that was chosen, typically the cross-linking polymer at 9-50 wt% and the aluminum salt at 50-91 wt%.
- the mixture dissolved in the solvent is heated between about 50 °C and 200 °C for 2-24 hours under constant stirring. In one example, the mixture was heated at 90 °C continuously for 2 hours under constant stirring. This step initiates the polymerization reaction. At the end of this step, the solution turns viscous indicating successful completion of the polymerization reaction.
- the mixture is then poured into a fiat glass petri dish or other suitable container and transferred to a vacuum furnace where it is heated between 50 °C and 200 °C overnight or for as long as necessary to completely remove the solvent.
- a free-standing SPE is obtained that can be released from the glass surface either mechanically (peeling off) or through the application of ethanol.
- a photograph of a SPE is shown in FIG. 16, which shows the cylindrical, free-standing, translucent solid polymer electrolyte that is about 1 mm thick and about 3 cm in diameter.
- hydroxides in SPEs The addition of hydroxides to the electrolyte, described in Example 3, above, can be achieved by introducing a suitable hydroxide in the mixture in addition to the cross-linking polymer and aluminum salt.
- a suitable hydroxide 100 mg lithium hydroxide and 900 mg aluminum nitrate were added to about 5 mL deionized water which resulted in the formation of aluminum hydroxide by the following reaction:
- PVDF-HFP (Sigma-Aldrich) was dissolved in acetone, at a concentration of 500 mg of the polymer in 5 mL acetone, through bath sonication for up to 6 hours, while the bath itself was maintained at a temperature of 60 °C. The volume of acetone was maintained at 5 mL through subsequent addition of the solvent as and when required.
- 5 niL of the solution was added to 5 niL of the aqueous electrolyte solution comprising the reaction products of lithium hydroxide and aluminum nitrate dispersed in DI water.
- the addition of the PVDF-HFP solution to the aqueous electrolyte solution initiated a polymerization reaction which resulted in the formation of a free-standing solid polymer electrolyte as shown in the inset of FIG. 17.
- a solid polymer electrolyte prepared by the method described in the above paragraph was tested in a 2032 coin cell comprising of a cathode comprising manganese oxide treated by acid-based delithiation followed by lithium hydroxide etching of the cathode, and an anode comprising aluminum foil treated as described in Example 1. No separators or liquid electrolytes were used and the solid polymer electrolyte was sandwiched between the anode and cathode.
- FIG. 17 illustrates the voltage profile of a battery having a solid-polymer electrolyte, showing a short duration of discharge at 50 ⁇ /cm 2 , followed by discharging at
- FIG. 10 An embodiment of a system useful for changing and discharging the disclosed aluminum ion batteries is illustrated in FIG. 10.
- potentiostatic or a combination of potentiostatic and galvanostatic charge cycles were shown to have an impact on the performance, specifically in terms of faster reaction kinetics (rate capability).
- the range of voltages for potentiostatic charge was identified to lie between 1.5 V and 2 V, while the optimum value was identified to be about 1.8 V. At voltages greater than 2 V significant electrolysis was observed, confirmed by a rapid rise in currents.
- a constant voltage sweep rate can be applied to charge the cell in certain embodiments.
- the dV/dt value of the constant voltage sweep rate is from 0.01 mV/second to 100 mV/second.
- Galvanostatic charge and constant voltage sweep rate charge can both be applied in conjunction with a final constant voltage charge to ensure completion of the charge cycle.
- the final constant voltage charge is maintained to achieve trickle charge until the current drops below a predetermined value ranging from 1% to 50% of the current applied during galvanostatic charge cycle.
- the discharge step can be a combination of high and low current density galvanostatic steps, allowing the cell chemistry to optimize coulombic efficiency and ensure maximum diffusion of active ions and its participation in electron- exchange reactions. Since the discharge process is a function of the rate at which aluminum ions diffuse through manganese oxide, such a combination of high and low current prevents the build-up of localized charge at the cathode-electrolyte interface and optimizes the efficiency of the cell.
- FIG. 18 shows a discharge profile produced by a combination of low-current and high-current pulses.
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 0.5 M aluminum nitrate (aq) electrolyte and a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ .
- the current densities were switched between 100 A/g (low-current pulse) and 500 A/g (high-current pulse), where the current is normalized with respect to the mass of the cathode. Similar approaches can be used with a system such as the one illustrated in FIG. 10 to improve the overall performance of the battery.
- Lithium manganese oxide is mixed with a polymer binder, a thickening agent, or a mixture thereof combined with a solvent to form a slurry.
- the polymer binder is selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene -butadiene rubber (SBR) and mixtures thereof.
- the thickening agent is a suitable polysaccharide gum known to the art, such as carboxymethyl cellulose (CMC).
- the mixture further comprises a conductive carbon additive, selected from the group consisting of activated carbon, Super-P carbon and mixtures thereof.
- the mixture is combined with a suitable nonaqueous solvent such as N-methyl pyrrolidone.
- a suitable solvents such as water, ethanol or a mixture of water and ethanol.
- a mixture to be used to form a non-aqueous slurry comprises polymer binders such as PVDF and PTFE in concentrations ranging from 0-20 percent by weight (wt%), based on the total weight of the mixture. In certain embodiments, the mixture comprises 2-20 wt% of a polymer binder, based on the total weight of the mixture. In certain embodiments, a mixture to be used to form an aqueous slurry comprises polymer binders such as SBR or polymethyl methacrylate (PMMA) in concentrations ranging from 0-20 wt%, based on the total weight of the mixture.
- polymer binders such as PVDF and PTFE in concentrations ranging from 0-20 percent by weight (wt%), based on the total weight of the mixture. In certain embodiments, the mixture comprises 2-20 wt% of a polymer binder, based on the total weight of the mixture. In certain embodiments, a mixture to be used to form an aqueous slurry comprises poly
- Thickening agents such as carboxymethyl cellulose (CMC) may also be introduced in the mixture in concentrations ranging from 0-20 wt%, based on the total weight of the mixture.
- Conductive additives such as activated carbon and Super-P carbon, when present, can be included in the mixture at concentrations up to 50 wt%, based on the total weight of the mixture.
- the amount of lithium manganese oxide in the mixture can constitute up to 98 wt%, based on the total weight of the mixture. In certain embodiments, the amount of lithium manganese oxide in the mixture is 2- 98%, based on the total weight of the mixture.
- Aqueous Slurry A mixture was made by combining 4 wt% CMC, 6 wt%
- aqueous slurry was then prepared by adding the mixture to deionized water and stirring at room temperature. The viscosity of the resulting slurry was controlled by maintaining the solvent volume to -2.5-4 mL per gram of mixture.
- the aqueous slurry was mixed (Thinky Planetary Centrifugal Mixer ARE-31) for up to 120 minutes at rotational speeds of up to 10,000 rpm before being cast on to a metal substrate.
- the substrate is aluminum.
- the substrate is stainless steel.
- Other suitable substrates include nickel, copper and pyrolytic graphite. The slurry was cast on the substrate using a standard doctor blade coating method.
- Non-aqueous Slurry A mixture was made by combining 10 wt% PVDF, 10 wt% Super-P conductive carbon and 80 wt% lithium manganese oxide by weight, based on the total weight of the mixture. A non-aqueous solution was then prepared by adding the mixture to N-methyl pyrrolidone. The viscosity of the resulting slurry was controlled by maintaining the solvent volume to -2.5-4 mL per gram of mixture. The non-aqueous slurry was mixed (Thinky Planetary Centrifugal Mixer ARE-31) at room temperature for up to 120 minutes and at rotational speeds of up to 10,000 rpm before casting the slurry on to a metal substrate. In certain embodiments, the substrate is aluminum.
- the substrate is stainless steel.
- suitable substrates include nickel, copper and pyrolytic graphite.
- the slurry was cast on the substrate using a standard doctor blade coating method.
- a constant voltage of up to 6 V is then applied to allow delithiation of the lithium manganese oxide cathode.
- An open-circuit voltage reading of above 3 V is indicative of successful delithiation.
- the cathode is removed, washed repeatedly with dimethyl carbonate and water, and dried to obtain electrochemically delithiated manganese oxide cathodes.
- Mn02 cathodes can be increased in terms of both power density (rate capability) and energy density (capacity) through the incorporation of additional structural porosity. Without wishing to be bound by theory, it is believed that porosity allows electrolytic pathways for active ions to reach reaction sites within the cathode, thereby overcoming diffusion limitations (the time active ions would take to diffuse through the bulk of the cathode material), while also ensuring that more active reaction sites are now available for the electrochemical reactions.
- lithium manganese oxide powder is immersed in a 0.1 M to 4 M solution of a hydroxide selected from the group consisting of lithium hydroxide (LiOH), potassium hydroxide (KOH), sodium hydroxide (NaOH), tetramethyl ammonium hydroxide (TMOH) and mixtures thereof.
- a hydroxide selected from the group consisting of lithium hydroxide (LiOH), potassium hydroxide (KOH), sodium hydroxide (NaOH), tetramethyl ammonium hydroxide (TMOH) and mixtures thereof.
- the concentration of the mixture ranges between 0.1 g of lithium manganese oxide in 1 mL of the hydroxide solution to 0.1 g of lithium manganese oxide in 10 mL of the hydroxide solution.
- the hydroxide solution can comprise aqueous solvents, such as water, organic solvents, such as ethanol, or N-methyl pyrrolidone, or a mixture thereof.
- coated lithium manganese oxide cathodes can be directly treated with an aqueous or organic solution of a 0.1 M to 4 M solution of a hydroxide selected from the group consisting of lithium hydroxide (LiOH), potassium hydroxide (KOH), sodium hydroxide (NaOH), tetramethyl ammonium hydroxide (TMOH) and mixtures thereof.
- a hydroxide selected from the group consisting of lithium hydroxide (LiOH), potassium hydroxide (KOH), sodium hydroxide (NaOH), tetramethyl ammonium hydroxide (TMOH) and mixtures thereof.
- FIG. 19 shows discharge voltage profiles illustrating that a combination of hydroxide etching and delithiation of a Mn0 2 cathode along with incorporation of LiOH in the electrolyte can produce about two-fold increase in current densities.
- Curve 1 was obtained from a battery having a 0.1 mAh rating discharged for 8 hours at a current density of 10 ⁇ /cm 2 .
- Curve 2 was obtained from a battery having a 0.1 mAh rating discharged for 5 hours at a current density of 20 ⁇ /cm 2 .
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1 , a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N0 3 )3 and 2 M LiOH (aq) electrolyte.
- FIG. 20 shows a discharging voltage profile (curve 1) and a charging voltage profile (curve 2) of a battery having a cathode comprising Mn0 2 synthesized by a combination of acid-based (nitric acid) delithiation followed by 2M LiOH treatment of the Mn0 2 coated cathode, where the discharge cut-off (dashed line) has been set at 1 V.
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N0 3 ) 3 (aq) electrolyte.
- cathodes produced by acid-based delithiation alone were shown to have an average discharge potential ranging between 0.9 V and 1.1 V. Since the energy density is a product of charge stored (capacity) and nominal voltage, an increased discharge potential directly corresponds to an improvement in energy density.
- FIG. 21 shows a discharging voltage profiles of batteries having different treatments of the delithiated Mn0 2 cathode.
- Curve 1 is the discharging voltage profile of a battery having a cathode comprising Mn02 that was delithiated using nitric acid.
- Curve 2 is the discharging voltage profile of a battery having a cathode comprising Mn0 2 that was delithiated electrochemical delithiation.
- Curve 3 is the discharging voltage profile of a battery having a cathode comprising Mn0 2 that was delithiated using nitric acid, followed by treatment of the cathode with 2M LiOH.
- Each battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, a cathode comprising acid-treated lithium manganese oxide, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N0 3 )3 (aq) electrolyte.
- Porosity may be introduced in the electrodes through incorporation of at least one sacrificial template selected from the group consisting of zeolite, MCM-41 , silicon dioxide, silicon, copper, copper oxide, nickel, nickel oxide, aluminum, aluminum oxide, tungsten, titanium, titanium nitride, gold, chromium, indium titanium oxide and mixtures thereof, followed by etching the sacrificial template either before or after coating the mixture of electrode material plus sacrificial template on to a current collector.
- sacrificial template selected from the group consisting of zeolite, MCM-41 , silicon dioxide, silicon, copper, copper oxide, nickel, nickel oxide, aluminum, aluminum oxide, tungsten, titanium, titanium nitride, gold, chromium, indium titanium oxide and mixtures thereof
- Suitable etchants include acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, buffer oxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, tetramethyl ammonium hydroxide, hydrogen peroxide, ethylenediamine pyrocatechol, water, aqua regia, iodine, potassium iodide and mixtures thereof.
- This method can be used to introduce porosity in both anodes and cathodes, except for when metal foils are directly used as the electrode.
- MCM-41 Mobil Composition of Matter No. 41
- MCM-41 is a mesoporous material with a hierarchical structure from a family of silicate solids that were first developed by researchers at Mobil Oil Corporation for use as catalysts or catalyst supports.
- the concentration of the porous template is between 5-50 wt%, based on the total weight of the MCM-41 and delithiated manganese oxide mixture. The mixture was then ball-milled for 5- 120 minutes to obtain porous manganese oxide.
- the MCM-41 content can be subjected to calcination, whereby the powder is subjected to temperatures ranging between 200 °C and 800 °C in an inert environment.
- MCM-41 can be further partially or completely etched through KOH or buffered oxide etching methods.
- KOH etchant can comprise of 5-60 wt.% of KOH in water.
- Buffered oxide etchant comprises 3: 1 to 9: 1 volume ratio of 5-40 wt% ammonium fluoride in water and 5-49 wt% of hydrofluoric acid in water. Following the etching process, the final product is washed repeatedly with deionized water to remove trace contaminants.
- electrochemical delithiation can also be mixed with zeolite to obtain a porous cathode structure.
- Zeolite is a micro-porous aluminosilicate mineral that can be mixed with the cathode material to achieve porosity.
- concentration of zeolite varies between 1-30 wt% based on the total weight of zeolite and delithiated manganese oxide mixture.
- additives such as polyvinyl alcohol may be introduced in concentrations between 1-30 wt% to further improve the hydrophilicity.
- the mixture was then ball-milled for 5-120 minutes to obtain porous hydrophilic manganese oxide.
- the zeolite template can be partially or completely removed by KOH etching or buffered oxide etching.
- KOH etchant can comprise of 5-60 wt.% of KOH in water.
- Buffered oxide etchant comprises 3: 1 to 9: 1 volume ratio of 5-40 wt% ammonium fluoride in water and 5-49 wt% of hydrofluoric acid in water.
- the final product is washed repeatedly with deionized water to remove trace contaminants.
- Porosity may also be introduced by growing manganese oxide directly on a porous substrate including silicon, silicon dioxide, aluminum, aluminum oxide, tin, tin oxide, copper, copper oxide, nickel, nickel oxide, titanium, titanium oxide, titanium nitride, titanium carbide, carbon, tungsten, gold, platinum, chromium, cobalt and indium titanium oxide.
- the porous substrates may have the morphology of mesh, wires, pillars, spirals or fibers. The porous substrates may or may not be removed using suitable etchants.
- Suitable etchants include acetic acid, phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, buffer oxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, tetramethyl ammonium hydroxide, hydrogen peroxide, ethylenediamine pyrocatechol, water, aqua regia, iodine, potassium iodide and mixtures thereof.
- the porous substrate is left unremoved or partially unremoved, specifically when the substrate is a conductive component, the substrate acts as an ion conducting pathway and participates in electron transfer kinetics.
- ⁇ - ⁇ 2 was synthesized by the reaction of IVfr ⁇ Cu in a 0.5 M ammonium persulfate solution. The pH of the solution was maintained at 8-9 during the reaction. The porous S1O 2 template was mixed in the above solution to deposit ⁇ - ⁇ 2 on the template. The solution was then refluxed at 80 °C to synthesize ⁇ - ⁇ 2. Chemical synthesis of ⁇ - ⁇ 2 was carried out by a reflux reaction method. Manganese acetate was reacted in the presence of dimethylsulfoxide (DMSO) and hydrazine. The porous template was mixed in the above solution for direct deposition of ⁇ - ⁇ 2 on the template. The solution was then refluxed at about 140 °C. The end product was then washed with water after which it was dried in a vacuum oven to obtain the final powder for use in cathodes.
- DMSO dimethylsulfoxide
- a porous-Mn0 2 cathode was produced by mixing the MCM-41 sacrificial template (10 nm to 40 ⁇ particle size, 5 wt% to 90 wt% based on the total weight of the mixture) with chemically delithiated manganese oxide powder.
- the MCM-41 is 5 wt% to 90 wt% of the mixture, based on the total weight of the manganese oxide and MCM-41 mixture.
- the manganese oxide is 10 wt% to 95 wt% of the mixture, based on the total weight of the manganese oxide and MCM-41 mixture.
- Conductive additives and binders may be added to this mixture manganese oxide and MCM- 41 as described above in Example 7. If present, the conductive additives and binders are 1 wt% - 20 wt% of the total weight of the mixture.
- the mixture is then added to a solvent - either aqueous (water) or non-aqueous (ethanol, methanol, tetrahydrofuran, N-methyl pyrrolidone and similar solvents).
- the resultant slurry is subjected to planetary mixing at 2000 rpm or more and for 2-20 minutes.
- the slurry is then cast on a substrate through a doctor-blade coating mechanism and allowed to dry to form a coated cathode.
- the coated cathode is then subjected to further chemical treatment to etch away the MCM-41 template.
- MCM-41 is primarily composed of S1O2 and the etchants are selected accordingly.
- the etchant is a buffered mixture of 0.1 -30 wt% hydrofluoric acid, 10-95 wt% water and 1-50 wt% ammonium fluoride.
- the etchant is a buffered potassium hydroxide solution comprising 5-80 wt% potassium hydroxide and 5-90 wt% of water or organic solvents including but not limited to acetone, methanol, dimethyl sulfoxide and dimethyl formamide.
- the cathode is washed repeatedly with water and acid to remove impurities and neutralize remnant hydroxyl ions. Once dried, the cathode is ready to be assembled into battery.
- Porous ⁇ (3 ⁇ 4 cathodes produced by the methods disclosed above have improved wettability compared to conventional ⁇ (3 ⁇ 4 cathodes.
- the typical spherical profile of an electrolyte droplet contacting the cathode is not observed, owing to excellent seepage of the liquid throughout the structure, thereby indicating superior wettability characteristics.
- a porous Mn(3 ⁇ 4 cathode was synthesized by using 80 wt% chemically delithiated Mn0 2 , 10 wt% MCM-41 and 10 wt% PVDF polymer binder, mixed in N-methyl pyrrolidone solvent. The viscosity of the resulting slurry was controlled by maintaining the solvent volume to -2.5-4 mL per gram of mixture. Following the casting of the electrode and its subsequent drying, it was immersed in a solution comprising 40 w% KOH for 90 minutes in a furnace maintained at 75 °C. At the end of this step, the cathode was retrieved from the solution, repeatedly washed with deionized water and dried prior to use.
- the ⁇ (3 ⁇ 4 layer of the cathode was about 100 ⁇ thick (range 80-120 ⁇ ).
- the cathode was then assembled in a coin cell configuration against an aluminum anode, separated by a polypropylene separator.
- the average discharge voltage was measured to be 1.08 V at 10 ⁇ /cm .
- Example 22 illustrates the discharge voltage profile with the discharge set at a cut-off of 1 V of a battery having a cathode with a 100 ⁇ thick layer of porous ⁇ 0 2 cathode, a 15 ⁇ thick aluminum foil anode that had been treated with LiOH as described in Example 1 , a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a current density of about 10 ⁇ /cm 2 .
- the electrolyte in the test example comprised 20 weight% aluminum nitrate in 80 weight% water.
- Hydrogen peroxide (3 ⁇ 4(3 ⁇ 4) treatment involves the reaction between 3 ⁇ 4(3 ⁇ 4 and Mn0 2 cathodes, resulting in the reduction of the peroxide and evolution of oxygen and water. Increased wettability and ionic access through incorporation of water pockets may be realized by treating delithiated manganese oxide with hydrogen peroxide, organophosphate esters and carbonitriles. Manganese oxide induces hydrolysis of the aforementioned additives, resulting in the generation of water pockets and oxygen. This treatment introduces water pockets within the core structure of the cathode coating that would otherwise not be wetted by the electrolyte. In addition, it is believed that the evolution of oxygen can expand the inter-sheet spacing of the Mn0 2 due to a pressure build-up within the bulk cathode material.
- the coated Mn0 2 cathode is treated with predetermined concentrations of 3 ⁇ 4(3 ⁇ 4, typically 1 wt% to 50 wt% aqueous solutions of 3 ⁇ 4(3 ⁇ 4 for 5-60 minutes room temperature to 80 °C. In certain embodiments, 1 wt% - 30 wt% 3 ⁇ 4(3 ⁇ 4 can be incorporated into the electrolyte as well. In certain embodiments, the volume of aqueous aluminum nitrate and hydrogen peroxide solution was maintained such that the resultant electrolyte was composed of 10 weight% hydrogen peroxide, 20 weight% aluminum nitrate and 70 weight% water.
- Mn0 2 cathode was treated with 30% hydrogen peroxide (Sigma- Aldrich) for 30 minutes.
- the electrolyte comprised 10 wt% 3 ⁇ 4(3 ⁇ 4, 20 wt% aluminum nitrate and 70 wt% deionized water.
- the cathode, along with the peroxide -based electrolyte, was assembled against a 15 ⁇ aluminum foil anode treated as described in Example 1, glass micro fiber separator with 1 ⁇ pore size.
- the cell was cycled at 10 ⁇ /cm 2 and recorded a maximum achievable capacity of 0.25 mAh at an average discharge potential of 1.08 V, as shown in FIG. 23.
- FIG. 23 illustrates the charge voltage profile (curve 1) and the discharge voltage profile (curve 2) of a Mn0 2 cathode with a cross-sectional thickness of 100 ⁇ , assembled against a 15 ⁇ thick aluminum foil that had been treated with LiOH, with a glass micro fiber separator and a current density of about 10 ⁇ /cm 2 .
- the cathode was treated with H 2 O 2 as described above and the electrolyte comprised 10 weight% 3 ⁇ 4(3 ⁇ 4.
- Iodine doping of manganese oxide was carried out using a gas-phase penetration technique.
- Manganese oxide powder was mixed with iodine crystals (less than 50 wt%) and the mixture was then placed inside a closed chamber and heated to about 50-200 °C (typically, above the sublimation temperature of iodine).
- the temperature at which sublimation of iodine was carried out was chosen to be 80 °C. This causes iodine to sublime (transform from solid phase to gas phase directly) and a purple vapor can be seen inside the chamber. The vapor results in doping the manganese oxide powder.
- the dopant concentration is largely limited by the ability of iodine to penetrate the spinel structure of manganese oxide and therefore, the dopant concentration is approximately about 10% or less of the weight of iodine crystals used (for example, 100 mg of iodine mixed with 900 mg of manganese oxide is expected to result in 10 mg of iodine penetration, i.e., about 1% doping). In general, 1% doping is sufficient. However, in order to achieve a greater dopant concentration, the ratio of the weight of iodine crystals and manganese oxide powder can be varied as desired.
- the chamber is re -heated at 80 °C in a vacuum furnace to ensure any unreacted iodine crystal sublimes and is removed from the doped manganese oxide powder.
- the process can be carried out on cathodes with lithium manganese oxide as well as cathodes with coated manganese oxide.
- Iodine-doped manganese oxide was tested as an example and was found to have an average discharge potential of about 1.16 V at about 20 ⁇ /cm 2 , compared to 1.01 V for undoped manganese oxide cathodes tested at the same current density.
- a standard polypropylene separator having 0.067 ⁇ pores was used in testing for comparison with previously obtained baseline data.
- FIG. 24 is charge-discharge voltage profile of acid- delithiated, iodine-doped manganese oxide cathode.
- the battery was assembled in a 2032 coin cell format and had an anode comprising an aluminum foil treated with LiOH as described in Example 1, an acid-delithiated, iodine-doped manganese oxide cathode, a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and a 0.5 M A1(N(3 ⁇ 4) 3 (aq) electrolyte. Even at about 2-times the discharge current density, the cathode displayed low charge and discharge hysteresis of 84 mV and 129 mV respectively.
- alternate dopants can also be incorporated to achieve the same effect. Some options in this regard would include but not be limited to nitrogen, boron and phosphorus.
- other approaches to increase charge transfer kinetics would include broadly conductive materials incorporating platinum, silver, gold, titanium, carbon allotropes or similar catalysts and combinations thereof (generally, ⁇ 5 weight%) into the manganese oxide cathode.
- the catalyst may be simply mixed with the manganese oxide powder and cast as a slurry or it can be deposited via physical vapor deposition whereby a thin film of the catalyst would be formed at the surface of the as-coated cathode.
- X-ray photoelectron spectroscopy (XPS) measurements were carried out on the surface of the anode and cathode following the completion of a deep discharge reaction (aluminum-based ion penetration into manganese oxide cathode), in order to ascertain the reaction mechanism.
- XPS X-ray photoelectron spectroscopy
- both manganese oxide (Mn0 2 ) cathode and aluminum (Al) anode showed significant presence of oxides on the surface, corresponding to 61.3 atomic % and 62.9 atomic %, respectively.
- Aluminum was measured to be 12.1 atomic % and 15.6 atomic % at the surfaces of Mn0 2 and Al respectively.
- the cathode and anode samples also showed traces of carbon (in the form of hydrocarbons, oxides and nitrides, attributed to polymer binders and carbon-based conductive additives present in the cathode as well as atmospheric contamination and adsorption on both anode and cathode surfaces), nitrogen (primarily in the form of nitrates and attributed to solid electrolyte interphase formation reaction between electrode surface and aluminum nitrate constituents in the electrolyte), fluorine (electrolyte used during electrochemical delithiation of lithium manganese oxide) and manganese (present in cathodes; trace amounts of manganese observed at the anode surface is attributed to electrolytic dissolution and transportation of manganese dioxide owing to deep discharge parameters).
- the XPS measurements are shown in FIG 25 (anode) and FIG. 26 (cathode).
- [0021 1 ] is estimated to have a theoretical reaction potential of 1.19 V.
- the practical operating voltage window observed in the proposed aluminum ion cells typically lies between a minimum and maximum range of 0.2 V and 2V respectively, thereby corresponding to and encompassing the theoretical reaction potentials calculated above.
- non-ideality factors such as atmospheric humidity, temperature, contamination, pH, internal resistance and other similar parameters can often contribute to a significant deviation of practical reaction potentials from the theoretical values. This observation therefore suggests that the concentration of Al(OH)3 may be higher than that of both AI2O 3 and AIOOH. Consequently, this observation is also supported by the XPS measurements.
- titanium oxide cathodes were also tested successfully.
- the host of cathodes capable of intercalating with aluminum hydroxide would include compounds with largely similar properties including but not limited to alpha, beta and lambda phases of manganese oxide, oxides of alternative metals (including but not limited to titanium oxide, tin oxide, iron oxide, vanadium oxide, molybdenum oxide, cobalt oxide), sulfides of alternative metals (including but not limited to molybdenum sulfide, tungsten sulfide, iron sulfide) or combination of at least one of such materials.
- titanium oxide cathodes were discharged successfully within a voltage window of 0.2 V and 1.5 V.
- FIG. 27 shows a charge / discharge voltage profile of a titanium oxide cathode assembled against an anode comprising an aluminum foil treated with LiOH as described in Example 1, using a standard 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ , and 0.5 M A1(N0 3 ) 3 electrolyte.
- Aluminum ion batteries were also tested in an organic electrolyte.
- the anode comprised hydroxide -treated aluminum foil, the separator was a 25 ⁇ thick polypropylene separator with an average pore size of 0.067 ⁇ and the cathode comprised acid-delithiated manganese dioxide.
- the electrolyte comprised 20 wt.% aluminum nitrate and 10 wt.% lithium bis(trifiuoromethanesulfonyl)imide in 35 wt.% diethyl carbonate and 35 wt.% dimethyl carbonate.
- the batteries displayed an average operating potential during the charging cycle of 3.9 V and an average operating potential during the discharging cycle of 3.4 V (FIG. 28). Such a system allows a marked improvement in energy density with ⁇ 3-fold increase in operating voltage.
- FIG. 29 compares the voltage profile of an aluminum ion battery having a 0.5 M A1(N0 3 ) 3 (aq) electrolyte (curve 1, filled triangles) to the voltage profile of an aluminum ion battery having a 0.45 M A1(N(3 ⁇ 4) 3 (aq) electrolyte containing 10% methanol (curve 2, filled circles).
- the anode comprised hydroxide-treated aluminum foil and the cathode comprised acid-delithiated manganese oxide.
- magnetic iron oxide particles were mixed in the slurry to form the cathode, in a weight ratio of 5% iron oxide nanoparticles ( ⁇ 50 nm, Sigma-Aldrich, St. Louis, MO), 75% acid delithiated manganese oxide, 10% conductive carbon and 10% PVDF binder.
- the mixture was added to N-methyl pyrrolidone and coated on a metal substrate using doctor-blade and slot-die coating.
- the slurry-coated substrate and at least one magnet were assembled in a closed chamber with a spacer placed between the magnet(s) and the surface of the slurry to avoid direct contact between the slurry and the magnet(s).
- the magnets (with a net magnetic force of 150 lbf) were placed above the wet slurry, at a distance of about 1 cm from the surface of the wet slurry.
- magnetic iron oxide particles mixed with manganese oxide were pulled by the magnet in the direction of the magnetic field and in the process, aligned the manganese oxide particles in the slurry uniformly and along the direction of the magnetic field.
- the cathodes prepared using this method displayed higher wettability with aqueous electrolytes than observed with cathodes prepared using other methods.
- nickel-plated neodymium-iron-boron magnets were used, but other magnets of similar size, mass and pull force would be suitable.
- Several magnets can be aligned so that the net magnetic pull force is a result of the summation of the pull forces of the individual magnets.
- the pull force of individual magnets was supplied by the vendor.
- a total pull force of about 10 lbf to 200 lbf is the ideal range. Magnetic pull forces less than 10 lbf are too low to properly align iron oxide nanoparticles, while magnets with pull forces greater than 200 lbf are difficult to handle in a laboratory environment and unnecessarily high for the desired nanoparticle alignment.
- the spacing between the slurry surface and the magnets can be adjusted as needed, with a larger spacing being suitable for higher magnetic pull forces.
- the drying time of the slurry can be adjusted by the humidity within the closed chamber. A high magnetic pull force can permit fasted drying times, while a lower magnetic pull force necessitates slower drying times.
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Abstract
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US201662406853P | 2016-10-11 | 2016-10-11 | |
US15/290,599 US9819220B2 (en) | 2015-10-08 | 2016-10-11 | Rechargeable aluminum ion battery |
US15/476,398 US10559855B2 (en) | 2015-10-08 | 2017-03-31 | Rechargeable aluminum ion battery |
PCT/US2017/056229 WO2018071602A1 (fr) | 2016-10-11 | 2017-10-11 | Batterie à ions aluminium rechargeable |
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CN112002937A (zh) * | 2020-08-07 | 2020-11-27 | 山东科技大学 | 一种用于铝离子电池的凝胶电解质及其制备方法和应用 |
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US10559855B2 (en) | 2015-10-08 | 2020-02-11 | Everon24 Llc | Rechargeable aluminum ion battery |
US9819220B2 (en) | 2015-10-08 | 2017-11-14 | Everon24 Llc | Rechargeable aluminum ion battery |
US11603321B2 (en) | 2015-10-08 | 2023-03-14 | Everon24, Inc. | Rechargeable aluminum ion battery |
WO2020056514A1 (fr) * | 2018-09-19 | 2020-03-26 | The Governing Council Of The University Of Toronto | Batterie aluminium-ion utilisant des solvants eutectiques profonds à base de chlorure d'aluminium/amide |
EP3935657A1 (fr) | 2019-03-08 | 2022-01-12 | Everon24, Inc. | Batteries au lithium-ion aqueuses, condensateurs de batterie hybrides, compositions desdites batteries et desdits condensateurs de batterie, et procédés de fabrication et d'utilisation associés |
CN110061206B (zh) * | 2019-03-28 | 2021-01-15 | 华南师范大学 | 一种SiO基纳米复合材料、负极及其制备方法 |
CN111769300B (zh) * | 2020-02-28 | 2023-06-30 | 上海市机电设计研究院有限公司 | 全钒液流电池用铝基镀铜集流板的制备方法 |
CN113651360B (zh) * | 2021-08-18 | 2022-08-05 | 江南大学 | 一种钒氧化物的合成方法及应用 |
US20230088564A1 (en) * | 2021-09-21 | 2023-03-23 | Apple Inc. | Looped battery tab with oxide coating |
CN115295785B (zh) * | 2022-08-23 | 2023-06-02 | 广东比沃新能源有限公司 | 一种纳米硅碳复合电极材料及其锂电池 |
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US2838591A (en) * | 1955-02-08 | 1958-06-10 | Aluminum Co Of America | Primary cell |
US6589692B2 (en) * | 2000-03-01 | 2003-07-08 | Kabushiki Kaisha Toshiba | Aluminum battery with aluminum-containing negative electrode |
US7179310B2 (en) * | 2003-07-03 | 2007-02-20 | The Gillette Company | Zinc/air cell with improved anode |
JP6228009B2 (ja) * | 2010-09-13 | 2017-11-08 | ザ、リージェンツ、オブ、ザ、ユニバーシティ、オブ、カリフォルニアThe Regents Of The University Of California | イオン性ゲル電解質、エネルギー貯蔵デバイス、およびそれらの製造方法 |
US20120082904A1 (en) * | 2010-09-30 | 2012-04-05 | Brown Gilbert M | High energy density aluminum battery |
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