WO2024069650A1 - Electrolyte supporting aluminate-ion battery and process for preparation thereof - Google Patents
Electrolyte supporting aluminate-ion battery and process for preparation thereof Download PDFInfo
- Publication number
- WO2024069650A1 WO2024069650A1 PCT/IN2023/050889 IN2023050889W WO2024069650A1 WO 2024069650 A1 WO2024069650 A1 WO 2024069650A1 IN 2023050889 W IN2023050889 W IN 2023050889W WO 2024069650 A1 WO2024069650 A1 WO 2024069650A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminium
- aluminate
- electrolyte
- ion battery
- conducting
- Prior art date
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims description 21
- 230000008569 process Effects 0.000 title description 14
- 238000002360 preparation method Methods 0.000 title description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 116
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000004411 aluminium Substances 0.000 claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 90
- 230000005496 eutectics Effects 0.000 claims abstract description 36
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 33
- 239000002608 ionic liquid Substances 0.000 claims abstract description 13
- 238000004146 energy storage Methods 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 56
- 239000010439 graphite Substances 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000011149 active material Substances 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 239000005703 Trimethylamine hydrochloride Substances 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 239000000374 eutectic mixture Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 239000002322 conducting polymer Substances 0.000 claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 230000009972 noncorrosive effect Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 abstract description 26
- 230000002687 intercalation Effects 0.000 abstract description 26
- 239000002841 Lewis acid Substances 0.000 abstract description 22
- 150000007517 lewis acids Chemical class 0.000 abstract description 21
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- -1 aluminate anion Chemical class 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002879 Lewis base Substances 0.000 description 8
- 150000007527 lewis bases Chemical class 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 2
- QSVCPXPVEZVSPY-UHFFFAOYSA-N 2-ethyl-1-methyl-1h-imidazol-1-ium;chloride Chemical compound [Cl-].CCC1=[NH+]C=CN1C QSVCPXPVEZVSPY-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- CEPNXVWPVOFQHL-UHFFFAOYSA-L magnesium;diethyl phosphate Chemical compound [Mg+2].CCOP([O-])(=O)OCC.CCOP([O-])(=O)OCC CEPNXVWPVOFQHL-UHFFFAOYSA-L 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- NYNZQNWKBKUAII-KBXCAEBGSA-N (3s)-n-[5-[(2r)-2-(2,5-difluorophenyl)pyrrolidin-1-yl]pyrazolo[1,5-a]pyrimidin-3-yl]-3-hydroxypyrrolidine-1-carboxamide Chemical compound C1[C@@H](O)CCN1C(=O)NC1=C2N=C(N3[C@H](CCC3)C=3C(=CC=C(F)C=3)F)C=CN2N=C1 NYNZQNWKBKUAII-KBXCAEBGSA-N 0.000 description 1
- SSORSZACHCNXSJ-UHFFFAOYSA-N 2-[2-(3,4-dichlorophenyl)-3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]imidazol-4-yl]acetonitrile Chemical compound ClC=1C=C(C=CC=1Cl)C=1N(C(=CN=1)CC#N)C1=NC(=NC=C1)NCC(C)O SSORSZACHCNXSJ-UHFFFAOYSA-N 0.000 description 1
- DILISPNYIVRDBP-UHFFFAOYSA-N 2-[3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]-2-naphthalen-2-ylimidazol-4-yl]acetonitrile Chemical compound OC(CNC1=NC=CC(=N1)N1C(=NC=C1CC#N)C1=CC2=CC=CC=C2C=C1)C DILISPNYIVRDBP-UHFFFAOYSA-N 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- JAWZAONCXMJLFT-UHFFFAOYSA-N 4-propylpyridine Chemical compound CCCC1=CC=NC=C1 JAWZAONCXMJLFT-UHFFFAOYSA-N 0.000 description 1
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 1
- ONPGOSVDVDPBCY-CQSZACIVSA-N 6-amino-5-[(1r)-1-(2,6-dichloro-3-fluorophenyl)ethoxy]-n-[4-(4-methylpiperazine-1-carbonyl)phenyl]pyridazine-3-carboxamide Chemical compound O([C@H](C)C=1C(=C(F)C=CC=1Cl)Cl)C(C(=NN=1)N)=CC=1C(=O)NC(C=C1)=CC=C1C(=O)N1CCN(C)CC1 ONPGOSVDVDPBCY-CQSZACIVSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- 235000013628 Lantana involucrata Nutrition 0.000 description 1
- 235000006677 Monarda citriodora ssp. austromontana Nutrition 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 240000007673 Origanum vulgare Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MCRWZBYTLVCCJJ-DKALBXGISA-N [(1s,3r)-3-[[(3s,4s)-3-methoxyoxan-4-yl]amino]-1-propan-2-ylcyclopentyl]-[(1s,4s)-5-[6-(trifluoromethyl)pyrimidin-4-yl]-2,5-diazabicyclo[2.2.1]heptan-2-yl]methanone Chemical compound C([C@]1(N(C[C@]2([H])C1)C(=O)[C@@]1(C[C@@H](CC1)N[C@@H]1[C@@H](COCC1)OC)C(C)C)[H])N2C1=CC(C(F)(F)F)=NC=N1 MCRWZBYTLVCCJJ-DKALBXGISA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
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- 239000004202 carbamide Substances 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
-
- 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 invention provides the ionic liquid-based eutectic electrolyte supporting aluminate-ion battery constructed with low-cost electrode materials with simple modifications. More particularly, the present invention relates to a rechargeable aluminate-ion-based battery utilizing an aluminum anode, carbonbased intercalation cathode and non-volatile triethylamine hydrochloride -based eutectic with the Lewis acid-based additives for energy storage applications at room temperature.
- Multivalent metal -based batteries are considered as alternative choices. However, much research efforts need to be put forth in realizing the successful commercialization of alternative technologies.
- Metal such as aluminium (Al) is considered as a promising potential candidate for the design of rechargeable battery due to various factors such as high abundance (82000 ppm vs. 65 ppm for Li) present in earth crust (10 times cheaper than Li)), multiple electron transfer (Je'per single metal atom reduction), similar ionic radius such as Li (0.535A for Al vs. 0.76 A for Li ) and high energy density when coupled with suitable electrodes and electrolytes.
- Aluminium is a safer-to-handle metal anode in ambient environmental conditions and cost-effective in battery fabrication.
- Aluminum-ion battery technology demands appropriate electrolytes that dissolute and deposit Al electrode reversibly and enables reversible intercalation and deintercalation of Al-ions from the positive electrode.
- the fabricated cells stated to behave as a primary and secondary batteries based on the choice of materials integrated in fabricating the cells.
- WO2015/131132 Al discloses a rechargeable aluminium battery consisting of aluminium as anode, graphite as cathode material and ethyl methyl imidazolium chloride: AICI3 electrolyte in appropriate ratio.
- the main objective of the present invention is to provide an energy storage device having aluminium anode, carbon-based intercalation cathode and nonvolatile triethylamine hydrochloride -based eutectic with the Lewis acid-based additives.
- Another objective of the present invention to disclose aluminium rechargeable battery comprising; (a) at least one carbon-based intercalation cathode, and/or (b) at least one of intercalation cathodes and/or composite with any other active material that undergoes de -/intercalation, de-/insertion or conversion type mechanism.
- Another objective of the present invention to disclose a non-aqueous electrolyte for an electrochemical cell, especially rechargeable aluminium batteries, comprising trialkyl hydrochloride -based Lewis base where alkyl group can be ethyl-, methyl- and/or butyl- derivatives fused with Lewis-acid, especially AICI3 and/or MgCh.
- Yet another objective of the present invention to disclose aluminium full cell having intercalation and/or doping mechanism-based cathode against an aluminium metal anode in triethylamine hydrochloride: AICI3: MgCh in appropriate weight ratio (56:41:3 wt%) have been developed that has a specific capacity 80 - 125mAh/g at c/10-rate.
- the cells exhibited nominal open circuit potential of ⁇ 1.0 - 1.5V, varying on the type of current collector used to fabricate the cathode.
- the cell has shown a coulombic efficiency of >90% during cycling.
- the present invention provides a present invention relates to a rechargeable aluminate-ion-based battery utilizing an aluminium anode, carbonbased intercalation cathode and non-volatile triethylamine hydrochloride -based eutectic with the Lewis acid-based additives for energy storage applications at room temperature.
- the invention relates to a rechargeable aluminate-ion-based battery and a process of making thereof.
- Another aspect of the present invention correlates to the electrodes casted on the carbon-based current collectors.
- another aspect of the present invention relates to a process of preparing electrolyte comprising trialkyl hydrochloride -based Lewis base where alkyl group can be ethyl-, methyl- and/or butyl-derivatives fused with Lewis-acid, especially AlCh.
- alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additives of metal halides such as MgCh to suppress the corrosion of Al anode in the acidic electrolyte.
- alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additives of metal halides such as FeCh to increase the operating potential window to >2.5 V vs. A1/A1 +3 .
- alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additive such as magnesium diethyl phosphate to increase the operating potential window (z.e., >2.5V vs. A1/A1 +3 ) and suppress the corrosion of metal anode.
- Another aspect of the present invention relates to a process of preparing electrolyte trialkyl hydrochloride-based Lewis-base where alkyl group can be ethyl, methyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additive such as RMgCl where R is alkyl group such as methyl, ethyl, butyl, phenyl etc. to increase the operating potential window (z.e.>2.5V vs. A1/A1 +3 ).
- alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additives of metal halides such as MgCh, FeChetc. or RMgCl where R is alkyl group such as methyl, ethyl, butyl, phenyl etc. or magnesium diethyl phosphate the combination of the additives to increase the operating potential window (/'. ⁇ ?. >2.5V vs. A1/A1 +3 ) and/or to suppress the corrosion of Al anode in the acidic electrolyte and/or to minimize the overpotential upon cycling of the cell.
- AICI3 additives of metal halides
- MgCh, FeChetc. or RMgCl where R is alkyl group such as methyl, ethyl, butyl, phenyl etc. or magnesium diethyl phosphate
- FIG. 1 Figure Idepicts the schematic cross-sectional representation of the fabricated rechargeable aluminate-ion battery, and designated materials used for fabricating the same, in accordance with an embodiment of the present disclosure.
- the denoted 1, 4 can be any metal strip/screw connected with a bolt 2, 5; 3 is the electronic current collector to connect aluminum anodes arranged in series manner denoted by 9; 6 is electronic current collector to connect cathodes arranged in series manner, denoted by 11 ; 10 is separator; 8 is electrolyte disposed in the battery casing denoted by 7.
- Figure 2 depicts the schematic representation of typical rechargeable aluminate-ion battery fabricated to study the cell performance, in accordance with an embodiment of the present disclosure.
- 101 is any electronically insulating ion- permeable separator placed between the anode and cathode, to prevent any possible short-circuit.
- Anode is comprised of 92, casted on any type of electronically conducting current collector denoted by 91; whereas 111 is any form of current collector sandwiched between double sided coating of cathode casted as 112.
- Figure 3 depicts the schematic representation of the typical rechargeable aluminate-ion battery fabricated to analyze the cell performance, in accordance with an embodiment of the present disclosure.
- 92-a is a free-standing aluminum metal foil/strip
- 112-a is cathode casted on the either side of current collector, 111-a. Both the electrodes are separated with an electronically insulating ion- permeable separator, 101, sandwiched between.
- Figure 4 depicts the schematic representation of the typical rechargeable aluminate-ion battery fabricated to analyze the cell performance, in accordance with an embodiment of the present disclosure.
- 92-b is a free-standing aluminum metal foil/strip
- 112-b is free-standing cathode
- both the electrodes are separated with an electronically insulating ion-permeable separator, 101, sandwiched between.
- Figure 5 depicts the schematic representation of the typical electrode arrangement followed in fabricating the rechargeable aluminate-ion battery, in accordance with an embodiment of the present disclosure.
- Figure 6 depicts the digital image of a typical anode used in fabricating the rechargeable aluminate-ion battery, in accordance with an embodiment of the present disclosure.
- Figure 7 depicts the digital image of a typical graphite (cathode) electrode coated on current collector used in fabricating the rechargeable aluminate-ion battery, in accordance with an embodiment of the present disclosure.
- Figure 9 depicts the cyclic voltammetry curves of a three electrode cell using Al as counter electrode, Al as reference electrode and Pt as working electrode in an electrolyte as (a) triethylamine hydrochloride: AICI3 and (b) triethylamine hydrochloride: AICI3: MgCh, in accordance with an embodiment of the present disclosure.
- Figure 10 depicts the Galvanostatic charge-discharge performance of aluminium-graphite cell flooded with triethylamine hydrochloride: AICI3: MgChas electrolyte(a) at fixed current density of 50mAh, and (b) at different current densities, in accordance with an embodiment of the present disclosure.
- Figure 11 shows the cyclic voltammetry curves recorded for aluminium- graphite cell flooded in the triethylamine hydrochloride: AlChiMgChas electrolyte in a potential window of 0.0-2.5 V vs. A1/A1 +3 at 0.3 mV/s slow-rate, in accordance with an embodiment of the present disclosure.
- Figure 12 shows the rate capability of Al-graphite cell recorded in the electrolyte comprising triethylamine hydrochloride: AICI3: MgCF charged and discharged at 50 mA/g current density.
- aluminate-ion battery refers to the class of rechargeable batteries in which aluminium ions serve as charge carriers wherein the Al ions are capable of exchanging three electrons. In aluminate-ion battery, Al-ion intercalates, whereas in aluminium-ion battery, Al in atomic form deposits and dissolves.
- separator refers to the permeable or semi-permeable membranelike materials used to separate two electrodes from each other so as to prevent any short circuit upon contact. In an aspect of the present disclosure, the separator used is an ion-permeable non-conducting separator.
- the term “prismatic -type cell” refers to a cell that have a rectangular shape and is enclosed in a rigid casing made of steel or aluminum.
- the prismatic-type cell has more surface area than traditional cylindrical cells, which allows them to produce more energy capacity for greater range on electric vehicles or provide more storage capacity.
- the present invention relates to the development of rechargeable aluminate-ion battery with graphite cathode and triethylamine hydrochloride-based eutectic mixture electrolyte for uninterrupted powering supply and solar energy storage etc.
- the present invention portrays the development of safe, eco-friendly, cost effective, rechargeable aluminate-ion battery.
- the anode used in this battery is aluminium plate having thickness of ⁇ 0.8mm, cathode is commercially procured natural graphite.
- the electrolyte used in this model battery design is eutectic triethylamine hydrochloride-AlCh mixture with or no additives such as MgCh, dissolved at higher temperature (>50 °C) with Mg-salt additive >0 wt%.
- the electrolyte consists of the chloroaluminate-ions such as AlCLf and AI2CI7’ when no additives are present in the eutectic mixture of triethylamine hydrochloride-AlCh.
- MgCh chloroaluminate-ions
- AI2CI7 an additives present in the eutectic mixture of triethylamine hydrochloride-AlCh.
- MgCh concentration of AI2CI7’ species in the electrolyte, increasing the A1CU’ concentration and involving concurrent aluminate and Mg +2 active ionic entities intercalation leading to the active electrochemical performance.
- the reaction can be followed as such; MgCh + 2A12C17 ⁇ - Mg +2 + 4A1C14’.
- Aluminium ions along with Mg-ions will diffuse from the electrolyte towards cathode and will intercalate into graphite.
- Triethyl or methylamine hydrochloride is solid at room temperature.
- the appropriate ratio of AICI3 addition to the ionic liquid brings eutectic nature.
- Mg additive such as MgCh is taken >0 wt% to the 56 wt% of AICI3 and 41 wt% of triethylamine hydrochloride.
- the electrolyte electrochemical stability window varies with respect to the current collector used to fabricate the electrodes accordingly shift in the observed red-ox potentials will be observed. Hence, the charge-discharge profiles can be engaged in the potential range of 0.0-2.7V vs.
- the disclosed materials assembly is capable of storing and delivering electricity repeatedly (>1000 times).
- the disclosed design can be upgraded by increasing the dimensions of the electrodes.
- the disclosed power source can be operated at room temperature. The performance of the power source to electrochemical energy generation was studied with reference to the constant current load applied and the corresponding voltage system displayed.
- the present invention provides a rechargeable aluminate-ion battery utilizing an aluminium anode, carbon-based intercalation cathode and nonvolatile triethylamine hydrochloride -based eutectic mixture ionic liquid with Lewis acid-based additives for energy storage applications at room temperature.
- an aluminate- ion battery comprising: Anodes [9]; Cathodes [11]; Non-conducting separator [10]; and Ionically conducting electrolyte [8], wherein at least one electrolyte is a eutectic mixture-based ionic liquid.
- an An ionic liquid-based eutectic electrolyte supporting aluminate-ion battery for energy storage applications at room temperature comprising: Anodes [9]; Cathodes [11]; Non-conducting separator [10]; and Ionically conducting electrolyte [8], wherein anodes [9] and the fabricated cathodes [11] are connected in parallel with a current collector [6] & [3] respectively and further attached to conducting metal -based connectors e.g. bolts and screws as [4], [5], [1], [2].
- an aluminate- ion battery as disclosed herein, wherein the anode [9] comprises an aluminium plate or aluminium powder pressed or coated on an conducting current collector, selected from aluminium plate, aluminium alloy having different portions of other metals, or aluminium composite made of aluminium and other conducting fillers.
- theanode [9] comprises an aluminium plate.
- the anode [9] comprises an aluminium plate pressed on an anode current collector.
- the anode [9] comprises an aluminium powder.
- the anode [9] is a free-standing aluminium-based anode.
- an aluminate- ion battery as disclosed herein, wherein the anode is an aluminium powder anode [92] coated on an anode current collector [91] and the cathode is an active material graphite [112] coated on either side of a cathode current collector [111], separated with the non-conducting separator [101].
- an aluminate- ion battery as disclosed herein, wherein the anodes [92-a & 92-b] are free-standing metal foils or strips and the cathode is coated with active materials like graphite [112-a] on either side of a current collector [111-a], separated with the nonconducting separator [101].
- an aluminate- ion battery as disclosed herein, wherein the cathode [11] comprises an active material selected from graphite, graphene, carbon nanotubes, hard carbons, soft carbons, a carbon composite with conducting polymers, or combinations thereof; a conducting filler selected from carbon black, acetylene carbon black, or combinations thereof; a binder selected form polyvinylidene fluoride, sodium alginate, sodium carboxymethyl cellulose, or combinations thereof; and optionally a current collector.
- the active material is graphite
- the conducting filler is acetylene carbon black
- the binder is polyvinylidene fluoride.
- the cathode comprises an active material, a conducting filler, and a binder are physically mixed or formed composite through chemical or electrochemical synthetic procedures.
- an aluminium- ion battery as disclosed herein, wherein the cathode [11] is in pristine or composite form or derivative of graphite, graphene, carbon nanotubes, hard or soft carbons or a composite of conducting polymers physically mixed or formed composite through chemical or electrochemical synthetic procedures.
- an aluminium- ion battery as disclosed herein, wherein the anode or cathode is free-standing or coated on a current collector [6] & [3] fabricated by making slurry using conducting fillers selected from the carbon black, acetylene black and binders are selected form polyvinylidene fluoride or sodium alginate or sodium carboxymethyl cellulose or mixture thereof.
- an aluminate- ion battery as disclosed herein, wherein the current collectors are metal-based corrosive current collectors Cu, Ni, stainless steel (SS), Al, Ag, Mo, metal alloys, metal composites, or non-corrosive current collectors in the electrolyte like carbon- cloth or fibre or any or any other electronically conducting non-reactive substrate optionally comprising conducting fillers, and additives.
- the anode current collector is selected from aluminium foil, aluminium alloy with various proportions of metals, or aluminium composites with conducting fillers.
- the electrolyte comprises triethylamine hydrochloride, and AICI3, and/or additives selected from MgCh, FeCh, or combinations thereof.
- the electrolyte comprises triethylamine hydrochloride, AICI3, and MgCh.
- an aluminate- ion battery as disclosed herein, wherein the at least one anode and the at least one cathode are separated with the non-conducting permeable membrane as separator [10], and the separator is an electronically insulating separator.
- the battery is made in a form of a coin-cell, cylindrical cell, prismatic-type cell.
- an aluminate- ion battery as disclosed herein, wherein the battery is made in a form of a coin-cell, cylindrical cell, prismatic-type cell, or any other form where the electrolyte quantity can be limited as per the electrode quantity or can be flooded in excess.
- the present invention discloses the cathode for electrochemical cell, especially for aluminium rechargeable batteries, comprising carbon-based intercalation cathode.
- the present invention discloses an intercalation cathode for an electrochemical cell, especially for aluminium rechargeable batteries, comprising a carbon-based compound; wherein carbon-based compound exemplifies graphite, graphene, carbon nanotubes, hard/soft carbons etc. or combinations thereof.
- the present invention discloses an aluminium rechargeable battery comprising; (a) at least one carbon-based intercalation cathode, and/or (b) at least one of intercalation cathodes and/or composite with any other active material that undergoes de -/intercalation, de-/insertion or conversion type mechanism.
- the present invention provides a non-aqueous electrolyte for an electrochemical cell, especially rechargeable aluminium batteries, comprising trialkyl hydrochloride -based Lewis base where alkyl group can be ethyl-, methyl- and/or butyl- derivatives fused with Lewis-acid, especially AICI3 and/or MgCh.
- the present invention provides aluminium rechargeable battery comprising: (a) at least one intercalation cathode; and (b) at least one aluminium anode; and (c) at least one non-aqueous electrolyte which comprises eutectic and/or non-eutectic electrolyte formed with Lewis’s acids.
- the present invention provides aluminium rechargeable battery as defined above, wherein the intercalation cathode can be carbon-based allotrope such as graphite, graphene, carbon nanotubes, hard/soft carbons in which it can be pure in the pristine state and/or partly and/or fully oxidized as graphene oxide etc.
- the intercalation cathode can be carbon-based allotrope such as graphite, graphene, carbon nanotubes, hard/soft carbons in which it can be pure in the pristine state and/or partly and/or fully oxidized as graphene oxide etc.
- the present invention provides aluminium rechargeable battery as defined above, wherein the cathode can be conducting polymer that undergoes conversion-type redox mechanism.
- the present invention provides aluminium rechargeable battery as defined above, wherein the cathode can be a blend of intercalation type or conversion-type cathode, or a composite made physically or chemically.
- the present invention provides aluminium rechargeable battery as defined above, wherein the cathode presented and/or deposited on the current collectors comprising a pure metal such as Cu, Ag, Ni, Aland/or any other metal and/or any form of alloy mixed with different proportion of metals.
- the present invention provides aluminium rechargeable battery as defined above, wherein cathode presented and/or deposited on the current collector comprising a carbon-based electronic conductor.
- the present invention provides rechargeable battery as defined above, wherein carbon-based current collector comprising carbon-fibre and/or foil and/or any other type of carbon-based current collector like foil and/or plate and/or cloth.
- the present invention provides aluminium rechargeable battery as defined above, wherein cathode can be synthesized chemically or electrochemically in pristine and/or composite form plated and/or deposited on the as defined above current collectors.
- the present invention provides aluminium rechargeable battery as defined above, wherein cathode can be casted in slurry form using the conducting fillers such as conducting super-P and/or acetylene black and/or carbon nanotubes and/or any other form with the plasticizer and/or binder such as PVDF, sodium alginate, sodium carboxymethyl cellulose and/or the combinations thereof coated and/or dried.
- the conducting fillers such as conducting super-P and/or acetylene black and/or carbon nanotubes and/or any other form
- the plasticizer and/or binder such as PVDF, sodium alginate, sodium carboxymethyl cellulose and/or the combinations thereof coated and/or dried.
- the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX in which Ri, R2, and R3 is selected from the group comprising alkyl groups like methyl, ethyl, butyl, phenyl and/or their derivatives; N is phosphonium, ammonium etc , X is fluoride, chloride, bromide or iodide.
- the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or R x AlCl y and/or MgCh.
- the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or R x AlCl y and/or FeCh.
- the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or R x AlCl y and/or RMgCl, where R is methyl, ethyl, butyl, phenyl etc.
- the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or R x AlCl y and/or Mg/RPCL , where R is methyl, ethyl, butyl, phenyl etc.
- the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or R x AlCl y and/or ZnCh.
- the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or R x AlCl y and/or combination of additives such as metal halides (i.e. MgCh, FeCh, ZnCh or RMgCl or Mg/RPCL where R is methyl, ethyl, butyl or phenyl etc.).
- additives from the class of Lewis acids such as AICI3 and/or R x AlCl y and/or combination of additives such as metal halides (i.e. MgCh, FeCh, ZnCh or RMgCl or Mg/RPCL where R is methyl, ethyl, butyl or phenyl etc.).
- the present invention provides aluminium rechargeable battery as described above, wherein intercalation cathode can be represented using the formula C x wherein x can be any integer and/or C x O y wherein x can be any number; >0.
- the present invention provides aluminium rechargeable battery as describe above, wherein cathode can be a composite formed physically and/or chemically through any synthetic procedure.
- the present invention provides aluminium rechargeable battery as describe above, wherein electrolyte can be an ionic liquid derivative formed eutectic and/or non-eutectic with any Lewis acid and/or the derivative of the same.
- the present invention provides aluminium rechargeable battery as describe above, wherein a non-aqueous electrolyte comprises of eutectic and/or non-eutectic composition prepared by addition of aluminium-based salts, especially halide-based salts such as A1CL, MgCh, MgBr2etc.
- the present invention provides aluminium rechargeable battery as describe above, wherein a non-aqueous electrolyte comprises of eutectic and/or non-eutectic composition prepared by the addition of aluminium-based salts, especially halide -based salts such as AIX3 where X can be F, Cl, Br and/or I.
- a non-aqueous electrolyte comprises of eutectic and/or non-eutectic composition prepared by the addition of aluminium-based salts, especially halide -based salts such as AIX3 where X can be F, Cl, Br and/or I.
- the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is triethylamine hydrochloride eutectic with AICI3 in defined proportion ratio with MgCh additive in >0 and/or ⁇ 40wt% to that of total eutectic composition formed from individual.
- the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is trimethylamine hydrochloride eutectic with AICI3.
- the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is trimethylamine hydrochloride eutectic with AICI3 It is another object of the invention to disclose aluminium rechargeable battery as defined above, wherein electrolyte is mixture of triethylamine hydrochloride and/or trimethylamine hydrochloride eutectic.
- the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is mixture of triethylamine hydrochloride and/or trimethylamine hydrochloride eutectic and/or AlCh.
- the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is mixture of triethylamine hydrochloride and/or trimethylamine hydrochloride eutectic and/or AICI3 with additives of MgCh.
- the present invention provides aluminium rechargeable battery as defined above, wherein battery undergoes charge and/or discharge to a maximum high current density of >1000 mA/g.
- the present invention provides aluminium rechargeable battery as defined above, wherein the full fabricated cell sustains >1000 cycles with capacity fade ⁇ 0.1% from each cycle.
- the present invention provides aluminium rechargeable battery as defined above, wherein the full fabricated cell sustains at all environmental conditions like temperature range of -30 to 80 °C and full fabricated cell delivers > 125m Ah/g, maintaining a two-stage plateaus at ⁇ 1.8 V and -0.6 V.
- the present invention provides aluminium rechargeable battery as defined above, wherein the full fabricated cell can be operated in the potential window of 0.0-3.5 V vs. A1/A1 +3 based on the current collector and active material used in fabricating the cell.
- the present invention provides aluminium full cell having intercalation and/or doping mechanism-based cathode against an aluminium metal anode in triethylamine hydrochloride: AICI3: MgCh in appropriate weight ratio (56:41:3 wt%) have been developed that has a specific capacity 80 - 125mAh/g at c/10-rate.
- the cells exhibited nominal open circuit potential of ⁇ 1.0 - 1.5V, varying on the type of current collector used to fabricate the cathode.
- the cell has shown a coulombic efficiency of >90% during cycling.
- FIG. 1 Schematic illustration of the fabricated prismatic cell cross section is shown in Figure 1, wherein the cell contains multiple anodes [9], multiple cathodes [11] separated with a non-conducting separator [10] flooded in the ionically conducting electrolyte [8].
- the anodes [9] present from the cell and the fabricated cathodes [11] are connected in parallel with a current collector [6] and [3] respectively, further attached to conducting metal-based connectors like bolts and screws as [4], [5], [1], [2].
- Figure 2 illustrates the schematic representation of the arrangement of anode [9], cathode [11] divided by a separator [10] as shown in Figure 1 described precisely wherein the aluminium powder anode, [92] is coated on the electronically conducting current collector [91] and cathode is coated with active materials like graphite [112] on either side of the current collector [111], separated with anon- conducting separator [101] to prevent any possible short-circuit.
- Figure 3 illustrates the schematic representation of the arrangement of anode [9], cathode [11] divided by a separator [10] as shown in Figure 1 described, herein, precisely wherein the aluminium anode [92-a] is free-standing metal foil or strip and cathode is coated with active materials like graphite [112-a] on either side of the current collector [111-a], separated with anon-conducting ion-permeable separator [101].
- Figure 4 illustrates the schematic representation of the arrangement of anode [9], cathode [11] divided by a separator [10] as shown in Figure 1 described herein, precisely wherein the aluminium anode [92-b] is free-standing metal foil or strip and cathode is a graphite sheet, block or plate [112-b] naturally occurring, synthesized or processed, separated with anon-conducting separator [101].
- Figure 5 is the schematic illustration of systematic arrangement of anodes and cathodes divided by separators in fabricating a prismatic cell.
- Figure 6 is the aluminium plate anode used in fabricating the cell.
- Figure 7 is the graphite coated electrode on the woven carbon-fibre used in fabricating the prismatic cell.
- Example - 1 Aluminium Prismatic cell-1
- Aluminium battery with Al plate anode and graphite coated on woven carbon-fibre was assembled in a eutectic electrolyte comprising triethylamine hydrochloride and AICI3 composition.
- About 1.5:1 molar ratio of AICI3: triethylamine hydrochloride respectivelywas taken as electrolyte.
- the assembled Aluminium Prismatic cell-1 exhibited a capacity of -300 mAh, with a capacity retention of >90%.
- Example - 2 Aluminium Prismatic cell-2
- Aluminium battery comprising Al plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte.
- 1.5:1 molar ratio of AICI3: triethylamine hydrochloride was taken as electrolyte to obtain Aluminium Prismatic cell-2 for which a capacity of -300 mAh was achieved, with a capacity retention of >90%.
- Example - 3 Aluminium Prismatic cell-3
- Aluminium battery with Al plate anode and graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte.
- 56:41:3 wt% ratio of AICI3: triethylamine hydrochloride: MgCh respectively was taken as electrolyte to obtain the Aluminium Prismatic cell-3 for which a capacity of -300 mAh was achieved, with a capacity retention of >90%.
- Example - 4 Aluminium Prismatic cell-4
- Aluminium battery with Al plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte.
- 56:41:3 wt% ratio of AICI3: trimethylamine hydrochloride: MgCh respectivelywas taken as electrolyte to obtain the Aluminium Prismatic cell-4 which exhibited a capacity of -300 mAh, with a capacity retention of >90%.
- Example - 5 Aluminium Prismatic cell-5
- Aluminium battery with aluminium plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte.
- Example - 6 Aluminium Prismatic cell-6
- Aluminium battery with aluminium plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte.
- Example - 7 Aluminium Prismatic cell-7
- Aluminium battery with aluminium plate anode and self- standing graphite plate having 1 mm thickness was assembled in the eutectic electrolyte.
- a capacity of -1100 mAh was achieved for the cell, with a capacity retention of >90%.
- Example - 8 Aluminium Prismatic cell-8
- Aluminium battery with aluminium plate anode and self- standing graphite plate having 1 mm thickness was assembled in the eutectic electrolyte with an approximate weight of 1.2 grams.
- a capacity of -1100 mAh is achieved, with a capacity retention of >90%.
- Graphite powder is commercially procured from Sigma Aldrich ( ⁇ 45 m, >99.99% trace metal basis).
- the conventional electrodes were prepared from an active material slurry which was made using 90 wt% active material, 5 wt.% acetylene carbon black (100% compressed, 99.9+% procured from Alfa Aesar) and 5 wt.% poly vinylidene fluoride (PVDF) as binder (average Mw -180,000 by GPC) in N-methyl-Pyrrolidone solvent (Avra Chemicals pvt. Ltd.).
- the slurry was coated on the current collectors such as stainless steel (SS)-mesh or conducting carbon-cloth/fibers, followed by drying under vacuum at 90 °C for 16 hours.
- the working electrode having dimension of 0.4x0.5 cm 2 area was used for further characterizations.
- the active material loading on the conventional current collector was controlled between 2.0 - 4.5 mgcm’ 2 .
- the electrolyte used for the study were prepared in an Argon-filled glove box (Make: MBraun, ⁇ 1 ppm of water and oxygen).
- triethylamine hydrochloride or trimethylamine hydrochloride was mixed with AICI3 in an appropriate molar ratio of 1:1.1 to 1.7 forming eutectic.
- 56 wt% of triethylamine hydrochloride or trimethylamine hydrochloride and 41 wt% of AICI3 were mixed via constant stirring, resulting in a eutectic mixture at room temperature.
- 3 wt.% of MgCh was added to the mixture and kept under stirring at 80°C for next 12 hours to obtain the electrolyte.
- a glass fibre having -0.1mm thickness was considered as separator to prevent any short-circuit.
- Example - 12 Assembly of the Al flooded cell.
- the cells were assembled in the Ar-filled glovebox (MBraun, ⁇ 1 ppm of water and oxygen).
- Al plate having 0.08 mm thickness and area of 0.2 cm 2 was taken as anode, graphite coated stainless-steel (dimensions similar to that of anode) was taken as cathode.
- Electrolyte obtained by the process as explained in Example-3 was used as electrolyte. Separator as stated in the example- 11 was used to obtain Al flooded cell.
- the fabricated test cells were comprehensively evaluated for their electrochemical performance employing cyclic voltammetry (CV) analysis on a multi-channel Electrochem Origalys Workstation (Model - OGF05A). Chargedischarge studies of the assembled cells were performed using GCD technique in the voltage window of 0.0V - 2.0V under constant current followed by a rest period of Ih between each charge/discharge cycle.
- CV cyclic voltammetry
- Example - 15 Half-cell cyclic voltammetry
- Al-anode plating and stripping in the eutectic electrolyte with and without Mg-salt was primarily investigated by fabricating a three-electrode cell using Al- Counter electrode, Mg-Reference electrode and Pt-wire as Working electrode in the potential window of -1.0V to 2.0V vs. A1/A1 +3 at the slew rate of 5.0 mV. s’ 1 .
- Example - 16 Galvanostatic charge-discharge analysis
- Al-Graphite cell at high current density of 200 mA/g shown a discharge capacity of -40 mAh/g.
- the GCD cycling of Al-Graphite has delivered two plateaus while charge and discharge depicting the two-stages of intercalation of ionic species occurring into the host electrode. It is expected that the concurrent intercalation of Al- and Mg-ionic species which contributes the overall performance of the cell.
- Example - 17 Full-cell cyclic voltammetry
- Example - 18 Reversible cycling performance of the fabricated cells
- Al-Graphite cell showed a stable discharge capacity of -80 mAh/g, charged and drained at 200 mA/g for, maintaining a stable efficiency of >85%. However, the capacity fade was found minimal, and sustained for >100 cycles charge-discharge cycles.
- Aluminate-Ion Battery of the present disclosure is very safe, even if the battery is pierced while discharge, it will not burst into flames or explode.
- Aluminate-Ion Battery is cost effective, affordable to common man and industrial viable.
- No composite electrode materials were used for preparation of Aluminate- Ion Battery.
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Abstract
The present invention provides the ionic liquid-based eutectic electrolyte supporting aluminate-ion battery constructed with low-cost electrode materials with simple modifications. More particularly, the present invention relates to a rechargeable aluminium-ion battery utilizing an aluminium anode, carbon-based intercalation cathode and non-volatile triethylamine hydrochloride-based eutectic with the Lewis acid-based additives for energy storage applications at room temperature.
Description
ELECTROLYTE SUPPORTING ALUMINATE-ION BATTERY AND PROCESS FOR PREPARATION THEREOF
FIELD OF THE INVENTION
[0001] The present invention provides the ionic liquid-based eutectic electrolyte supporting aluminate-ion battery constructed with low-cost electrode materials with simple modifications. More particularly, the present invention relates to a rechargeable aluminate-ion-based battery utilizing an aluminum anode, carbonbased intercalation cathode and non-volatile triethylamine hydrochloride -based eutectic with the Lewis acid-based additives for energy storage applications at room temperature.
BACKGROUND AND PRIOR ART OF THE INVENTION
[0002] Development of energy storage devices is vital for storing the energy output from renewable sources. Most of the portable electronic devices nowadays are driven by Li-ion battery technology. Upgrading of such technology towards gridstorage or electric vehicle applications has limitations due to cost and safety parameters. Hence, the alternative battery technologies are in quest.
[0003] Multivalent metal -based batteries are considered as alternative choices. However, much research efforts need to be put forth in realizing the successful commercialization of alternative technologies.
[0004] Metal such as aluminium (Al) is considered as a promising potential candidate for the design of rechargeable battery due to various factors such as high abundance (82000 ppm vs. 65 ppm for Li) present in earth crust (10 times cheaper than Li)), multiple electron transfer (Je'per single metal atom reduction), similar ionic radius such as Li (0.535A for Al vs. 0.76 A for Li ) and high energy density when coupled with suitable electrodes and electrolytes.
[0005] Aluminium is a safer-to-handle metal anode in ambient environmental conditions and cost-effective in battery fabrication.
[0006] Aluminum-ion battery technology demands appropriate electrolytes that dissolute and deposit Al electrode reversibly and enables reversible intercalation and deintercalation of Al-ions from the positive electrode.
[0007] Reference may be made to the patent application US 2012/0082904 Al, wherein electrochemical cells having an aluminum anode, intercalation cathode such as M C , Ti/AlCU , MnCl (A1CU), Co/AlCU , and V2O5 comprising aluminate anion-based ionic liquid electrolytes with metal halide additives such as AICI3, NaCl, KC1, NH4CI disclosed. The fabricated cells stated to behave as a primary and secondary batteries based on the choice of materials integrated in fabricating the cells.
[0008] Reference may be made to the patent application WO 2017/106337 Aldiscloses electrolyte alternative to type-1 ionic liquids made by acid-base reaction (ethyl methyl imidazolium chloride: AICI3) with type-IV ionic liquids formed by the ligand-Lewis acid interactions such as urea: A1C13, acetamide: AICI3 or 4-propylpyridine: AICI3. The system reported to function in the temperature from -40 °C to 70 °C, delivering at least 71 Wh/kg. Nonetheless, the discharge voltage plateau is reported to be occurring at 1.75 V vs. A1/A1+3.
[0009] Reference may be made to the patent application WO 2019/024560 Al discloses the rechargeable aluminium ion battery consisting aluminium metal as anode, graphene foam as cathode and triethylamine hydrochloride and aluminium chloride in a molar ratio of 1:1.4- 1.6 as electrolyte solution. Though superior cyclability of >25000 achieved, the processing of positive electrode involves multiple step synthetic procedure. The upper cut-off voltage for the system is 2.54 V and retained -108 mAh/g specific capacity with >99% coulombic efficiency.
[0010] Reference may be made to the patent application WO2015/131132 Al discloses a rechargeable aluminium battery consisting of aluminium as anode, graphite as cathode material and ethyl methyl imidazolium chloride: AICI3 electrolyte in appropriate ratio.
[0011] Various electrodes such as polyaniline (PANI)/Graphite fluoride (Pat. No. CN102558856B),NiAlMn2O4 (Pat. No. US9466853), MxOy, or MxFy where M=Cu, P, Pb, Fe, Co, Ni, Ag or Sn (Pat. No. US8715853B 1), sulfur/oregano sulfur(Pat. No. CN104078705A or CN104078705B), Prussian blue (Pat. No. CN107240714A), LiO2 (Pat. No. US2017/0033397A1), CuS (Pat. No. CN105449271A), graphite (Pat. No. CN104868179A), MoS2 (Pat. No. CN104393290A) etc. are explored as positive cathode materials for rechargeable aluminium batteries.
[0012] Reference may be made to the article Adv. Energy Mater. 2019, 9, 1901749; Chem. Rev. 2021, 121, 4903-4961; Nat. Comm.2017, 8,14283; Chem. Mater.2017 , 29, 4484; ACS Appl. Energy Mater. 2019, 2, 7799, wherein carbonaceous materials such as graphite, graphene etc. are considered as promising cathode, allowing reversible de-/intercalation of chloroaluminate ions or aluminium ions.
[0013] Much scope in research exists in finding the electrolytes circumventing the challenges present in the existing aluminate-ion battery technology such as Alanode corrosion upon electrochemical cycling in acidic electrolytes, release of toxic chloride gases by the oxidation of chloroaluminate ions.
[0014] Rechargeable aluminium batteries integrated with electrolytes with minimized negative impacts as mentioned above could be successfully fuel-up such technology commercialization. Thus, keeping in view the drawbacks of the hitherto reported prior arts, there is much scope to research on rechargeable aluminate-ion battery in designing the same prototype for commercial applications.
OBJECTIVES OF THE INVENTION
[0015] The main objective of the present invention is to provide an energy storage device having aluminium anode, carbon-based intercalation cathode and nonvolatile triethylamine hydrochloride -based eutectic with the Lewis acid-based additives. Another objective of the present invention to disclose aluminium rechargeable battery comprising; (a) at least one carbon-based intercalation cathode, and/or (b) at least one of intercalation cathodes and/or composite with any
other active material that undergoes de -/intercalation, de-/insertion or conversion type mechanism.
[0016] Another objective of the present invention to disclose a non-aqueous electrolyte for an electrochemical cell, especially rechargeable aluminium batteries, comprising trialkyl hydrochloride -based Lewis base where alkyl group can be ethyl-, methyl- and/or butyl- derivatives fused with Lewis-acid, especially AICI3 and/or MgCh.
[0017] Yet another objective of the present invention to disclose aluminium full cell having intercalation and/or doping mechanism-based cathode against an aluminium metal anode in triethylamine hydrochloride: AICI3: MgCh in appropriate weight ratio (56:41:3 wt%) have been developed that has a specific capacity 80 - 125mAh/g at c/10-rate. The cells exhibited nominal open circuit potential of ~1.0 - 1.5V, varying on the type of current collector used to fabricate the cathode. The cell has shown a coulombic efficiency of >90% during cycling.
SUMMARY OF THE INVENTION
[0018] Accordingly, the present invention provides a present invention relates to a rechargeable aluminate-ion-based battery utilizing an aluminium anode, carbonbased intercalation cathode and non-volatile triethylamine hydrochloride -based eutectic with the Lewis acid-based additives for energy storage applications at room temperature.
[0019] In one aspect, the invention relates to a rechargeable aluminate-ion-based battery and a process of making thereof.
[0020] In another aspect of the present invention relates to a process for preparing carbon-based electrode casted on current collector or as a free-standing electrode either fabricated using binder and conducting additives or a plate/strip with no foreign additives.
[0021] Yet, another aspect of the present invention correlates to the electrodes casted on the carbon-based current collectors.
[0022] In another aspect of the present invention relates to a process of preparing electrolyte comprising trialkyl hydrochloride -based Lewis base where alkyl group can be ethyl-, methyl- and/or butyl-derivatives fused with Lewis-acid, especially AlCh.
[0023] Yet, another aspect of the present invention relates to a process of preparing electrolyte trialkyl hydrochloride -based Lewis base where alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additives of metal halides such as MgCh to suppress the corrosion of Al anode in the acidic electrolyte.
[0024] Yet, another aspect of the present invention relates to a process of preparing electrolyte trialkyl hydrochloride -based Lewis base where alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additives of metal halides such as FeCh to increase the operating potential window to >2.5 V vs. A1/A1+3.
[0025] Yet, another aspect of the present invention relates to a process of preparing electrolyte trialkyl hydrochloride -based Lewis-base where alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additive such as magnesium diethyl phosphate to increase the operating potential window (z.e., >2.5V vs. A1/A1+3) and suppress the corrosion of metal anode.
[0026] Yet, another aspect of the present invention relates to a process of preparing electrolyte trialkyl hydrochloride-based Lewis-base where alkyl group can be ethyl, methyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additive such as RMgCl where R is alkyl group such as methyl, ethyl, butyl, phenyl etc. to increase the operating potential window (z.e.>2.5V vs. A1/A1+3).
[0027] Yet, another aspect of the present invention relates to a process of preparing electrolyte trialkyl hydrochloride -based Lewis base where alkyl group can be methyl-, ethyl- and/or butyl-derivatives fused with Lewis-acid, especially AICI3 and additives of metal halides such as MgCh, FeChetc. or RMgCl where R is alkyl group such as methyl, ethyl, butyl, phenyl etc. or magnesium diethyl phosphate the
combination of the additives to increase the operating potential window (/'.<?. >2.5V vs. A1/A1+3) and/or to suppress the corrosion of Al anode in the acidic electrolyte and/or to minimize the overpotential upon cycling of the cell.
BRIEF DESCRIPTION OF THE DRAWING
[0028] The invention has other advantages and features which will be more readily apparent from the following detailed description of the invention and the appended claims, when taken in conjunction with the accompanying drawings, in which:
[0029] Figure Idepicts the schematic cross-sectional representation of the fabricated rechargeable aluminate-ion battery, and designated materials used for fabricating the same, in accordance with an embodiment of the present disclosure. The denoted 1, 4 can be any metal strip/screw connected with a bolt 2, 5; 3 is the electronic current collector to connect aluminum anodes arranged in series manner denoted by 9; 6 is electronic current collector to connect cathodes arranged in series manner, denoted by 11 ; 10 is separator; 8 is electrolyte disposed in the battery casing denoted by 7.
[0030] Figure 2 depicts the schematic representation of typical rechargeable aluminate-ion battery fabricated to study the cell performance, in accordance with an embodiment of the present disclosure. 101 is any electronically insulating ion- permeable separator placed between the anode and cathode, to prevent any possible short-circuit. Anode is comprised of 92, casted on any type of electronically conducting current collector denoted by 91; whereas 111 is any form of current collector sandwiched between double sided coating of cathode casted as 112.
[0031] Figure 3 depicts the schematic representation of the typical rechargeable aluminate-ion battery fabricated to analyze the cell performance, in accordance with an embodiment of the present disclosure. 92-a is a free-standing aluminum metal foil/strip, whereas 112-a is cathode casted on the either side of current collector, 111-a. Both the electrodes are separated with an electronically insulating ion- permeable separator, 101, sandwiched between.
[0032] Figure 4 depicts the schematic representation of the typical rechargeable aluminate-ion battery fabricated to analyze the cell performance, in accordance with an embodiment of the present disclosure. 92-b is a free-standing aluminum metal foil/strip, whereas 112-b is free-standing cathode, and both the electrodes are separated with an electronically insulating ion-permeable separator, 101, sandwiched between.
[0033] Figure 5 depicts the schematic representation of the typical electrode arrangement followed in fabricating the rechargeable aluminate-ion battery, in accordance with an embodiment of the present disclosure.
[0034] Figure 6 depicts the digital image of a typical anode used in fabricating the rechargeable aluminate-ion battery, in accordance with an embodiment of the present disclosure.
[0035] Figure 7 depicts the digital image of a typical graphite (cathode) electrode coated on current collector used in fabricating the rechargeable aluminate-ion battery, in accordance with an embodiment of the present disclosure.
[0036] Figure 8depicts the digital image of fabricated lab-scale rechargeable aluminate-ion battery having dimensions: Ixwxh = 7cmx3cmxl l cm, in accordance with an embodiment of the present disclosure.
[0037] Figure 9 depicts the cyclic voltammetry curves of a three electrode cell using Al as counter electrode, Al as reference electrode and Pt as working electrode in an electrolyte as (a) triethylamine hydrochloride: AICI3 and (b) triethylamine hydrochloride: AICI3: MgCh, in accordance with an embodiment of the present disclosure.
[0038] Figure 10 depicts the Galvanostatic charge-discharge performance of aluminium-graphite cell flooded with triethylamine hydrochloride: AICI3: MgChas electrolyte(a) at fixed current density of 50mAh, and (b) at different current densities, in accordance with an embodiment of the present disclosure.
[0039] Figure 11 shows the cyclic voltammetry curves recorded for aluminium- graphite cell flooded in the triethylamine hydrochloride: AlChiMgChas electrolyte in a potential window of 0.0-2.5 V vs. A1/A1+3 at 0.3 mV/s slow-rate, in accordance with an embodiment of the present disclosure.
[0040] Figure 12 shows the rate capability of Al-graphite cell recorded in the electrolyte comprising triethylamine hydrochloride: AICI3: MgCF charged and discharged at 50 mA/g current density.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0041] The foregoing detailed description of the disclosure is elaborated to provide a clear understanding to the person who is skilled in the art. Additional features, embodiments and advantages of the invention will be described hereinafter which form the subject of the claims of the disclosure, However, the set forth disclosure provide in the specification will best be understood in conjunction with the appended claims and figures as provide heretofore. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present disclosure. It should also be realized by those skilled in the art that such equivalent processes do not depart from the spirit and scope of the disclosure as set forth in the appended claims. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the figures, can be arranged, substituted, combined, and designed in a wide variety of different configurations, all of which are explicitly contemplated and make part of this disclosure.
[0042] While the invention has been disclosed with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made, and equivalents may be substituted without departing from the scope of the invention. In addition, many modifications may be made to adapt to a particular situation or material to the teachings of the invention without departing from its scope.
Definitions
[0043] For convenience, before further description of the present disclosure, certain terms employed in the specification, and examples are delineated here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have the meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.
[0044] The articles "a", "an" and "the" are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. Throughout the specification and claims, the following terms take the meanings explicitly associated herein unless the context clearly dictates otherwise. The meaning of "a", "an", and "the" include plural references. The meaning of "in" includes "in" and "on." Referring to the drawings, like numbers indicate like parts throughout the views. Additionally, a reference to the singular includes a reference to the plural unless otherwise stated or inconsistent with the disclosure herein.
[0045] The terms "comprise" and "comprising" are used in the inclusive, open sense, meaning that additional elements may be included. It is not intended to be construed as "consists of only". Throughout this specification, unless the context requires otherwise the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.
[0046] The terms “include” and “including” is used to mean “including but not limited to”. “Including” and “including but not limited to” are used interchangeably. [0047] The term “aluminate-ion battery” refers to the class of rechargeable batteries in which aluminium ions serve as charge carriers wherein the Al ions are capable of exchanging three electrons. In aluminate-ion battery, Al-ion intercalates, whereas in aluminium-ion battery, Al in atomic form deposits and dissolves.
[0048] The term “separator” refers to the permeable or semi-permeable membranelike materials used to separate two electrodes from each other so as to prevent any short circuit upon contact. In an aspect of the present disclosure, the separator used is an ion-permeable non-conducting separator.
[0049] The term “prismatic -type cell” refers to a cell that have a rectangular shape and is enclosed in a rigid casing made of steel or aluminum. The prismatic-type cell has more surface area than traditional cylindrical cells, which allows them to produce more energy capacity for greater range on electric vehicles or provide more storage capacity.
[0050] As discussed in the background, there are innumerous drawbacks associated with Aluminium- ion batteries. The most serious challenge being the problems associated with acquiring appropriate electrolytes that dissolute and deposit Al electrode reversibly and enables reversible intercalation and deintercalation of Aliens from the positive electrode. In view of the above, there is a need to develop a cost effective, affordable, and industrially viablealuminate-ion battery-based energy storage device with enhanced battery capacity and avoiding the usage of harsh chemicals, tedious process parameters, or metal composites as electrodes.
[0051] In line with the above objectives, the present invention relates to the development of rechargeable aluminate-ion battery with graphite cathode and triethylamine hydrochloride-based eutectic mixture electrolyte for uninterrupted powering supply and solar energy storage etc.
[0052] The present invention portrays the development of safe, eco-friendly, cost effective, rechargeable aluminate-ion battery. The anode used in this battery is aluminium plate having thickness of ~0.8mm, cathode is commercially procured natural graphite. The electrolyte used in this model battery design is eutectic triethylamine hydrochloride-AlCh mixture with or no additives such as MgCh, dissolved at higher temperature (>50 °C) with Mg-salt additive >0 wt%. The electrolyte consists of the chloroaluminate-ions such as AlCLf and AI2CI7’ when no additives are present in the eutectic mixture of triethylamine hydrochloride-AlCh. Upon addition of MgCh that is appropriately dissolved at elevated temperature in the eutectic mixture, it is likely intended to suppress the concentration of AI2CI7’
species in the electrolyte, increasing the A1CU’ concentration and involving concurrent aluminate and Mg+2active ionic entities intercalation leading to the active electrochemical performance. The reaction can be followed as such; MgCh + 2A12C17~ - Mg+2 + 4A1C14’. Aluminium ions along with Mg-ions will diffuse from the electrolyte towards cathode and will intercalate into graphite. Triethyl or methylamine hydrochloride is solid at room temperature. The appropriate ratio of AICI3 addition to the ionic liquid brings eutectic nature. Finally, Mg additive such as MgCh is taken >0 wt% to the 56 wt% of AICI3 and 41 wt% of triethylamine hydrochloride. The electrolyte electrochemical stability window varies with respect to the current collector used to fabricate the electrodes accordingly shift in the observed red-ox potentials will be observed. Hence, the charge-discharge profiles can be engaged in the potential range of 0.0-2.7V vs. A1/A1+3. The disclosed materials assembly is capable of storing and delivering electricity repeatedly (>1000 times). The disclosed design can be upgraded by increasing the dimensions of the electrodes. The disclosed power source can be operated at room temperature. The performance of the power source to electrochemical energy generation was studied with reference to the constant current load applied and the corresponding voltage system displayed.
[0053] Accordingly, the present invention provides a rechargeable aluminate-ion battery utilizing an aluminium anode, carbon-based intercalation cathode and nonvolatile triethylamine hydrochloride -based eutectic mixture ionic liquid with Lewis acid-based additives for energy storage applications at room temperature.
[0054] In an embodiment of the present disclosure, there is provided an aluminate- ion battery comprising: Anodes [9]; Cathodes [11]; Non-conducting separator [10]; and Ionically conducting electrolyte [8], wherein at least one electrolyte is a eutectic mixture-based ionic liquid.
[0055] In an embodiment of the present disclosure, there is provided an An ionic liquid-based eutectic electrolyte supporting aluminate-ion battery for energy storage applications at room temperature comprising: Anodes [9]; Cathodes [11];
Non-conducting separator [10]; and Ionically conducting electrolyte [8], wherein anodes [9] and the fabricated cathodes [11] are connected in parallel with a current collector [6] & [3] respectively and further attached to conducting metal -based connectors e.g. bolts and screws as [4], [5], [1], [2].
[0056] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the anode [9] comprises an aluminium plate or aluminium powder pressed or coated on an conducting current collector, selected from aluminium plate, aluminium alloy having different portions of other metals, or aluminium composite made of aluminium and other conducting fillers. In another embodiment of the present disclosure, theanode [9] comprises an aluminium plate. In yet another embodiment of the present disclosure, the anode [9] comprises an aluminium plate pressed on an anode current collector. In still another embodiment of the present disclosure, the anode [9] comprises an aluminium powder. In more embodiments of the present disclosure, comprises an aluminium powder coated on an anode current collector. In a further embodiment of the present disclosure, the anode [9] is a free-standing aluminium-based anode.
[0057] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the anode is an aluminium powder anode [92] coated on an anode current collector [91] and the cathode is an active material graphite [112] coated on either side of a cathode current collector [111], separated with the non-conducting separator [101].
[0058] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the anodes [92-a & 92-b] are free-standing metal foils or strips and the cathode is coated with active materials like graphite [112-a] on either side of a current collector [111-a], separated with the nonconducting separator [101].
[0059] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the cathode [11] comprises an active material selected from graphite, graphene, carbon nanotubes, hard carbons, soft
carbons, a carbon composite with conducting polymers, or combinations thereof; a conducting filler selected from carbon black, acetylene carbon black, or combinations thereof; a binder selected form polyvinylidene fluoride, sodium alginate, sodium carboxymethyl cellulose, or combinations thereof; and optionally a current collector.In another embodiment of the present disclosure, the active material is graphite, the conducting filler is acetylene carbon black, and the binder is polyvinylidene fluoride. In another embodiment the cathode comprises an active material, a conducting filler, and a binder are physically mixed or formed composite through chemical or electrochemical synthetic procedures.
[0060] In an embodiment of the present disclosure, there is provided an aluminium- ion battery as disclosed herein, wherein the cathode [11] is in pristine or composite form or derivative of graphite, graphene, carbon nanotubes, hard or soft carbons or a composite of conducting polymers physically mixed or formed composite through chemical or electrochemical synthetic procedures.
[0061] In an embodiment of the present disclosure, there is provided an aluminium- ion battery as disclosed herein, wherein the anode or cathode is free-standing or coated on a current collector [6] & [3] fabricated by making slurry using conducting fillers selected from the carbon black, acetylene black and binders are selected form polyvinylidene fluoride or sodium alginate or sodium carboxymethyl cellulose or mixture thereof.
[0062] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the current collectors are metal-based corrosive current collectors Cu, Ni, stainless steel (SS), Al, Ag, Mo, metal alloys, metal composites, or non-corrosive current collectors in the electrolyte like carbon- cloth or fibre or any or any other electronically conducting non-reactive substrate optionally comprising conducting fillers, and additives. In another embodiment of the present disclosure, the anode current collector is selected from aluminium foil, aluminium alloy with various proportions of metals, or aluminium composites with conducting fillers.
[0063] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the electrolyte is selected from first- generation classification of eutectic mixtures -based ionic liquids comprising triethylamine hydrochloride, trimethylamine hydrochloride, AICI3 or combinations thereof and/or mixed with additives selected from MgCh, FeCh, Mg/RPCU ; R=ethyl, methyl, phenyl, butyl, or combinations thereof. In another embodiment of the present disclosure, the electrolyte comprises triethylamine hydrochloride, and AICI3, and/or additives selected from MgCh, FeCh, or combinations thereof. In yet another embodiment of the present disclosure, the electrolyte comprises triethylamine hydrochloride, AICI3, and MgCh.
[0064] In an embodiment of the present disclosure, there is provided an anionic liquid-based eutectic electrolyte supporting aluminate-ion battery for energy storage applications at room temperaturecomprising: i. Anodes [9]; ii. Cathodes [11]; iii. Non-conducting separator [10]; and iv. Ionically conducting electrolyte [8], wherein anodes [9] and the fabricated cathodes [11] are connected in parallel with a current collector [6] & [3] respectively and further attached to conducting metalbased connectors e.g., bolts and screws as [4], [5], [1], [2] and the electrolyte is selected from first-generation classification of eutectic mixtures-based ionic liquids comprising triethylamine hydrochloride or trimethylamine hydrochloride with AICI3 or combinations thereof and/or mixed with additives selected from MgCh, FeCh, or Mg/RPCU ; R is ethyl, methyl, phenyl, or butyl.
[0065] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the at least one anode and the at least one cathode are separated with the non-conducting permeable membrane as separator [10], and the separator is an electronically insulating separator.
[0066] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the battery is made in a form of a coin-cell, cylindrical cell, prismatic-type cell.
[0067] In an embodiment of the present disclosure, there is provided an aluminate- ion battery as disclosed herein, wherein the battery is made in a form of a coin-cell, cylindrical cell, prismatic-type cell, or any other form where the electrolyte quantity can be limited as per the electrode quantity or can be flooded in excess.
[0068] In an embodiment of the present disclosure, there is provided a process of making rechargeable aluminate-ion battery, comprising an electrolyte and carbonaceous cathode against aluminium metal anode.
[0069] In another embodiment, the present invention discloses the cathode for electrochemical cell, especially for aluminium rechargeable batteries, comprising carbon-based intercalation cathode.
[0070] In yet another embodiment, the present invention discloses an intercalation cathode for an electrochemical cell, especially for aluminium rechargeable batteries, comprising a carbon-based compound; wherein carbon-based compound exemplifies graphite, graphene, carbon nanotubes, hard/soft carbons etc. or combinations thereof.
[0071] It is another object of the invention to disclose an organic-based conversiontype conducting polymer cathode where an active material undergoes doping mechanism wherein the conducting polymer can be any form of organic and/or inorganic polymer and/or the composite made from both.
[0072] In yet another embodiment, the present invention discloses an aluminium rechargeable battery comprising; (a) at least one carbon-based intercalation cathode, and/or (b) at least one of intercalation cathodes and/or composite with any other active material that undergoes de -/intercalation, de-/insertion or conversion type mechanism.
[0073] In yet another embodiment, the present invention provides a non-aqueous electrolyte for an electrochemical cell, especially rechargeable aluminium batteries, comprising trialkyl hydrochloride -based Lewis base where alkyl group can be ethyl-, methyl- and/or butyl- derivatives fused with Lewis-acid, especially AICI3 and/or MgCh.
[0074] In yet another embodiment, the present invention provides aluminium rechargeable battery comprising: (a) at least one intercalation cathode; and (b) at least one aluminium anode; and (c) at least one non-aqueous electrolyte which comprises eutectic and/or non-eutectic electrolyte formed with Lewis’s acids.
[0075] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein the intercalation cathode can be carbon-based allotrope such as graphite, graphene, carbon nanotubes, hard/soft carbons in which it can be pure in the pristine state and/or partly and/or fully oxidized as graphene oxide etc.
[0076] In yet another embodiment, the present invention providesaluminium rechargeable battery as defined above, wherein the cathode can be conducting polymer that undergoes conversion-type redox mechanism.
[0077] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein the cathode can be a blend of intercalation type or conversion-type cathode, or a composite made physically or chemically.
[0078] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein the cathode presented and/or deposited on the current collectors comprising a pure metal such as Cu, Ag, Ni, Aland/or any other metal and/or any form of alloy mixed with different proportion of metals.
[0079] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein cathode presented and/or deposited on the current collector comprising a carbon-based electronic conductor.
[0080] In yet another embodiment, the present invention provides rechargeable battery as defined above, wherein carbon-based current collector comprising carbon-fibre and/or foil and/or any other type of carbon-based current collector like foil and/or plate and/or cloth.
[0081] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein cathode can be synthesized chemically or electrochemically in pristine and/or composite form plated and/or deposited on the as defined above current collectors.
[0082] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein cathode can be casted in slurry form using the conducting fillers such as conducting super-P and/or acetylene black and/or carbon nanotubes and/or any other form with the plasticizer and/or binder such as PVDF, sodium alginate, sodium carboxymethyl cellulose and/or the combinations thereof coated and/or dried.
[0083] In yet another embodiment, the present invention providesaluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX in which Ri, R2, and R3 is selected from the group comprising alkyl groups like methyl, ethyl, butyl, phenyl and/or their derivatives; N is phosphonium, ammonium etc , X is fluoride, chloride, bromide or iodide.
[0084] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or RxAlCly, where x=l or 2 and Y=1 or 2.
[0085] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the
formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or RxAlCly and/or MgCh.
[0086] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or RxAlCly and/or FeCh.
[0087] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or RxAlCly and/or RMgCl, where R is methyl, ethyl, butyl, phenyl etc.
[0088] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or RxAlCly and/or Mg/RPCL , where R is methyl, ethyl, butyl, phenyl etc.
[0089] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or RxAlCly and/or ZnCh.
[0090] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, comprising electrolyte represented by the formula R1R2R3NHX with additives from the class of Lewis acids such as AICI3 and/or RxAlCly and/or combination of additives such as metal halides (i.e. MgCh, FeCh, ZnCh or RMgCl or Mg/RPCL where R is methyl, ethyl, butyl or phenyl etc.).
[0091] In yet another embodiment, the present invention provides aluminium rechargeable battery as described above, wherein intercalation cathode can be represented using the formula Cx wherein x can be any integer and/or CxOy wherein x can be any number; >0.
[0092] In yet another embodiment, the present invention provides aluminium rechargeable battery as describe above, wherein cathode can be a composite formed physically and/or chemically through any synthetic procedure.
[0093] In yet another embodiment, the present invention provides aluminium rechargeable battery as describe above, wherein electrolyte can be an ionic liquid derivative formed eutectic and/or non-eutectic with any Lewis acid and/or the derivative of the same.
[0094] In yet another embodiment, the present invention provides aluminium rechargeable battery as describe above, wherein a non-aqueous electrolyte comprises of eutectic and/or non-eutectic composition prepared by addition of aluminium-based salts, especially halide-based salts such as A1CL, MgCh, MgBr2etc.
[0095] In yet another embodiment, the present invention provides aluminium rechargeable battery as describe above, wherein a non-aqueous electrolyte comprises of eutectic and/or non-eutectic composition prepared by the addition of aluminium-based salts, especially halide -based salts such as AIX3 where X can be F, Cl, Br and/or I.
[0096] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is triethylamine hydrochloride eutectic with AICI3 in defined proportion ratio with MgCh additive in >0 and/or <40wt% to that of total eutectic composition formed from individual.
[0097] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is trimethylamine hydrochloride eutectic with AICI3.
[0098] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is trimethylamine hydrochloride eutectic with AICI3 It is another object of the invention to disclose
aluminium rechargeable battery as defined above, wherein electrolyte is mixture of triethylamine hydrochloride and/or trimethylamine hydrochloride eutectic.
[0099] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is mixture of triethylamine hydrochloride and/or trimethylamine hydrochloride eutectic and/or AlCh.
[0100] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein electrolyte is mixture of triethylamine hydrochloride and/or trimethylamine hydrochloride eutectic and/or AICI3 with additives of MgCh.
[0101] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein battery undergoes charge and/or discharge to a maximum high current density of >1000 mA/g.
[0102] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein the full fabricated cell sustains >1000 cycles with capacity fade <0.1% from each cycle.
[0103] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein the full fabricated cell sustains at all environmental conditions like temperature range of -30 to 80 °C and full fabricated cell delivers > 125m Ah/g, maintaining a two-stage plateaus at ~1.8 V and -0.6 V.
[0104] In yet another embodiment, the present invention provides aluminium rechargeable battery as defined above, wherein the full fabricated cell can be operated in the potential window of 0.0-3.5 V vs. A1/A1+3 based on the current collector and active material used in fabricating the cell.
[0105] In yet another embodiment, the present invention provides aluminium full cell having intercalation and/or doping mechanism-based cathode against an aluminium metal anode in triethylamine hydrochloride: AICI3: MgCh in
appropriate weight ratio (56:41:3 wt%) have been developed that has a specific capacity 80 - 125mAh/g at c/10-rate. The cells exhibited nominal open circuit potential of ~1.0 - 1.5V, varying on the type of current collector used to fabricate the cathode. The cell has shown a coulombic efficiency of >90% during cycling.
Characterization of cathode of present invention
Description of the Schematic Illustrations
[0106] Schematic illustration of the fabricated prismatic cell cross section is shown in Figure 1, wherein the cell contains multiple anodes [9], multiple cathodes [11] separated with a non-conducting separator [10] flooded in the ionically conducting electrolyte [8]. The anodes [9] present from the cell and the fabricated cathodes [11] are connected in parallel with a current collector [6] and [3] respectively, further attached to conducting metal-based connectors like bolts and screws as [4], [5], [1], [2].
[0107] Figure 2 illustrates the schematic representation of the arrangement of anode [9], cathode [11] divided by a separator [10] as shown in Figure 1 described precisely wherein the aluminium powder anode, [92] is coated on the electronically conducting current collector [91] and cathode is coated with active materials like graphite [112] on either side of the current collector [111], separated with anon- conducting separator [101] to prevent any possible short-circuit.
[0108] Figure 3 illustrates the schematic representation of the arrangement of anode [9], cathode [11] divided by a separator [10] as shown in Figure 1 described, herein, precisely wherein the aluminium anode [92-a] is free-standing metal foil or strip and cathode is coated with active materials like graphite [112-a] on either side of the current collector [111-a], separated with anon-conducting ion-permeable separator [101].
[0109] Figure 4 illustrates the schematic representation of the arrangement of anode [9], cathode [11] divided by a separator [10] as shown in Figure 1 described herein, precisely wherein the aluminium anode [92-b] is free-standing metal foil or strip
and cathode is a graphite sheet, block or plate [112-b] naturally occurring, synthesized or processed, separated with anon-conducting separator [101].
[0110] Figure 5 is the schematic illustration of systematic arrangement of anodes and cathodes divided by separators in fabricating a prismatic cell.
[0111] Figure 6 is the aluminium plate anode used in fabricating the cell.
[0112] Figure 7 is the graphite coated electrode on the woven carbon-fibre used in fabricating the prismatic cell.
[0113] Figure 8 is the full prismatic cell with dimension (lengthxwidthxheight=7cmx3cmx 11 cm) .
[0114] Although the subject matter has been described in considerable detail with reference to certain examples and implementations thereof, other implementations are possible.
EXAMPLES
[0115] The following examples are given by way of illustration and serve to provide the best mode of practice for the present invention and should not be constructed to limit the scope of the present invention in any manner.
Example - 1: Aluminium Prismatic cell-1
[0116] Aluminium battery with Al plate anode and graphite coated on woven carbon-fibre was assembled in a eutectic electrolyte comprising triethylamine hydrochloride and AICI3 composition. The assembled cell dimension was (length xheight xwidth, lx hx w) 7cmx l0cmx4cm in which 5A1 plate anodes and 6 graphite coated cathodes had lxw= 6cmx7.5cm dimensions with an active material graphite coating of ~2.0 grams on each electrode. About 1.5:1 molar ratio of AICI3: triethylamine hydrochloriderespectivelywas taken as electrolyte. The assembled
Aluminium Prismatic cell-1 exhibited a capacity of -300 mAh, with a capacity retention of >90%.
Example - 2: Aluminium Prismatic cell-2
[0117] Aluminium battery comprising Al plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte. The assembled cell dimension was kept as (Ixhxw =) 7cmx 10cmx4cm in which 6 Al plate anodes and 5 graphite coated cathodes had lxw= 6cmx7.5cm with an active graphite coating of -2.0 grams on each electrode. 1.5:1 molar ratio of AICI3: triethylamine hydrochloriderespectivelywas taken as electrolyte to obtain Aluminium Prismatic cell-2 for which a capacity of -300 mAh was achieved, with a capacity retention of >90%.
Example - 3: Aluminium Prismatic cell-3
[0118] Aluminium battery with Al plate anode and graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte. The assembled cell dimension was kept as (Ixhxw) 7cmx 10cmx4cm in which 6 Al plate anodes and 5 graphite coated cathodes had Ixb = 6 cm x 7.5 cm with an active graphite coating of -2.0 grams on each electrode. 56:41:3 wt% ratio of AICI3: triethylamine hydrochloride: MgCh respectively was taken as electrolyte to obtain the Aluminium Prismatic cell-3 for which a capacity of -300 mAh was achieved, with a capacity retention of >90%.
Example - 4: Aluminium Prismatic cell-4
[0119] Aluminium battery with Al plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte. The assembled cell dimension was kept as (Ixhxw) 7cmx 10cmx4cm in which 5 Al plate anodes and 6 graphite coated cathodes had Ixb = 6 cm x 7.5 cm with an active graphite coating of -2.0 grams on each electrode. 56:41:3 wt% ratio of AICI3: trimethylamine hydrochloride: MgCh respectivelywas taken as electrolyte to obtain the Aluminium
Prismatic cell-4 which exhibited a capacity of -300 mAh, with a capacity retention of >90%.
Example - 5: Aluminium Prismatic cell-5
[0120] Aluminium battery with aluminium plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte. The assembled cell dimension was kept as (Ixhxw =) 7cmx 10cmx4cm in which 9 Al plate anodes and
8 graphite coated cathodes had Ixb = 6 cm x 7.5 cm with an active graphite coating of -2.0 grams on each electrode. 56:41:3 wt.% ratio of AICI3: triethylamine hydrochloride: MgCh respectivelywas taken as electrolyte to obtain the Aluminium Prismatic cell-5. A capacity of ~900mAh was achieved for the Aluminium Prismatic cell— 5, with a capacity retention of >90%.
Example - 6: Aluminium Prismatic cell-6
[0121] Aluminium battery with aluminium plate anode and Graphite coated on woven carbon-fibre was assembled in the eutectic electrolyte. The assembled cell dimension was kept as (Ixhxw =) 7cm x 10cm x 4cm in which 9 Al plate anodes and
9 graphite coated cathodes had Ixb = 6 cm x 7.5 cm with an active graphite coating of -2.0 grams on each electrode. 56:41:3 wt% ratio of AICI3: triethylamine hydrochloride: MgCh respectivelywas taken as electrolyte to obtain Aluminium Prismatic cell-6. A capacity of -1100 mAh is achieved, with a capacity retention of >90%.
Example - 7: Aluminium Prismatic cell-7
[0122] Aluminium battery with aluminium plate anode and self- standing graphite plate having 1 mm thickness was assembled in the eutectic electrolyte. The assembled cell dimension was kept as (Ixhxw =) 7cmx l0cmx4cm in which 10 Al plate anodes and 9 graphite coated cathodes had Ixb = 6 cm x 7.5 cm with an active graphite coating of -2.0 grams on each electrode. 56:41:3 wt% ratio of AICI3: triethylamine hydrochloride: MgCh respectivelywas taken as electrolyte to obtain
Aluminium Prismatic cell-7. A capacity of -1100 mAh was achieved for the cell, with a capacity retention of >90%.
Example - 8: Aluminium Prismatic cell-8
[0123] Aluminium battery with aluminium plate anode and self- standing graphite plate having 1 mm thickness was assembled in the eutectic electrolyte with an approximate weight of 1.2 grams. The assembled cell dimension was kept fixed as(lxhxw=) 7cmx l0cmx4cm in which 10 Al plate anodes and 9 graphite coated cathodes having Ixb = 6 cm x 7.5 cm with an active graphite coating of -2.0 grams on each electrode on woven carbon cloth (having weight of 0.7 g). 56:41:3 wt% of AICI3: triethylamine hydrochloride: MgCh respectively is taken as electrolyte. A capacity of -1100 mAh is achieved, with a capacity retention of >90%.
Example - 9: Electrode fabrication
[0124] Graphite powder is commercially procured from Sigma Aldrich (<45 m, >99.99% trace metal basis). The conventional electrodes were prepared from an active material slurry which was made using 90 wt% active material, 5 wt.% acetylene carbon black (100% compressed, 99.9+% procured from Alfa Aesar) and 5 wt.% poly vinylidene fluoride (PVDF) as binder (average Mw -180,000 by GPC) in N-methyl-Pyrrolidone solvent (Avra Chemicals pvt. Ltd.). Then the slurry was coated on the current collectors such as stainless steel (SS)-mesh or conducting carbon-cloth/fibers, followed by drying under vacuum at 90 °C for 16 hours. The working electrode having dimension of 0.4x0.5 cm2 area was used for further characterizations. The active material loading on the conventional current collector was controlled between 2.0 - 4.5 mgcm’2.
Example - 10: Synthesis of electrolyte
[0125] The electrolyte used for the study were prepared in an Argon-filled glove box (Make: MBraun, < 1 ppm of water and oxygen). Typically, triethylamine hydrochloride or trimethylamine hydrochloride was mixed with AICI3 in an appropriate molar ratio of 1:1.1 to 1.7 forming eutectic. In another procedure, 56
wt% of triethylamine hydrochloride or trimethylamine hydrochloride and 41 wt% of AICI3 were mixed via constant stirring, resulting in a eutectic mixture at room temperature. Further, 3 wt.% of MgChwas added to the mixture and kept under stirring at 80°C for next 12 hours to obtain the electrolyte.
Example - 11: Separator
[0126] A glass fibre having -0.1mm thickness was considered as separator to prevent any short-circuit.
Example - 12: Assembly of the Al flooded cell.
[0127] The cells were assembled in the Ar-filled glovebox (MBraun, <1 ppm of water and oxygen). Al plate having 0.08 mm thickness and area of 0.2 cm2was taken as anode, graphite coated stainless-steel (dimensions similar to that of anode) was taken as cathode. Electrolyte obtained by the process as explained in Example-3 was used as electrolyte. Separator as stated in the example- 11 was used to obtain Al flooded cell.
Example - 13: Assembly of the Al coin-cell
[0128] The cells were assembled in the Ar-filled glovebox (MBraun, <1 ppm of water and oxygen). Al plate having 0.08 mm thickness and 1.2 cm diameter (area of 1.13 cm2) was taken as anode, graphite coated stainless-steel (dimensions similar to that of anode) was taken as cathode. Electrolyte obtained by the process as described in Example- lOwas used as electrolyte. Separator as stated in the Example-1 Iwas used.
Example - 14: Electrochemical Characterisations
[0129] The fabricated test cells were comprehensively evaluated for their electrochemical performance employing cyclic voltammetry (CV) analysis on a multi-channel Electrochem Origalys Workstation (Model - OGF05A). Chargedischarge studies of the assembled cells were performed using GCD technique in
the voltage window of 0.0V - 2.0V under constant current followed by a rest period of Ih between each charge/discharge cycle.
Example - 15: Half-cell cyclic voltammetry
[0130] Al-anode plating and stripping in the eutectic electrolyte with and without Mg-salt was primarily investigated by fabricating a three-electrode cell using Al- Counter electrode, Mg-Reference electrode and Pt-wire as Working electrode in the potential window of -1.0V to 2.0V vs. A1/A1+3 at the slew rate of 5.0 mV. s’1.
Example - 16: Galvanostatic charge-discharge analysis
[0131] Galvanostatic charge-discharge analysis on the Al-graphite cell in the MgCh containing triethylamine hydrochloride: AICI3 electrolyte as depicted in Figure 10 (a) and (b) respectively. The cells were charged and discharged at the current density of 50 mA/g within the potential window of 2.5V to 0.0V vs. A1/A1+3 shown in Figure 10 (a). Al-graphite cell shown a specific capacity of -125 mAh/g. Al-Graphite cell cycled at different current density from 50 mA/g to 200 mA/g are depicted in Figure 10 (b). Al-Graphite cell at high current density of 200 mA/g shown a discharge capacity of -40 mAh/g. The GCD cycling of Al-Graphite has delivered two plateaus while charge and discharge depicting the two-stages of intercalation of ionic species occurring into the host electrode. It is expected that the concurrent intercalation of Al- and Mg-ionic species which contributes the overall performance of the cell.
Example - 17: Full-cell cyclic voltammetry
[0132] Cyclic voltammetry recorded on Al-Graphite cells depicted in Figure 11 in the triethylamine hydrochloride: AICI3: MgCh electrolyte in the potential window of 0.0V to 2.5V vs. A1/A1+3 at the scan rate of 0.3 mV/s.
Example - 18: Reversible cycling performance of the fabricated cells
[0133] The rate capability of Al-Graphite is shown in Figure 12. Al-graphite cell showed a stable discharge capacity of -80 mAh/g, charged and drained at 200 mA/g
for, maintaining a stable efficiency of >85%. However, the capacity fade was found minimal, and sustained for >100 cycles charge-discharge cycles.
ADVANTAGES OF THE INVENTION i. Aluminium, graphite, triethylamine hydrochloride and aluminium chloride used for preparation of Aluminate-Ion Battery are abundant, safe, eco-friendly, and indigenous. ii. Aluminate-Ion Battery of the present disclosure is very safe, even if the battery is pierced while discharge, it will not burst into flames or explode. iii. Aluminate-Ion Battery is cost effective, affordable to common man and industrial viable. iv. Higher battery capacity since Aluminium element is capable of transferring three ions or packets of currentAl3+ at a same time. v. No composite electrode materials were used for preparation of Aluminate- Ion Battery.
Claims
1. Anionic liquid -based eutectic electrolyte supporting aluminate-ion battery for energy storage applications at room temperature comprising: i. Anodes [9]; ii. Cathodes [11]; iii. Non-conducting separator [10]; and iv. Ionically conducting electrolyte [8], wherein anodes [9] and the fabricated cathodes [11] are connected in parallel with a current collector [6] & [3] respectively and further attached to conducting metal-based connectors e.g., bolts and screws as [4], [5], [1], [2]; and the electrolyte is selected from first-generation classification of eutectic mixtures-based ionic liquids comprising triethylamine hydrochloride or trimethylamine hydrochloride with AlCh or combinations thereof and/or mixed with additives selected from MgCh, FeCh, or Mg/RPC ; R is ethyl, methyl, phenyl, or butyl.
2. The aluminate-ion battery as claimed in claim 1, wherein the anode [9] comprises an aluminium plate or aluminium powder pressed or coated on a conducting current collector, selected from aluminium plate, aluminium alloy having different portions of other metals, or aluminium composite made of aluminium and other conducting fillers.
3. The aluminate-ion battery as claimed in claim 1, wherein the anode is an aluminium powder anode [92] coated on an anode current collector [91] and the cathode is an active material graphite [112] coated on either side of a cathode current collector [111], separated with the non-conducting separator [101].
4. The aluminate-ion battery as claimed in claim 1, wherein the anodes [92-a & 92-b] are free-standing metal foils or strips and the cathode is coated with active materials like graphite [112-a] on either side of a current collector [111-a], separated with the non-conducting separator [101].
The aluminate-ion battery as claimed in claim 1, wherein the cathode [11] is in pristine or composite form or derivative of graphite, graphene, carbon nanotubes, hard or soft carbons or a composite of conducting polymers physically mixed or formed composite through chemical or electrochemical synthetic procedures. The aluminate-ion battery as claimed in claim 1, wherein the anode or the cathode is free-standing or coated on a current collector [6] & [3], fabricated by making slurry using conducting fillers selected from the carbon black, acetylene black; and binders are selected form polyvinylidene fluoride or sodium alginate or sodium carboxymethyl cellulose or mixture thereof. The aluminate-ion battery as claimed in claims 2 to 3, wherein the current collectors are metal-based corrosive current collectors Cu, Ni, SS, Al, Ag, Mo or alloys or non-corrosive current collectors in the electrolyte like carbon-cloth or fibre or any other electronically conducting non-reactive substrate for the anode. The aluminate-ion battery as claimed in claim 1, wherein the anodes and the cathodes are separated with the non-conducting permeable membrane as separator [10]. The aluminate-ion battery as claimed in claim 1 , wherein the battery is made in a form of a coin-cell, cylindrical cell, prismatic-type cell or any other form where the electrolyte quantity can be limited as per the electrode quantity or can be flooded in excess.
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| WO2017106337A1 (en) * | 2015-12-15 | 2017-06-22 | The Board Of Trustees Of The Leland Stanford Junior University | Improved electrolytes, current collectors, and binders for rechargeable metal-ion batteries |
| WO2021168553A1 (en) * | 2020-02-24 | 2021-09-02 | The Governing Council Of The University Of Toronto | Aluminum-ion battery using aluminum chloride/trimethylamine ionic liquid as electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017106337A1 (en) * | 2015-12-15 | 2017-06-22 | The Board Of Trustees Of The Leland Stanford Junior University | Improved electrolytes, current collectors, and binders for rechargeable metal-ion batteries |
| WO2021168553A1 (en) * | 2020-02-24 | 2021-09-02 | The Governing Council Of The University Of Toronto | Aluminum-ion battery using aluminum chloride/trimethylamine ionic liquid as electrolyte |
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