JP7200264B2 - リチウム硫黄およびナトリウム硫黄電池カソード - Google Patents
リチウム硫黄およびナトリウム硫黄電池カソード Download PDFInfo
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- JP7200264B2 JP7200264B2 JP2020560826A JP2020560826A JP7200264B2 JP 7200264 B2 JP7200264 B2 JP 7200264B2 JP 2020560826 A JP2020560826 A JP 2020560826A JP 2020560826 A JP2020560826 A JP 2020560826A JP 7200264 B2 JP7200264 B2 JP 7200264B2
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- Prior art keywords
- metal
- lithium
- uio
- sulfur
- organic framework
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims description 38
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims description 13
- 239000012621 metal-organic framework Substances 0.000 claims description 228
- 230000007547 defect Effects 0.000 claims description 86
- 229910052744 lithium Inorganic materials 0.000 claims description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 55
- 239000005077 polysulfide Substances 0.000 claims description 55
- 229920001021 polysulfide Polymers 0.000 claims description 55
- 150000008117 polysulfides Polymers 0.000 claims description 55
- 230000002950 deficient Effects 0.000 claims description 52
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 44
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- 239000011593 sulfur Substances 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 18
- 230000014759 maintenance of location Effects 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 238000004873 anchoring Methods 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010348 incorporation Methods 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 230000007847 structural defect Effects 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000011343 solid material Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 3
- 230000002000 scavenging effect Effects 0.000 claims 2
- 229910052729 chemical element Inorganic materials 0.000 claims 1
- 239000013207 UiO-66 Substances 0.000 description 73
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 48
- 210000004027 cell Anatomy 0.000 description 45
- 239000000243 solution Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 27
- 239000003607 modifier Substances 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 230000001965 increasing effect Effects 0.000 description 21
- 230000001351 cycling effect Effects 0.000 description 20
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000002131 composite material Substances 0.000 description 18
- 238000006138 lithiation reaction Methods 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 229910014103 Na-S Inorganic materials 0.000 description 14
- 229910014147 Na—S Inorganic materials 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 239000003446 ligand Substances 0.000 description 14
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 12
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 241000894007 species Species 0.000 description 9
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- -1 zinc(II) porphyrin Chemical class 0.000 description 8
- 238000005538 encapsulation Methods 0.000 description 7
- 238000007306 functionalization reaction Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 150000007942 carboxylates Chemical class 0.000 description 6
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 6
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QNVNLUSHGRBCLO-UHFFFAOYSA-N H2BDC Natural products OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 5
- 229910013553 LiNO Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000001994 activation Methods 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000009881 electrostatic interaction Effects 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 239000013183 functionalized metal-organic framework Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000014233 sulfur utilization Effects 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910001216 Li2S Inorganic materials 0.000 description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 4
- 238000002479 acid--base titration Methods 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000005595 deprotonation Effects 0.000 description 4
- 238000010537 deprotonation reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 210000003771 C cell Anatomy 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910018091 Li 2 S Inorganic materials 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 239000012924 metal-organic framework composite Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000013384 organic framework Substances 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- ZOQCTFVIEBUWIT-UHFFFAOYSA-N 1,2,3,3a-tetrahydropyrene-2,7-dicarboxylic acid Chemical compound C1=C2CC(C(=O)O)CC(C=C3)C2=C2C3=CC(C(O)=O)=CC2=C1 ZOQCTFVIEBUWIT-UHFFFAOYSA-N 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- DAWHTISAONTGQE-UHFFFAOYSA-N 3-(2-phenylphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1C(O)=O DAWHTISAONTGQE-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SAVROPQJUYSBDD-UHFFFAOYSA-N formyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CO SAVROPQJUYSBDD-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OTAJGWQCQIEFEV-UHFFFAOYSA-N pyrene-2,7-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=C2C=CC3=CC(C(=O)O)=CC4=CC=C1C2=C43 OTAJGWQCQIEFEV-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 1
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 1
- CAWMOPYMZTVESL-UHFFFAOYSA-N 2-[1-(2-carboxyphenyl)-2-adamantyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1C(C=2C(=CC=CC=2)C(O)=O)(C2)CC3CC2CC1C3 CAWMOPYMZTVESL-UHFFFAOYSA-N 0.000 description 1
- NMOWIPGGZPVCKI-UHFFFAOYSA-N 2-[3,4-bis(2-carboxyphenyl)phenyl]benzoic acid Chemical compound C=1(C(=CC=C(C=1)C1=CC=CC=C1C(=O)O)C1=CC=CC=C1C(=O)O)C1=CC=CC=C1C(=O)O NMOWIPGGZPVCKI-UHFFFAOYSA-N 0.000 description 1
- SVAJWMFPXLZPHL-UHFFFAOYSA-N 2-[3,5-bis(2-carboxyphenyl)phenyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC(C=2C(=CC=CC=2)C(O)=O)=CC(C=2C(=CC=CC=2)C(O)=O)=C1 SVAJWMFPXLZPHL-UHFFFAOYSA-N 0.000 description 1
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- JRMAQQQTXDJDNC-UHFFFAOYSA-N 2-ethoxy-2-oxoacetic acid Chemical compound CCOC(=O)C(O)=O JRMAQQQTXDJDNC-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- YROTZTMCXKTYMW-UHFFFAOYSA-N 4-[4-(4-carboxyphenyl)buta-1,3-diynyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C#CC#CC1=CC=C(C(O)=O)C=C1 YROTZTMCXKTYMW-UHFFFAOYSA-N 0.000 description 1
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- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ORAAZVDXWSKZHK-UHFFFAOYSA-N Bis-(1-chloro-2-propyl) phosphate Chemical compound CC(CCl)OP(O)(=O)OC(C)CCl ORAAZVDXWSKZHK-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 241001414890 Delia Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
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- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 description 1
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- QMKYBPDZANOJGF-UHFFFAOYSA-K benzene-1,3,5-tricarboxylate(3-) Chemical compound [O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-K 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
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- FKSLYSSVKFYJKE-UHFFFAOYSA-N n,n-diethylethanamine;methanol Chemical compound OC.CCN(CC)CC FKSLYSSVKFYJKE-UHFFFAOYSA-N 0.000 description 1
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- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 230000000284 resting effect Effects 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WAWVSIXKQGJDBE-UHFFFAOYSA-K trilithium thiophosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=S WAWVSIXKQGJDBE-UHFFFAOYSA-K 0.000 description 1
- QMKYBPDZANOJGF-UHFFFAOYSA-N trimesic acid Natural products OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
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Description
本発明の分野は概して、高容量リチウム硫黄電池および環境温度ナトリウム硫黄電池に関する。
S8 → Li2S8→ Li2S6 → Li2S4→ LiS3 ● → Li2S2→ Li2S
電池の充電サイクル中、多硫化物はカソードにて形成され、例えば、次の順序に従うようなものである:
Li2S → Li2S2→ LiS3 ● → Li2S4→ Li2S6 → Li2S8→ S8。
2 Na + xS ⇔ Na2Sx
Li-S電池と同様、RT Na-Sデバイスには、商品化、例えば、理論に近い充電容量を達成し、および繰り返しサイクル(repeated cycling)により電荷を保持するなどのようなものを妨げてきたという重大な難題がある。
本発明の簡便な説明
82mgのLiNO3(70ミリモル)を10.5mLのDMFにおいて溶解することによってリチウム取込み溶液を調製した。溶解したら、6.3mLのトリエチルアミン(TEA、45mmol)を脱プロトン化用の塩基として溶液に加えた。次に、この溶液を、約150mgのHCl活性化UiO-66(MOD)を含む20mLのシンチレーションバイアルに加え、次いで混合するために振とうすることによって続けた。混合物を反応させた(例は、室温にて、または60または80℃に設定したオーブンにおいて24時間)。24時間後溶液をデカントし、および20mLのアセトンと置き換えた。固形物を遠心分離によって収集し、20mLのアセトンにより洗浄し、および新しいアセトン溶液において夜通し浸漬した。固形物をアセトンによりさらに4回洗浄し(washed four more times)、および追加的な一回の洗浄後、固形物をアセトンにおいて夜通し浸した。アセトン洗浄に続き、溶媒をDCMに切り替え、および上記の洗浄プロセスを繰り返した。最後のDCM洗浄後、溶媒を除去し、およびLi-UiO-66(MOD)固形物を空気において乾燥させた。サンプルは更なる使用または特性評価までデシケーターにおいて貯蔵した。
Claims (14)
- 電池カソードであって、複数の欠陥のある金属有機フレームワークの部分を含み:
(i)そのときにそれぞれの欠陥のある金属有機フレームワークの部分には、構造的欠陥および組成的特色から選ばれる少なくとも一の欠陥が無関係に含まれ;および
(ii)そのときにそれぞれの欠陥は電池アノード金属イオンの捕捉、多硫化物の捕捉のための化学的アンカー置換基の組込み、またはそれらの組合せを無関係に可能にさせるものであり、および
そのときに前記金属有機フレームワークの金属はジルコニウム、ハフニウム、セシウム、チタン、バナジウム、モリブデン、ニオブ、およびクロムから選ばれる、カソード。 - 前記金属有機フレームワークの金属はジルコニウムである、請求項1に記載された電池カソード。
- 前記欠陥は金属配位部位およびプロトン性部位から無関係に選ばれる、請求項1または請求項2に記載された電池カソード。
- 前記カソードには、硫黄が含まれ、およびリチウム硫黄電池カソードであり、前記欠陥は前記プロトン性部位であり、そのときに前記プロトン性部位の実体的部分はリチウムにより機能化される、請求項3に記載された電池カソード。
- 前記カソードには、硫黄が含まれ、およびナトリウム硫黄電池カソードであり、前記欠陥は前記プロトン性部位であり、そのときに前記プロトン性部位の実体的部分はナトリウムにより機能化される、請求項3に記載された電池カソード。
- 以下の:
(i)リチウムが含まれるアノード;
(ii)電解質;および
(iii)硫黄および複数の欠陥のある金属有機フレームワークの部分が含まれるカソードであり、そこでは
(1)そのときにそれぞれの欠陥のある金属有機フレームワークの部分には、構造的欠陥および組成的特色から選ばれる少なくとも一の欠陥が無関係に含まれ;および
(2)そのときにそれぞれの欠陥は電池アノード金属イオンの捕捉、または多硫化物の捕捉のための化学的アンカー置換基の組込みを無関係に可能にさせる
もの
を含み、そこで
前記金属有機フレームワークの金属はジルコニウム、ハフニウム、セシウム、チタン、バナジウム、モリブデン、ニオブ、およびクロムから選ばれる、リチウム硫黄電池。 - 前記金属有機フレームワークの金属はジルコニウムである、請求項6に記載されたリチウム硫黄電池。
- 前記欠陥は金属配位部位およびプロトン性部位から無関係に選ばれる、請求項6または請求項7に記載されたリチウム硫黄電池。
- 前記複数の欠陥のある金属有機フレームワークの部分の一部分には、プロトン性部位である少なくとも一の欠陥が含まれ、そこで前記プロトン性部位の実体的部分はリチウムにより機能化される、請求項6ないし8のいずれか一項に記載されたリチウム硫黄電池。
- 20回の充放電サイクル後に少なくとも60%の容量保持を有し、および20回の充放電サイクル後に少なくとも800mAh g-1の絶対容量を有する、請求項6ないし9のいずれか一項に記載されたリチウム硫黄電池。
- リチウム伝導性を有する固形物質であって、リチウムおよび複数の欠陥のある金属有機フレームワークの部分を含み:
(i)そのときにそれぞれの欠陥のある金属有機フレームワークの部分には、金属配位部位、組成的特色およびプロトン性部位から選ばれる欠陥が無関係に含まれ;および
(ii)そのときにリチウムは欠陥に結合または捕捉される
ものであり、
(iii)前記複数の欠陥のある金属有機フレームワークの部分の一部分には、プロトン性部位である少なくとも一の欠陥が含まれ、前記プロトン性部位の実体的な部分はリチウムまたはナトリウムで機能化されている、物質。 - 前記金属有機フレームワークの金属はジルコニウム、ハフニウム、セシウム、銅、亜鉛、チタン、鉄、バナジウム、モリブデン、ニオブ、およびクロムから選ばれる、請求項11に記載された固形物質。
- 前記金属はジルコニウムである、請求項12に記載された固形物質。
- 前記固形物質は電解質である、請求項11ないし13のいずれか一項に記載された固形物質。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102336774A (zh) | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | 一种合成基于btc的纳米级金属有机骨架材料的方法 |
CN102738510A (zh) | 2012-06-25 | 2012-10-17 | 中南大学 | 一种锂离子电池固态电解质及应用 |
CN103236542A (zh) | 2013-04-17 | 2013-08-07 | 浙江大学 | 一种以金属-有机框架材料为硫载体的锂硫电池正极材料的制备方法 |
JP2015145454A (ja) | 2014-02-03 | 2015-08-13 | 国立大学法人京都大学 | イオン伝導性複合体およびその製造方法 |
US20170207446A1 (en) | 2016-01-19 | 2017-07-20 | Korea Advanced Institute Of Science And Technology | Material for electrode in energy storage device using metal organic frameworks with element with unshared electron pair, energy storage device comprising the same, and method for analyzing the same |
WO2017152171A1 (en) | 2016-03-04 | 2017-09-08 | Cornell University | Stable room-temperature sodium-sulfur battery |
Family Cites Families (2)
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CN105633418B (zh) * | 2015-12-25 | 2018-09-14 | 华南理工大学 | 一种锂空电池阴极用Pt/UIO-66复合材料及其制法 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102336774A (zh) | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | 一种合成基于btc的纳米级金属有机骨架材料的方法 |
CN102738510A (zh) | 2012-06-25 | 2012-10-17 | 中南大学 | 一种锂离子电池固态电解质及应用 |
CN103236542A (zh) | 2013-04-17 | 2013-08-07 | 浙江大学 | 一种以金属-有机框架材料为硫载体的锂硫电池正极材料的制备方法 |
JP2015145454A (ja) | 2014-02-03 | 2015-08-13 | 国立大学法人京都大学 | イオン伝導性複合体およびその製造方法 |
US20170207446A1 (en) | 2016-01-19 | 2017-07-20 | Korea Advanced Institute Of Science And Technology | Material for electrode in energy storage device using metal organic frameworks with element with unshared electron pair, energy storage device comprising the same, and method for analyzing the same |
WO2017152171A1 (en) | 2016-03-04 | 2017-09-08 | Cornell University | Stable room-temperature sodium-sulfur battery |
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