WO2022270561A1 - 非水電解液、非水ナトリウムイオン電池、非水カリウムイオン電池、非水ナトリウムイオン電池の製造方法、及び非水カリウムイオン電池の製造方法 - Google Patents
非水電解液、非水ナトリウムイオン電池、非水カリウムイオン電池、非水ナトリウムイオン電池の製造方法、及び非水カリウムイオン電池の製造方法 Download PDFInfo
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- WO2022270561A1 WO2022270561A1 PCT/JP2022/024992 JP2022024992W WO2022270561A1 WO 2022270561 A1 WO2022270561 A1 WO 2022270561A1 JP 2022024992 W JP2022024992 W JP 2022024992W WO 2022270561 A1 WO2022270561 A1 WO 2022270561A1
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- carbon atoms
- optionally substituted
- anion
- aqueous
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 62
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 58
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 57
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 28
- 229940037179 potassium ion Drugs 0.000 title abstract 5
- -1 sulfone compounds Chemical class 0.000 claims abstract description 209
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
- 150000004045 organic chlorine compounds Chemical class 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 139
- 239000008151 electrolyte solution Substances 0.000 claims description 71
- 125000001424 substituent group Chemical group 0.000 claims description 56
- 239000000654 additive Substances 0.000 claims description 38
- 150000001450 anions Chemical class 0.000 claims description 36
- 125000000304 alkynyl group Chemical group 0.000 claims description 31
- 230000000996 additive effect Effects 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 22
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 22
- 125000004104 aryloxy group Chemical group 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 125000001153 fluoro group Chemical group F* 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 15
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 15
- 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 14
- 150000001768 cations Chemical class 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 11
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 10
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 9
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 9
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 8
- 150000005678 chain carbonates Chemical group 0.000 claims description 7
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- LNKQQZFLNUVWQQ-UHFFFAOYSA-N 1-chloro-2,2-bis(4'-chlorophenyl)ethylene Chemical compound C=1C=C(Cl)C=CC=1C(=CCl)C1=CC=C(Cl)C=C1 LNKQQZFLNUVWQQ-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229940074371 monofluorophosphate Drugs 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 6
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 5
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 5
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 claims description 5
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-M chlorosulfate Chemical compound [O-]S(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-M 0.000 claims description 5
- 150000004292 cyclic ethers Chemical class 0.000 claims description 5
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 claims description 5
- QKPIQPBNFUNZSJ-UHFFFAOYSA-N dichlorophosphorylimino(oxo)methane Chemical compound ClP(Cl)(=O)N=C=O QKPIQPBNFUNZSJ-UHFFFAOYSA-N 0.000 claims description 5
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- DKZQZHQHDMVGHE-UHFFFAOYSA-N methanedisulfonyl chloride Chemical compound ClS(=O)(=O)CS(Cl)(=O)=O DKZQZHQHDMVGHE-UHFFFAOYSA-N 0.000 claims description 5
- PVMUVDSEICYOMA-UHFFFAOYSA-N n-chlorosulfonylsulfamoyl chloride Chemical class ClS(=O)(=O)NS(Cl)(=O)=O PVMUVDSEICYOMA-UHFFFAOYSA-N 0.000 claims description 5
- YNECJZSONMVFHE-UHFFFAOYSA-N phosphoric dichloride fluoride Chemical compound FP(Cl)(Cl)=O YNECJZSONMVFHE-UHFFFAOYSA-N 0.000 claims description 5
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 5
- QHABYFQJNLKLOR-UHFFFAOYSA-N propane-1,3-disulfonyl chloride Chemical compound ClS(=O)(=O)CCCS(Cl)(=O)=O QHABYFQJNLKLOR-UHFFFAOYSA-N 0.000 claims description 5
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 5
- OQHXCCQBSGTCGM-UHFFFAOYSA-N 1,2,5-oxadithiolane 2,2,5,5-tetraoxide Chemical compound O=S1(=O)CCS(=O)(=O)O1 OQHXCCQBSGTCGM-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 4
- GKFGCJGPBOCQQW-UHFFFAOYSA-N 2-ethoxy-1,2,2,6,6-pentafluoro-1,3,5-triaza-2lambda5,4,6lambda5-triphosphacyclohex-5-ene Chemical compound C(C)OP1(N(P(=NPN1)(F)F)F)(F)F GKFGCJGPBOCQQW-UHFFFAOYSA-N 0.000 claims description 4
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 4
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims description 4
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 4
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 4
- FOLJHXWWJYUOJV-UHFFFAOYSA-N 4-ethynyl-1,3-dioxolan-2-one Chemical compound O=C1OCC(C#C)O1 FOLJHXWWJYUOJV-UHFFFAOYSA-N 0.000 claims description 4
- PXTRGXMFFGBWFT-UHFFFAOYSA-N 4-propyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CCCC1COS(=O)(=O)O1 PXTRGXMFFGBWFT-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- HXIYLEMRVRJBAG-UHFFFAOYSA-N OP(O)(O)=O.Cl.Cl.Cl.Cl.Cl.Cl Chemical compound OP(O)(O)=O.Cl.Cl.Cl.Cl.Cl.Cl HXIYLEMRVRJBAG-UHFFFAOYSA-N 0.000 claims description 4
- ZJDLLSMETLKVLS-UHFFFAOYSA-N OP(O)(O)=O.F.Cl.Cl.Cl.Cl.Cl Chemical compound OP(O)(O)=O.F.Cl.Cl.Cl.Cl.Cl ZJDLLSMETLKVLS-UHFFFAOYSA-N 0.000 claims description 4
- USNRYPYNVNANRB-UHFFFAOYSA-N P(=O)(N=C=O)(F)Cl Chemical compound P(=O)(N=C=O)(F)Cl USNRYPYNVNANRB-UHFFFAOYSA-N 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- PMGNOQUKCGLETL-TYYBGVCCSA-N carbonic acid;(e)-1,2-difluoroethene Chemical compound OC(O)=O.F\C=C\F PMGNOQUKCGLETL-TYYBGVCCSA-N 0.000 claims description 4
- AENDXYYGTYFGOX-UHFFFAOYSA-N chloro(difluoro)phosphane Chemical compound FP(F)Cl AENDXYYGTYFGOX-UHFFFAOYSA-N 0.000 claims description 4
- HFRXFRBDWDLMMR-UHFFFAOYSA-N chloro(tetrafluoro)-$l^{5}-phosphane Chemical compound FP(F)(F)(F)Cl HFRXFRBDWDLMMR-UHFFFAOYSA-N 0.000 claims description 4
- KQDDQXNVESLJNO-UHFFFAOYSA-N chloromethanesulfonyl chloride Chemical compound ClCS(Cl)(=O)=O KQDDQXNVESLJNO-UHFFFAOYSA-N 0.000 claims description 4
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 claims description 4
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 4
- HEHHDHIDWXZMFB-UHFFFAOYSA-N dichloro(fluoro)phosphane Chemical compound FP(Cl)Cl HEHHDHIDWXZMFB-UHFFFAOYSA-N 0.000 claims description 4
- PYMHWNZNAIBFHU-UHFFFAOYSA-N dichloro(trifluoro)-$l^{5}-phosphane Chemical compound FP(F)(F)(Cl)Cl PYMHWNZNAIBFHU-UHFFFAOYSA-N 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- KNWQLFOXPQZGPX-UHFFFAOYSA-N methanesulfonyl fluoride Chemical compound CS(F)(=O)=O KNWQLFOXPQZGPX-UHFFFAOYSA-N 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 4
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 4
- XZTAZFYWRDQNAV-UHFFFAOYSA-N tetrachloro(fluoro)-$l^{5}-phosphane Chemical compound FP(Cl)(Cl)(Cl)Cl XZTAZFYWRDQNAV-UHFFFAOYSA-N 0.000 claims description 4
- MTFNUCIFLCOJRC-UHFFFAOYSA-N trichloro(difluoro)-$l^{5}-phosphane Chemical compound FP(F)(Cl)(Cl)Cl MTFNUCIFLCOJRC-UHFFFAOYSA-N 0.000 claims description 4
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- ZLJKQOWJEZSNBE-UHFFFAOYSA-N 2-methylpropane-2-sulfinyl chloride Chemical compound CC(C)(C)S(Cl)=O ZLJKQOWJEZSNBE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- CXAVWUXAKZJEBR-UHFFFAOYSA-N ethanesulfinyl chloride Chemical compound CCS(Cl)=O CXAVWUXAKZJEBR-UHFFFAOYSA-N 0.000 claims description 3
- LURSUHVHQZXABT-UHFFFAOYSA-N methanesulfinyl chloride Chemical compound CS(Cl)=O LURSUHVHQZXABT-UHFFFAOYSA-N 0.000 claims description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 3
- MJNHIYILRDOOTC-UHFFFAOYSA-N tetrachlorophosphanium Chemical compound Cl[P+](Cl)(Cl)Cl MJNHIYILRDOOTC-UHFFFAOYSA-N 0.000 claims description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 3
- BJHSNICXDHWUGU-UHFFFAOYSA-N chlorodifluorophosphorus oxide Chemical compound FP(F)(Cl)=O BJHSNICXDHWUGU-UHFFFAOYSA-N 0.000 claims description 2
- ICRGCTYTLVGZOU-UHFFFAOYSA-N ctk4c2791 Chemical compound FS(Cl)=O ICRGCTYTLVGZOU-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- IWOKCMBOJXYDEE-UHFFFAOYSA-N sulfinylmethane Chemical class C=S=O IWOKCMBOJXYDEE-UHFFFAOYSA-N 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 62
- 238000012360 testing method Methods 0.000 description 51
- 238000011156 evaluation Methods 0.000 description 47
- 239000007789 gas Substances 0.000 description 38
- 229940021013 electrolyte solution Drugs 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 24
- 239000007774 positive electrode material Substances 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 19
- 239000007773 negative electrode material Substances 0.000 description 19
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003125 aqueous solvent Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 125000001033 ether group Chemical group 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
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- YZBOZNXACBQJHI-UHFFFAOYSA-N 1-dichlorophosphoryloxyethane Chemical compound CCOP(Cl)(Cl)=O YZBOZNXACBQJHI-UHFFFAOYSA-N 0.000 description 1
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- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
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- ZQHLMWUFVRLDRK-UHFFFAOYSA-N 2,3-dichlorooxolane Chemical compound ClC1CCOC1Cl ZQHLMWUFVRLDRK-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- SBMUNILHNJLMBF-UHFFFAOYSA-N 2-chloro-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound ClP1(=O)OCCO1 SBMUNILHNJLMBF-UHFFFAOYSA-N 0.000 description 1
- VHCSBTPOPKFYIU-UHFFFAOYSA-N 2-chloroethanesulfonyl chloride Chemical compound ClCCS(Cl)(=O)=O VHCSBTPOPKFYIU-UHFFFAOYSA-N 0.000 description 1
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- DAGAQTLMZAEUKX-UHFFFAOYSA-N 3-bromo-1h-pyrrolo[2,3-c]pyridine Chemical compound N1=CC=C2C(Br)=CNC2=C1 DAGAQTLMZAEUKX-UHFFFAOYSA-N 0.000 description 1
- GPKDGVXBXQTHRY-UHFFFAOYSA-N 3-chloropropane-1-sulfonyl chloride Chemical compound ClCCCS(Cl)(=O)=O GPKDGVXBXQTHRY-UHFFFAOYSA-N 0.000 description 1
- QYIOFABFKUOIBV-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxol-2-one Chemical compound CC=1OC(=O)OC=1C QYIOFABFKUOIBV-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- NZSICTQUKULOSA-UHFFFAOYSA-N 5-azoniaspiro[4.4]nonane Chemical compound C1CCC[N+]21CCCC2 NZSICTQUKULOSA-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 229910018085 Al-F Inorganic materials 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 229910018179 Al—F Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910005933 Ge—P Inorganic materials 0.000 description 1
- DOJXGHGHTWFZHK-UHFFFAOYSA-N Hexachloroacetone Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl DOJXGHGHTWFZHK-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910020588 KCrO2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 1
- 229910004563 Na2Fe2 (SO4)3 Inorganic materials 0.000 description 1
- 229910021271 NaCrO2 Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 229910021290 NaFe0.5Co0.5O2 Inorganic materials 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910009038 Sn—P Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- WSNZLQGGHKYFAZ-UHFFFAOYSA-M [Na+].[O-]S(Cl)(=O)=O Chemical compound [Na+].[O-]S(Cl)(=O)=O WSNZLQGGHKYFAZ-UHFFFAOYSA-M 0.000 description 1
- SFLLDHFSAKVEOB-UHFFFAOYSA-N [chloro(fluoro)phosphoryl]oxybenzene Chemical compound FP(Cl)(=O)OC1=CC=CC=C1 SFLLDHFSAKVEOB-UHFFFAOYSA-N 0.000 description 1
- GUDIWCZJEDSHOE-UHFFFAOYSA-N [chloro(fluoro)phosphoryl]oxymethane Chemical compound COP(F)(Cl)=O GUDIWCZJEDSHOE-UHFFFAOYSA-N 0.000 description 1
- NGFFLHMFSINFGB-UHFFFAOYSA-N [chloro(methoxy)phosphoryl]oxymethane Chemical compound COP(Cl)(=O)OC NGFFLHMFSINFGB-UHFFFAOYSA-N 0.000 description 1
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- ALIQZUMMPOYCIS-UHFFFAOYSA-N benzene-1,3-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 ALIQZUMMPOYCIS-UHFFFAOYSA-N 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- UCYIKXVPERYUJJ-UHFFFAOYSA-N bis(1,1,1,3,3,3-hexafluoropropan-2-yl) carbonate Chemical compound FC(F)(F)C(C(F)(F)F)OC(=O)OC(C(F)(F)F)C(F)(F)F UCYIKXVPERYUJJ-UHFFFAOYSA-N 0.000 description 1
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 description 1
- UQWLFOMXECTXNQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F UQWLFOMXECTXNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- FZXSSJIKXCFPDP-UHFFFAOYSA-N chloro(dichlorophosphoryl)methane Chemical compound ClCP(Cl)(Cl)=O FZXSSJIKXCFPDP-UHFFFAOYSA-N 0.000 description 1
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 description 1
- JYWJULGYGOLCGW-UHFFFAOYSA-N chloromethyl chloroformate Chemical compound ClCOC(Cl)=O JYWJULGYGOLCGW-UHFFFAOYSA-N 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- GRTGGSXWHGKRSB-UHFFFAOYSA-N dichloromethyl methyl ether Chemical compound COC(Cl)Cl GRTGGSXWHGKRSB-UHFFFAOYSA-N 0.000 description 1
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- FRYHCSODNHYDPU-UHFFFAOYSA-N ethanesulfonyl chloride Chemical compound CCS(Cl)(=O)=O FRYHCSODNHYDPU-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- QRSIIRMRJKPRGW-UHFFFAOYSA-N ethyl chloromethanesulfonate Chemical compound CCOS(=O)(=O)CCl QRSIIRMRJKPRGW-UHFFFAOYSA-N 0.000 description 1
- XVOCEVMHNRHJMX-UHFFFAOYSA-N ethyl-hydroxy-oxogermane Chemical compound CC[Ge](O)=O XVOCEVMHNRHJMX-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- PMGBATZKLCISOD-UHFFFAOYSA-N methyl 3,3,3-trifluoropropanoate Chemical compound COC(=O)CC(F)(F)F PMGBATZKLCISOD-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- SCLFRABIDYGTAZ-UHFFFAOYSA-N methylphosphonic acid dichloride Chemical compound CP(Cl)(Cl)=O SCLFRABIDYGTAZ-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- HXQOOYKLTKQCRR-UHFFFAOYSA-N oxalyl fluoride Chemical class FC(=O)C(F)=O HXQOOYKLTKQCRR-UHFFFAOYSA-N 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- PWQOZRPSDQKNPW-UHFFFAOYSA-N pentane-1-sulfonyl chloride Chemical compound CCCCCS(Cl)(=O)=O PWQOZRPSDQKNPW-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- AAHFRWRQQDVWPX-UHFFFAOYSA-N prop-2-ene-1-sulfonyl chloride Chemical compound ClS(=O)(=O)CC=C AAHFRWRQQDVWPX-UHFFFAOYSA-N 0.000 description 1
- IVRIRQXJSNCSPQ-UHFFFAOYSA-N propan-2-yl carbonochloridate Chemical compound CC(C)OC(Cl)=O IVRIRQXJSNCSPQ-UHFFFAOYSA-N 0.000 description 1
- KPBSJEBFALFJTO-UHFFFAOYSA-N propane-1-sulfonyl chloride Chemical compound CCCS(Cl)(=O)=O KPBSJEBFALFJTO-UHFFFAOYSA-N 0.000 description 1
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229960004711 sodium monofluorophosphate Drugs 0.000 description 1
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- 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
- One of the embodiments of the present disclosure is a non-aqueous electrolyte, a non-aqueous sodium ion battery and a non-aqueous potassium ion battery using the same, a method for manufacturing a non-aqueous sodium ion battery, and a method for manufacturing a non-aqueous potassium ion battery Regarding.
- Lithium-ion batteries are attracting attention as power storage systems for large-scale and power applications.
- the price of lithium is soaring, and less expensive sodium ion batteries and potassium ion batteries are attracting attention as next-generation secondary batteries.
- non-aqueous sodium ion batteries and non-aqueous potassium ion batteries use a non-aqueous electrolyte or a non-aqueous electrolyte that is quasi-solidified with a gelling agent as an ionic conductor.
- a non-aqueous electrolyte or a non-aqueous electrolyte that is quasi-solidified with a gelling agent as an ionic conductor.
- an aprotic solvent is used as a solvent
- a sodium salt is used as a solute in a non-aqueous sodium ion battery
- a potassium salt is used in a non-aqueous potassium ion battery.
- Patent Document 1 a saturated cyclic carbonate having a fluoro group or a chain carbonate having a fluoro group is used as an additive in the electrolyte of the non-aqueous sodium ion battery, so that the electrolyte on the surface of the negative electrode It has been shown that decomposition is suppressed and durability is improved.
- Patent Document 2 shows that the battery life is improved by using sodium monofluorophosphate or sodium difluorophosphate as an additive in a non-aqueous sodium ion battery electrolyte.
- Patent Document 3 shows that negative electrode resistance is reduced by adding a cyclic sulfate ester as an additive to a non-aqueous sodium ion battery electrolyte.
- Non-Patent Document 1 shows that the use of fluoroethylene carbonate as an additive in the non-aqueous potassium ion battery electrolyte improves the charge-discharge efficiency.
- Non-aqueous sodium ion batteries and non-aqueous potassium ion batteries have already begun to be put into practical use, but there are various problems that need to be improved in applications where they are used in high temperature locations for long periods of time, such as for automobiles. Therefore, one of the embodiments of the present disclosure is to improve the cycle characteristics at high temperatures of 60 ° C. or higher, suppress the increase in resistance, and generate gas in a non-aqueous sodium ion battery or a non-aqueous potassium ion battery.
- a non-aqueous electrolyte a non-aqueous sodium ion battery and a non-aqueous potassium ion battery using the same, a method for manufacturing a non-aqueous sodium ion battery, and a non-aqueous potassium ion battery
- One of the subjects is to provide a manufacturing method of.
- Non-aqueous sodium ion electrolyte improves the cycle characteristics of non-aqueous sodium ion batteries and non-aqueous potassium ion batteries, suppresses increase in resistance, and suppresses gas generation in high-temperature environments.
- the inventors have found effects unique to batteries and non-aqueous potassium ion batteries, leading to the present disclosure.
- the present disclosure includes the following embodiments.
- the organic chlorine compound is an aliphatic hydrocarbon compound having a C-Cl bond, an aromatic hydrocarbon compound having a C-Cl bond, a compound represented by the following formula (1), and a compound represented by the following formula (2).
- each R a is independently a fluorine atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, optionally substituted C2-C10 alkenyl group, optionally substituted C2-C10 alkenyloxy group, optionally substituted C2-C2 to 10 alkynyl groups, optionally substituted alkynyloxy groups of 2 to 10 carbon atoms, aryl groups of optionally substituted carbon atoms of 6 to 15, optionally substituted represents an aryloxy group having 6 to 15 carbon atoms, or N(R x ) 2.
- Each R x is independently a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms , represents an optionally substituted alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent.
- a plurality of R x may be bonded to each other, at least one of the plurality of R a has a C—Cl bond, and each R a may be the same or different (A plurality of R a may be bonded to each other.)
- each R b is independently a fluorine atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, optionally substituted C2-C10 alkenyl group, optionally substituted C2-C10 alkenyloxy group, optionally substituted C2-C2 to 10 alkynyl groups, optionally substituted alkynyloxy groups of 2 to 10 carbon atoms, aryl groups of optionally substituted carbon atoms of 6 to 15, optionally substituted represents an aryloxy group having 6 to 15 carbon atoms, or N(R y ) 2.
- Each R y is independently a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms , represents an optionally substituted alkenyl group having 2 to 10 carbon atoms, or an optionally substituted alkynyl group having 2 to 10 carbon atoms.
- a plurality of R y may be bonded to each other, at least one of the plurality of R b has a C—Cl bond, and R b may be the same or different (A plurality of R b may be bonded to each other.)
- the phosphorus compound having a P-Cl bond is phosphorus trichloride, phosphorus dichloride monofluoride, phosphorus monochloride difluoride, phosphoryl chloride, phosphoryl dichloride monofluoride, phosphoryl monochloride difluoride, phosphorus pentachloride, Phosphorus tetrachloride monofluoride, Phosphorus trichloride difluoride, Phosphorus dichloride trifluoride, Phosphorus monochloride tetrafluoride, Phosphate hexachloride, Phosphate pentachloride monofluoride, Phosphorus tetrachloride difluoride Salt, trichlorotrifluorophosphate, dichlorotetrafluorophosphate, monochloropentafluorophosphate, monochlorophosphate, dichlorophosphate, monochloromonofluorophosphate, bis(dichlor
- each R 1 independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, a substituent optionally substituted C2-10 alkenyl group, optionally substituted C2-10 alkenyloxy group, optionally substituted C2-10 alkynyl group group, an optionally substituted alkynyloxy group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms which may have a substituent, or a carbon which may have a substituent represents an aryloxy group of numbers 6 to 15.
- Multiple R 1 's may be the same or different from each other.R 1 's may be bonded to each other.
- R 2 is an optionally substituted C 1-10 alkyl group, an optionally substituted C 1-10 alkoxy group, a substituted an alkenyl group having 2 to 10 carbon atoms which may be substituted, an alkenyloxy group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a substituent an alkynyloxy group having 2 to 10 carbon atoms which may have, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an optionally substituted represents the aryloxy group of.
- R 3 is an optionally substituted C 1-10 alkyl group, an optionally substituted C 1-10 alkoxy group, a substituted an alkenyl group having 2 to 10 carbon atoms which may be substituted, an alkenyloxy group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a substituent an alkynyloxy group having 2 to 10 carbon atoms which may have, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an optionally substituted represents the aryloxy group of.
- R 4 is an optionally substituted C 1-10 alkyl group, an optionally substituted C 1-10 alkoxy group, a substituted an alkenyl group having 2 to 10 carbon atoms which may be substituted, an alkenyloxy group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a substituent an alkynyloxy group having 2 to 10 carbon atoms which may have, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an optionally substituted represents the aryloxy group of.
- the silicon compound having a Si—Cl bond is at least one selected from the group consisting of trialkylchlorosilanes, dialkyldichlorosilanes, alkyltrichlorosilanes, tetrachlorosilanes, dialkylchlorohydrosilanes, alkyldichlorohydrosilanes, and alkylchlorodihydrosilanes. , [1] or the non-aqueous electrolytic solution according to [2].
- (II) is a cation consisting of sodium, a hexafluorophosphate anion, a difluorophosphate anion, a monofluorophosphate anion, a tetrafluoroborate anion, a difluorooxalatoborate anion, a tetrafluorooxalate anion, difluorobisoxalate anion, trisoxalate anion, trifluoromethanesulfonate anion, fluorosulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion, (trifluoromethanesulfonyl)(fluorosulfonyl) ) imide anion, bis(difluorophosphoryl)imide anion, (difluorophosphoryl)(fluorosulfonyl)imide anion, and (diflufluor
- (II) is a cation consisting of potassium, a hexafluorophosphate anion, a difluorophosphate anion, a monofluorophosphate anion, a tetrafluoroborate anion, a difluorooxalatoborate anion, a tetrafluorooxalate anion, difluorobisoxalate anion, trisoxalate anion, trifluoromethanesulfonate anion, fluorosulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion, (trifluoromethanesulfonyl)(fluorosulfonyl) ) imide anion, bis(difluorophosphoryl)imide anion, (difluorophosphoryl)(fluorosulfonyl)imide anion, and (diflufluor
- (I) is ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, 1,3-dioxolane, 2 -methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxyethane, diethoxyethane, ethoxymethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether, from The nonaqueous electrolytic solution according to any one of [1] to [12], containing at least one selected from the group consisting of:
- a non-aqueous sodium ion battery comprising at least a positive electrode, a negative electrode, and the non-aqueous electrolyte according to any one of [1] to [8] and [10] to [14].
- a nonaqueous potassium ion battery comprising at least a positive electrode, a negative electrode, and the nonaqueous electrolyte solution according to any one of [1] to [7] and [9] to [14].
- a step of preparing the non-aqueous electrolyte according to any one of [1] to [8] and [10] to [14], and supplying the non-aqueous electrolyte to an empty cell having at least a positive electrode and a negative electrode A method for manufacturing a non-aqueous sodium ion battery, comprising a step of filling.
- a non-aqueous sodium ion battery or a non-aqueous potassium ion battery improving cycle characteristics at high temperatures of 60 ° C. or higher, suppressing resistance increase, and suppressing gas generation
- a non-aqueous electrolyte that can achieve at least one of the above, a non-aqueous sodium ion battery and a non-aqueous potassium ion battery using the same, and a method for manufacturing a non-aqueous sodium ion battery and a method for manufacturing a non-aqueous potassium ion battery. be done.
- fluoride ions generated by decomposition of fluorine-containing ionic salts such as lithium hexafluorophosphate and lithium tetrafluoroborate contained as solutes during the initial charge and the positive electrode current collector aluminum reacts to form a stable passive film on the aluminum surface.
- This coating is mainly composed of AlF3 or similar compounds, but when a high concentration of chloride ions is present, the Al-F bonds are replaced by Al-Cl bonds due to the reaction with chloride ions, eventually resulting in aluminum chloride and The passivation film is destroyed by conversion to lithium tetrachloroaluminate and elution into the electrolyte.
- lithium chloride is produced when chloride ions are generated by charging.
- the dissolution of the produced lithium chloride in the non-aqueous lithium ion battery electrolyte promotes the destruction reaction of the passive film.
- non-aqueous sodium ion batteries using the non-aqueous electrolyte solution of the present disclosure containing a chlorine-containing compound that generates chloride ions upon charging It was clarified that in a non-aqueous potassium ion battery, the cycle performance was improved in a high temperature environment, the resistance increase was suppressed, and the gas generation was suppressed. Although the details of this mechanism are not clear at present, it can be considered as follows.
- Non-aqueous organic solvents used in the non-aqueous electrolyte of the present disclosure include, for example, esters (including carbonates), ethers, lactones, nitriles, imides, and sulfones.
- the non-aqueous organic solvent preferably contains at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, and chain ethers.
- Cyclic esters include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate and fluoroethylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone and the like.
- Chain esters include chain carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, methyl acetate, ethyl acetate, 2,2-difluoroethyl acetate, and propionate. methyl acid, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, methyl 3,3,3-trifluoropropionate and the like.
- Cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1 , 4-dioxane and the like.
- Chain ethers include dimethoxyethane, diethoxyethane, diethyl ether, dibutyl ether, diisopropyl ether, ethoxymethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether and the like.
- the content of at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, and chain ethers (if there are more than one, the total content) is the non-aqueous organic solvent is preferably 70 to 100% by volume, more preferably 80 to 100% by volume, based on the total amount of
- the non-aqueous organic solvent contains a cyclic ester, and part or all of the cyclic ester is a cyclic carbonate. Moreover, it is preferable that the non-aqueous organic solvent contains a chain ester, and part or all of the chain ester is a chain carbonate.
- the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonates and chain carbonates, it is preferable from the viewpoint of excellent cycle characteristics at high temperatures.
- the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic esters and chain esters, it is preferable from the viewpoint of excellent input/output characteristics at low temperatures.
- the content of at least one selected from the group consisting of cyclic carbonates and chain carbonates (if more than one are present, the total amount) is 10 to 10 with respect to the total amount of the non-aqueous organic solvent. 100% by volume is preferred, and 30 to 100% by volume is more preferred.
- non-aqueous organic solvent examples include ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, methyl acetate, and ethyl acetate.
- the non-aqueous organic solvent includes, among others, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, 1,3- Dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethoxyethane, diethoxyethane, ethoxymethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol It is preferable to include at least one selected from the group consisting of dimethyl ether.
- the non-aqueous electrolyte of the present disclosure may also contain a polymer and may be generally called a polymer solid electrolyte.
- Polymer solid electrolytes also include those containing non-aqueous organic solvents as plasticizers.
- the polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the solute and additives (component (III) and other additives) described below.
- aprotic polymer capable of dissolving the solute and additives (component (III) and other additives) described below.
- examples thereof include polymers having polyethylene oxide as a main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile, and the like.
- an aprotic nonaqueous organic solvent is used among the above nonaqueous organic solvents.
- solute that is an ionic salt
- solute for example, cations composed of sodium ions in the case of sodium ion batteries and potassium ions in the case of potassium ion batteries, hexafluorophosphate anions, difluorophosphate anions, and monofluorophosphate anion, tetrafluoroborate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, difluorooxalatoborate anion, tetrafluorooxalatorate anion, difluorobisoxalatorate anion, trisoxalatorate anion, trifluoro romethanesulfonate anion, fluorosulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl
- solutes are cations composed of sodium ions in the case of sodium ion batteries and potassium ions in the case of potassium ion batteries, hexafluorophosphate anions, difluorophosphate anions, monofluorophosphate anions, tetrafluoroborate anions, and difluorooxalates.
- the concentration of these solutes is not particularly limited, but the lower limit is 0.3 mol/L or more, preferably 0.5 mol/L or more, and more preferably 0.7 mol/L or more with respect to the total amount of the non-aqueous electrolyte. and the upper limit is 5.0 mol/L or less, preferably 3.0 mol/L or less, more preferably 2.0 mol/L or less. By making it 0.3 mol / L or more, the deterioration of the cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to the decrease in ionic conductivity is suppressed.
- the temperature of the non-aqueous electrolyte may rise due to the heat of dissolution of the solute. , there is a risk of coloring the non-aqueous electrolyte and degrading its performance.
- the liquid temperature when dissolving the solute in the non-aqueous organic solvent is not particularly limited, but is preferably -20 to 50°C, more preferably 0 to 40°C.
- organic chlorine compound include aliphatic hydrocarbon compounds having a C-Cl bond, aromatic hydrocarbon compounds having a C-Cl bond, compounds represented by the following formula (1), and represented by the following formula (2). It is preferably at least one selected from the group consisting of compounds.
- each R a is independently a fluorine atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, optionally substituted C2-C10 alkenyl group, optionally substituted C2-C10 alkenyloxy group, optionally substituted C2-C2 to 10 alkynyl groups, optionally substituted alkynyloxy groups of 2 to 10 carbon atoms, aryl groups of optionally substituted carbon atoms of 6 to 15, optionally substituted represents an aryloxy group having 6 to 15 carbon atoms, or N(R x ) 2.
- Each R x is independently a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms , represents an optionally substituted alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms which may have a substituent.
- a plurality of R x may be bonded to each other, at least one of the plurality of R a has a C—Cl bond, and each R a may be the same or different (A plurality of R a may be bonded to each other.)
- each R b is independently a fluorine atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, optionally substituted C2-C10 alkenyl group, optionally substituted C2-C10 alkenyloxy group, optionally substituted C2-C2 to 10 alkynyl groups, optionally substituted alkynyloxy groups of 2 to 10 carbon atoms, aryl groups of optionally substituted carbon atoms of 6 to 15, optionally substituted represents an aryloxy group having 6 to 15 carbon atoms, or N(R y ) 2.
- Each R y is independently a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms , represents an optionally substituted alkenyl group having 2 to 10 carbon atoms, or an optionally substituted alkynyl group having 2 to 10 carbon atoms.
- a plurality of R y may be bonded to each other, at least one of the plurality of R b has a C—Cl bond, and R b may be the same or different (A plurality of R b may be bonded to each other.)
- alkyl groups having 1 to 10 carbon atoms represented by R a include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n -hexyl group and the like, preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, more preferably a methyl group or an ethyl group.
- alkenyl group having 2 to 10 carbon atoms represented by R a include a vinyl group and an allyl group.
- Examples of the alkynyl group having 2 to 10 carbon atoms represented by R a include an ethynyl group and a propargyl group.
- Examples of the aryl group having 6 to 15 carbon atoms represented by R a include a phenyl group and a naphthyl group, with a phenyl group being preferred.
- the alkyl group, alkenyl group, alkynyl group, and aryl group in the alkoxy group, alkenyloxy group, alkynyloxy group, and aryloxy group represented by Ra are the alkyl group, alkenyl group, alkynyl group, and aryl group represented by Ra, respectively. and the same groups as above, and preferred examples are also the same.
- Examples of substituents that each group represented by R a may have include a chlorine atom, a fluorine atom, an ether group, a carbonyl group, and a group formed by combining two or more of these groups.
- Examples of the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the alkynyl group having 2 to 10 carbon atoms represented by R x include the groups exemplified for Ra , and preferred examples are also the same. .
- Examples of substituents that each group represented by Rx may have include a chlorine atom, a fluorine atom, an ether group, a carbonyl group, and a group formed by combining two or more of these groups. As described above, at least one of the multiple R a has a C—Cl bond.
- R b represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, Examples of the alkynyloxy group having 2 to 10 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the aryloxy group having 6 to 15 carbon atoms include the groups exemplified for R a , and preferable examples are the same. Examples of the substituent that each group represented by R b may have include a chlorine atom, a fluorine atom, an ether group, a carbonyl group, and a group formed by combining two or more of these groups.
- Examples of the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the alkynyl group having 2 to 10 carbon atoms represented by R y include the groups exemplified for R 2 x , and preferred examples are also the same.
- Examples of the substituent that each group represented by Ry may have include a chlorine atom, a fluorine atom, an ether group, a carbonyl group, and a group formed by combining two or more of these groups. As described above, at least one of a plurality of Rb 's has a C—Cl bond.
- chloromethane dichloromethane, trichloromethane, tetrachloromethane, chloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,1, 2-tetrachloroethane, hexachloroethane, chloroethene, 1,2-dichloroethene, trichloroethene, tetrachloroethene, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2- Dichloropropane, 1,1,2-trichloropropane, 1,1,2,3-tetrachloropropane, 1,2,2,3-tetrachloropropane, allyl chloride, propargyl chloride, 1-chlorobutane, 2-chloro-2- Methyl
- dichloromethane trichloromethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane, trichloroethene, tetrachloroethene, acetyl chloride, dichloroacetyl chloride, Bistrichloromethyl carbonate, hexachloro-2-propanone, oxalyl chloride, difluoride chloromethylphosphonate, dimethyl chloromethylphosphonate, chloromethylsulfonate fluoride, 2-chloroethanesulfonate fluoride, methyl chloromethylsulfonate, chloromethyl fluorosulfonate are preferred. .
- Phosphorus compounds having a P-Cl bond include phosphorus trichloride, phosphorus dichloride monofluoride, phosphorus monochloride difluoride, phosphoryl chloride, phosphoryl dichloride monofluoride, phosphoryl dichloride difluoride, phosphorus pentachloride , Phosphorus tetrachloride monofluoride, Phosphorus trichloride difluoride, Phosphorus dichloride trifluoride, Phosphorus monochloride tetrafluoride, Phosphate hexachloride, Phosphate pentachloride monofluoride, Phosphorus tetrachloride difluoride phosphate trichloride, tetrafluorophosphate dichloride, phosphate monochloropentafluoride, monochlorophosphate, dichlorophosphate, monochloromonofluorophosphat
- each R 1 independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms, a substituent optionally substituted C2-10 alkenyl group, optionally substituted C2-10 alkenyloxy group, optionally substituted C2-10 alkynyl group group, an optionally substituted alkynyloxy group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms which may have a substituent, or a carbon which may have a substituent represents an aryloxy group of numbers 6 to 15.
- Multiple R 1 's may be the same or different from each other.R 1 's may be bonded to each other.
- R 2 is an optionally substituted C 1-10 alkyl group, an optionally substituted C 1-10 alkoxy group, a substituted an alkenyl group having 2 to 10 carbon atoms which may be substituted, an alkenyloxy group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a substituent an alkynyloxy group having 2 to 10 carbon atoms which may have, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an optionally substituted represents the aryloxy group of.
- R 3 is an optionally substituted C 1-10 alkyl group, an optionally substituted C 1-10 alkoxy group, a substituted an alkenyl group having 2 to 10 carbon atoms which may be substituted, an alkenyloxy group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a substituent an alkynyloxy group having 2 to 10 carbon atoms which may have, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an optionally substituted represents the aryloxy group of.
- alkyl groups having 1 to 10 carbon atoms represented by R 1 to R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and n-pentyl. group, n-hexyl group and the like, preferably methyl group, ethyl group, n-propyl group or isopropyl group, more preferably methyl group or ethyl group.
- alkenyl group having 2 to 10 carbon atoms represented by R 1 to R 3 include a vinyl group and an allyl group.
- Examples of the alkynyl group having 2 to 10 carbon atoms represented by R 1 to R 3 include ethynyl group and propargyl group.
- Examples of the aryl group having 6 to 15 carbon atoms represented by R 1 to R 3 include a phenyl group and a naphthyl group, with a phenyl group being preferred.
- the alkyl group, alkenyl group, alkynyl group and aryl group in the alkoxy group, alkenyloxy group, alkynyloxy group and aryloxy group represented by R 1 to R 3 are respectively the alkyl group and alkenyl group represented by R 1 to R 3 , an alkynyl group, and an aryl group, and preferred examples are also the same.
- substituents that each group represented by R 1 to R 3 may have include a chlorine atom, a fluorine atom, an ether group, a carbonyl group, and a group formed by combining two or more of these groups.
- phosphorus compound having a P-Cl bond examples include phosphorus trichloride, phosphorus dichloride monofluoride, phosphorus difluoride monochloride, phosphoryl chloride, phosphoryl dichloride monofluoride, phosphoryl dichloride difluoride, Phosphorus pentachloride, Phosphorus tetrachloride monofluoride, Phosphorus trichloride difluoride, Phosphorus dichloride trifluoride, Phosphorus monochloride tetrafluoride, Phosphate hexachloride, Phosphate pentachloride monofluoride, Dichloride tetrachloride fluorophosphate, trichlorotrifluorophosphate, dichlorotetrafluorophosphate, monochloropentafluorophosphate, monochlorophosphate, dichlorophosphate, monochloromonofluorophosphate, In addition to bis(d
- (2,2,2-trichloroethyl), 2-chloro-2-oxo-1,3,2-dioxaphospholane, and compounds represented by formula (B) include methylphosphonic acid dichloride, chloromethylphosphonic acid dichloride, Ethylphosphonic acid dichloride, methyl dichlorophosphate, ethyl dichlorophosphate, 2-chloroethyl dichlorophosphate, phenyl dichlorophosphate, 2-chlorophenyl phosphorodichloridate, 4-chlorophenyl phosphorodichloridate, represented by the formula (C)
- Examples of such compounds include methyl chlorofluorophosphate, ethyl chlorofluorophosphate, and phenyl chlorofluorophosphate.
- phosphoryl chloride phosphoryl dichloride monofluoride, dichlorophosphate, monochloromonofluorophosphate, bis(dichlorophosphoryl)imide salt, dichlorophosphoryl isocyanate, and methyl dichlorophosphate are preferred.
- R 4 is an optionally substituted C 1-10 alkyl group, an optionally substituted C 1-10 alkoxy group, a substituted an alkenyl group having 2 to 10 carbon atoms which may be substituted, an alkenyloxy group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, a substituent an alkynyloxy group having 2 to 10 carbon atoms which may have, an aryl group having 6 to 15 carbon atoms which may have a substituent, and an optionally substituted carbon number of 6 to 15 represents the aryloxy group of.
- R 4 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, Examples of the alkynyloxy group having 2 to 10 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the aryloxy group having 6 to 15 carbon atoms include the groups exemplified for R 1 to R 3 , and preferred examples are also the same. be.
- substituents that each group represented by R 4 may have include a chlorine atom, a fluorine atom, an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), a chlorosulfonyl group, an ether group, a carbonyl group, or A group formed by combining two or more of these groups, and the like are included.
- the non-aqueous electrolytic solution, non-aqueous sodium ion battery, and non-aqueous potassium according to the present embodiment are used.
- the type is not particularly limited as long as it does not impair the performance of the ion battery, and various types can be selected.
- metal cations such as lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, magnesium ion, calcium ion, barium ion, silver ion, copper ion, iron ion, tetraalkylammonium ion, tetraalkyl
- Onium cations such as phosphonium ions, imidazolium ions, and ammonium ions having a spiro skeleton are included.
- lithium ions, sodium ions, potassium ions, tetraalkylammonium ions, or tetraalkylphosphonium ions are preferred, particularly from the viewpoint of helping ion conduction in the nonaqueous sodium ion battery.
- Lithium ions, sodium ions, tetraalkylammonium ions, or ammonium ions having a spiro skeleton are more preferred.
- lithium ions, sodium ions, potassium ions, tetraalkylammonium ions, or tetraalkylphosphonium ions are preferred, particularly from the viewpoint of helping ion conduction in the nonaqueous potassium ion battery.
- a potassium ion, a tetraalkylammonium ion, or an ammonium ion having a spiro skeleton is more preferable.
- the alkyl group in the tetraalkylammonium ion preferably has 1 to 6 carbon atoms, and the alkyl group in the tetraalkylphosphonium ion preferably has 1 to 6 carbon atoms.
- the four alkyl groups in the tetraalkylammonium ion may be the same or different, and the four alkyl groups in the tetraalkylphosphonium ion may be the same or different.
- Ammonium ions having a spiro skeleton are preferably, for example, 5-azoniaspiro[4.4]nonane.
- sulfinyl chloride methylsulfinyl chloride, ethylsulfinyl chloride, and t-butylsulfinyl chloride are preferred.
- the silicon compound having a Si—Cl bond is at least one selected from the group consisting of trialkylchlorosilanes, dialkyldichlorosilanes, alkyltrichlorosilanes, tetrachlorosilanes, dialkylchlorohydrosilanes, alkyldichlorohydrosilanes, and alkylchlorodihydrosilanes. mentioned.
- alkyl group that may be contained in the silicon compound having the Si—Cl bond an optionally substituted alkyl group having 1 to 10 carbon atoms is preferable.
- examples of the substituent include a chlorine atom, a fluorine atom, an ether group, a carbonyl group, or a combination of two or more of these groups.
- the alkyl group that may be contained in the silicon compound having a Si—Cl bond is preferably a methyl group or an ethyl group, more preferably a methyl group.
- trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane are particularly preferable.
- the component (III) may be added as a raw material, or the component (III) may remain ((III) contained in the manufacturing process). It may be indirectly added by using a fluorine-containing imide salt, a fluorine-containing sulfonate, a fluorine-containing phosphate, or a solute that does not completely remove the component by purification.
- the concentration x of (III) is 0.005% by mass ⁇ x ⁇ 10.00% by mass with respect to the total amount of the non-aqueous electrolyte in terms of chlorine atoms. is preferred, and 0.01% by mass ⁇ x ⁇ 3.20% by mass is more preferred. By making it 0.005% by mass or more, the effect of improving each characteristic of the non-aqueous sodium ion battery and the non-aqueous potassium ion battery is likely to be obtained.
- the concentration x of (III) is 0.05% by mass ⁇ x ⁇ 1.20% by mass in terms of chlorine atoms.
- the concentration x of (III) above is calculated based on the content of chlorine atoms in the non-aqueous electrolyte.
- the amount of chlorine atoms contained in the non-aqueous electrolyte is a value quantified as chloride ions by the following method. It was completely decomposed by the flask combustion method, and an aqueous solution of silver nitrate was added to the absorption liquid obtained there, and silver chloride was precipitated, and the solid sample collected by filtration was measured with a fluorescent X-ray analyzer.
- a fluorescent X-ray analyzer for example, ZSX Primus IV manufactured by Rigaku can be used.
- additive components generally used in the non-aqueous electrolytic solution of the present disclosure may be further added at any ratio.
- Specific examples include cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, difluoroanisole, t-butylbenzene, t-amylbenzene, fluorobenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, vinylene carbonate oligomer (number average molecular weight of 170 to 5000), dimethylvinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, 1,6-diisocyanatohexane, ethynylethylene carbonate, trans-difluoroethylene carbonate, maleic anhydride, succinic anhydride, 1,3- propanesultone, 1,3-propenesultone, 1,4-but
- the non-aqueous electrolyte can be quasi-solidified with a gelling agent or a cross-linked polymer.
- Fluorinated alcohols such as hexafluoroisopropanol do not generate hydrogen fluoride by reacting with solutes such as hexafluorophosphate due to their low nucleophilicity, improving input/output characteristics, for example. It is used as an additive to
- additives include, among others, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, fluorobenzene, vinylene carbonate, oligomers of vinylene carbonate (having a number average molecular weight of 170 to 5000), vinylethylene carbonate, fluoroethylene carbonate, 1 ,6-diisocyanatohexane, ethynylethylene carbonate, trans-difluoroethylene carbonate, 1,3-propanesultone, 1,3-propenesultone, 1,3,2-dioxathiolane-2,2-dioxide, 4- Propyl-1,3,2-dioxathiolane-2,2-dioxide, methylene methanedisulfonate, 1,2-ethanedisulfonic anhydride, tris(trimethylsilyl)borate, succinonitrile, adiponitrile, (ethoxy)pentafluor
- the content is preferably 0.01% by mass or more and 3.0% by mass or less with respect to the total amount of the non-aqueous electrolyte. .
- the nonaqueous electrolyte battery of the present disclosure is a nonaqueous sodium ion battery or a nonaqueous potassium ion battery.
- a non-aqueous sodium ion battery according to an embodiment of the present disclosure includes at least a positive electrode, a negative electrode, and the non-aqueous electrolyte.
- a non-aqueous potassium ion battery according to an embodiment of the present disclosure includes at least a positive electrode, a negative electrode, and the non-aqueous electrolyte.
- the non-aqueous electrolyte battery of the present disclosure includes a positive electrode, a negative electrode made of sodium or a negative electrode material capable of absorbing and releasing sodium, the non-aqueous electrolyte, a current collector, a separator, a container, etc. consists of Alternatively, the non-aqueous electrolyte battery of the present disclosure comprises a positive electrode, a negative electrode made of potassium or a negative electrode material capable of intercalating and deintercalating potassium, the non-aqueous electrolytic solution, a current collector, a separator, a container, and the like.
- the positive electrode consists of a positive electrode active material, an aluminum foil as a current collector, a conductive material, and a binder. available materials are used.
- As the material of the aluminum foil pure aluminum 1000 series (for example, A1085, A1N30, etc.) with high aluminum purity, and aluminum manganese alloy 3000 series (for example, A3003) to which manganese is added for the purpose of increasing strength are generally used. be done.
- aluminum-magnesium alloys of 5000 series to which magnesium is added for the purpose of similarly increasing strength, and 8000 series to which iron is added (alloys that do not correspond to the 1000 to 7000 series) are often used.
- Aluminum foils having a thickness of several micrometers to several tens of micrometers are generally used.
- the positive electrode material ( positive electrode active material) is not particularly limited, but examples include NaCrO2 , NaFe0.5Co0.5O2 , NaFe0.4Mn0.3Ni0.3O 2 , NaNi0.5Ti0.3Mn0.2O2 , NaNi1 / 3Ti1 / 3Mn1 / 3O2 , NaNi0.33Ti0.33Mn0.16Mg0.17O2 _ , Na 2/3 Ni 1/3 Ti 1/6 Mn 1/2 O 2 , Na 2/3 Ni 1/3 Mn 2/3 O 2 and other sodium-containing transition metal composite oxides, and sodium-containing transition metals thereof Composite oxides in which a plurality of transition metals such as Co, Mn, and Ni are mixed, transition metals of these sodium-containing transition metal composite oxides are partially substituted with other metals other than transition metals, NaFePO4 , NaVPO 4 F, Na 3 V 2 (PO 4 ) 3 , Na 2 Fe 2 (SO 4 ) 3 and other polyanionic compounds
- a positive electrode active material layer is formed on at least one surface of the positive electrode current collector.
- the positive electrode active material layer is composed of, for example, the positive electrode active material described above, a binder, and, if necessary, a conductive agent.
- the binder include polytetrafluoroethylene, polyvinylidene fluoride, styrene-butadiene rubber (SBR) resin, and the like.
- SBR styrene-butadiene rubber
- the conductive agent for example, a carbon material such as acetylene black, ketjen black, carbon fiber, or graphite (granular graphite or flake graphite) can be used, and acetylene black or ketjen black with low crystallinity is used. is preferred.
- One type of these binders and conductive agents may be used alone, or two or more types may be used in combination.
- the negative electrode consists of a negative electrode active material, a current collector, a conductive material, and a binder, and the type of the negative electrode active material is not particularly limited. Used.
- the negative electrode active material is not particularly limited, but includes sodium metal or a material capable of occluding and releasing sodium ions.
- sodium metal alloys of sodium metal and other metals such as tin, intermetallic compounds, various carbon materials including hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (simple substance), Tin compounds, activated carbon, conductive polymers, etc. are used.
- phosphorus such as red phosphorus and black phosphorus
- phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, Mo-P, antimony (single substance), Sb/C , Bi--Sb, and other antimony compounds.
- phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, Mo-P, antimony (single substance), Sb/C , Bi--Sb, and other antimony compounds.
- One type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
- the negative electrode active material is not particularly limited, but examples include materials capable of intercalating and deintercalating potassium metal or potassium ions.
- potassium metal alloys of potassium metal and other metals such as tin and bismuth, intermetallic compounds, phosphorus (elemental) such as red phosphorus and black phosphorus, various carbon materials, and metal oxides such as titanium oxide are used. be done.
- the carbon material include graphitizable carbon, non-graphitizable carbon (also called hard carbon) having a (002) plane spacing of 0.37 nm or more, and carbon having a (002) plane spacing of 0. .37 nm or less graphite, etc., and the latter is artificial graphite, natural graphite, or the like.
- One type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
- a negative electrode active material layer is formed on at least one surface of the negative electrode current collector.
- the negative electrode active material layer is composed of, for example, the negative electrode active material described above, a binder, and, if necessary, a conductive agent.
- the binder include polytetrafluoroethylene, polyvinylidene fluoride, styrene-butadiene rubber (SBR) resin, and the like.
- SBR styrene-butadiene rubber
- the conductive agent for example, a carbon material such as acetylene black, ketjen black, carbon fiber, or graphite (granular graphite or flake graphite) can be used.
- binders and conductive agents may be used alone, or two or more types may be used in combination.
- Copper, aluminum, stainless steel, nickel, titanium, alloys thereof, or the like can be used for current collectors of the positive electrode and the negative electrode.
- An active material layer is formed on at least one surface of the current collector.
- Nonwoven fabrics, porous sheets, and films made of polyolefin (eg, polypropylene, polyethylene), paper, glass fiber, or the like are used as separators for preventing contact between the positive electrode and the negative electrode. These are preferably microporous so that the electrolytic solution permeates and the ions easily permeate.
- outer package for example, a coin-shaped, cylindrical, square-shaped metal can, or a laminated outer package can be used.
- Metal can materials include, for example, nickel-plated steel plates, stainless steel plates, nickel-plated stainless steel plates, aluminum or its alloys, nickel, and titanium.
- laminated exterior body for example, an aluminum laminated film, a SUS laminated film, a silica-coated polypropylene or polyethylene laminated film, or the like can be used.
- the present disclosure also relates to a method for manufacturing a non-aqueous sodium ion battery, comprising the steps of preparing the non-aqueous electrolyte and filling an empty cell having at least a positive electrode and a negative electrode with the non-aqueous electrolyte.
- the present disclosure also relates to a method for manufacturing a non-aqueous potassium ion battery, comprising the steps of preparing the non-aqueous electrolyte and filling an empty cell having at least a positive electrode and a negative electrode with the non-aqueous electrolyte. .
- Electrolyte No. 1 was used except that no additive having a C--Cl bond was used.
- Electrolyte No. 1 57 was prepared. The above preparation was carried out while maintaining the liquid temperature in the range of 20°C to 30°C.
- Electrolyte Solution Containing Additive Having P-Cl Bond (Preparation of Electrolyte No. 58 to Electrolyte No. 100) Except for using PC as a non-aqueous solvent and dissolving an additive having a P-Cl bond instead of an additive having a C-Cl bond so as to have the concentration shown in Tables 3 and 4, electrolysis Liquid No. Electrolyte No. 1 58-Electrolyte No. 99 was prepared. Also, electrolyte solution No. 1 was used except that an additive having a P—Cl bond was not used. 58, electrolytic solution No. 100 was prepared.
- Electrolyte solution No. 2 except that an additive having a 2 -Cl bond was dissolved so as to have the concentration shown in Tables 5 and 6.
- Electrolyte No. 1 101-Electrolyte No. 143 was prepared.
- Electrolyte No. 101 was used.
- 144 was prepared.
- DMC dimethyl carbonate
- Examples 1-1 to 1-56 and Comparative Example 1-1 A test was prepared using the electrolytic solution shown in Table 1 as the test electrolytic solution, NaNi 0.5 Ti 0.3 Mn 0.2 O 2 as the positive electrode material, and hard carbon (Carbotron P, manufactured by Kureha Co., Ltd.) as the negative electrode material. A high-temperature cycle test was performed on the cell for use, and the cycle characteristics, the resistance increase rate during the cycle test, and the amount of gas generated were evaluated. These evaluation results are shown in Tables 10 and 11. In addition, the test cell was produced as follows.
- a test positive electrode was produced by the following procedure. 90% by mass of NaNi 0.5 Ti 0.3 Mn 0.2 O 2 as a positive electrode active material, 5% by mass of acetylene black as a conductive agent, and 5% by mass of polyvinylidene fluoride (PVDF) as a binder. were mixed, and N-methylpyrrolidone as a solvent was added so as to be 82% by mass with respect to the total mass of the positive electrode active material, the conductive agent, and the binder to prepare a slurry solution. This slurry solution was applied onto an aluminum foil as a positive electrode current collector and dried at 150° C. for 12 hours to obtain a test positive electrode in which a positive electrode active material layer was formed on the current collector.
- PVDF polyvinylidene fluoride
- a negative electrode for testing was produced in the following procedure. 90% by mass of hard carbon powder (Carbotron P, manufactured by Kureha Co., Ltd.) as a negative electrode active material and 10% by mass of polyvinylidene fluoride (PVDF) as a binder are mixed, and N-methylpyrrolidone is added as a solvent to the negative electrode active material. and the binder in an amount of 50% by mass to prepare a slurry solution. This slurry solution was applied onto a copper foil as a negative electrode current collector and dried at 150° C. for 12 hours to obtain a test negative electrode having a negative electrode active material layer formed on the current collector.
- PVDF polyvinylidene fluoride
- test positive electrode and a test negative electrode were placed through a polyethylene separator impregnated with a test electrolyte, and a 50mAh test cell with an aluminum laminate exterior was assembled.
- Example 1-1 to 1-56 are relative values with the evaluation result of Comparative Example 1-1 as 100%. A larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- Examples 2-1 to 2-42 and Comparative Example 2-1 Cells were fabricated in the same manner as in Example 1-1, except that NaFe 0.4 Mn 0.3 Ni 0.3 O 2 was used as the positive electrode active material and the electrolyte solutions shown in Tables 3 and 4 were used. A cycle test was conducted to evaluate the cycle characteristics, the rate of resistance increase during the cycle test, and the amount of gas generated. These evaluation results are shown in Tables 12 and 13.
- Example 2-1 to 2-42 are relative values with the evaluation result of Comparative Example 2-1 as 100%. A larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- Examples 3-1 to 3-43 and Comparative Example 3-1 Cells were produced in the same manner as in Example 1-1 except that NaNi 1/3 Ti 1/3 Mn 1/3 O 2 was used as the positive electrode active material and the electrolyte solutions shown in Tables 5 and 6 were used. A cycle test was conducted to evaluate the cycle characteristics, the rate of resistance increase during the cycle test, and the amount of gas generated. These evaluation results are shown in Tables 14 and 15.
- Example 3-1 to 3-43 are relative values with the evaluation result of Comparative Example 3-1 as 100%.
- a larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- Examples 4-1 to 4-14 and Comparative Example 4-1 A cell was prepared in the same manner as in Example 1-1 except that Na 2/3 Ni 1/3 Ti 1/6 Mn 1/2 O 2 was used as the positive electrode active material and the electrolyte solution shown in Table 7 was used. A high-temperature cycle test was performed to evaluate the cycle characteristics, the resistance increase rate during the cycle test, and the amount of gas generated. These evaluation results are shown in Table 16.
- Example 16 the evaluation results of Examples 4-1 to 4-14 are relative values with the evaluation result of Comparative Example 4-1 as 100%. A larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- Examples 5-1 to 5-8 and Comparative Example 5-1 A cell was prepared in the same manner as in Example 1-1 except that NaCrO 2 was used as the positive electrode active material and the electrolyte solution shown in Table 8 was used, and the upper limit charging voltage was changed to 3.3 V, and an initial charge-discharge test was performed. Then, a high-temperature cycle test was performed, and the cycle characteristics, the resistance increase rate during the cycle test (the upper limit charging voltage was changed to 3.3 V), and the amount of gas generated were evaluated. These evaluation results are shown in Table 17.
- Example 17 the evaluation results of Examples 5-1 to 5-8 are relative values with the evaluation result of Comparative Example 5-1 as 100%. A larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- Example 6-1 to 6-11 and Comparative Example 6-1 A high-temperature cycle test was performed on a test cell prepared using the electrolyte described in Table 9 as the test electrolyte, K 2 Mn[Fe(CN) 6 ] as the positive electrode material, and artificial graphite as the negative electrode material. The characteristics, resistance increase rate during the cycle test, and gas generation amount were evaluated. These evaluation results are shown in Table 18. In addition, the test cell was produced as follows.
- a test positive electrode was produced by the following procedure. 85% by mass of K 2 Mn[Fe(CN) 6 ] as a positive electrode active material, 8% by mass of acetylene black as a conductive agent, and 7% by mass of polyvinylidene fluoride (PVDF) as a binder are mixed, Furthermore, N-methylpyrrolidone was added as a solvent so as to be 82% by mass with respect to the total mass of the positive electrode active material, conductive agent, and binder to prepare a slurry solution. This slurry solution was applied onto an aluminum foil as a positive electrode current collector and dried at 150° C. for 12 hours to obtain a test positive electrode in which a positive electrode active material layer was formed on the current collector.
- PVDF polyvinylidene fluoride
- a negative electrode for testing was produced in the following procedure. 90% by mass of artificial graphite as a negative electrode active material and 10% by mass of polyvinylidene fluoride (PVDF) as a binder are mixed, and N-methylpyrrolidone is added as a solvent to the total mass of the negative electrode active material and the binder. was added so as to be 50% by mass to prepare a slurry solution. This slurry solution was applied onto a copper foil as a negative electrode current collector and dried at 150° C. for 12 hours to obtain a test negative electrode having a negative electrode active material layer formed on the current collector.
- PVDF polyvinylidene fluoride
- test positive electrode and a test negative electrode were placed through a polyethylene separator impregnated with a test electrolyte, and a 20mAh test cell with an aluminum laminate exterior was assembled.
- AC impedance measurement of the fully charged cell was performed with an electrochemical analyzer (ALS model 604E BAS Co., Ltd.). The resistance value calculated from the arc observed at this time was taken as the initial resistance. Thereafter, discharge was performed at a current density of 0.13 mA/cm 2 by a constant current method with a discharge lower limit voltage of 2.0 V.
- Example 18 the evaluation results of Examples 6-1 to 6-11 are relative values with the evaluation result of Comparative Example 6-1 as 100%. A larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- Electrolyte No. 181 as well. 182 to electrolyte No. 186 was prepared. Furthermore, electrolyte solution No. 1 was used except that sodium chlorosulfonate was not added. 181-Electrolyte No. 186, electrolyte solution No. 187-Electrolyte No. 192 was prepared.
- Example 21 the evaluation results of Examples 7-1 to 7-6 are relative values with the evaluation result of the electrolyte solution to which only the second compound was added without adding a chlorine-containing compound as 100%. is. A larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- Examples 8-1 to 8-3 are relative values with the evaluation result of the electrolytic solution to which only the second compound was added without adding the chlorine-containing compound being 100%. A larger value for the "discharge capacity retention rate after high temperature cycle” is desirable, a smaller value for the “resistance increase rate during high temperature cycle” is desirable, and a smaller value for the "gas generation amount during high temperature cycle” is desirable.
- a non-aqueous sodium ion battery or a non-aqueous potassium ion battery improving cycle characteristics at high temperatures of 60 ° C. or higher, suppressing resistance increase, and suppressing gas generation
- a non-aqueous electrolyte that can achieve at least one of the above, a non-aqueous sodium ion battery and a non-aqueous potassium ion battery using the same, and a method for manufacturing a non-aqueous sodium ion battery and a method for manufacturing a non-aqueous potassium ion battery. be done.
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Abstract
Description
したがって、本開示の実施形態の一つは、非水ナトリウムイオン電池又は非水カリウムイオン電池において、60℃以上の高温でのサイクル特性を向上すること、抵抗増加を抑制すること、及び、ガス発生を抑制すること、のうち少なくとも1つを達成できる非水電解液、それを用いた非水ナトリウムイオン電池及び非水カリウムイオン電池、並びに、非水ナトリウムイオン電池の製造方法及び非水カリウムイオン電池の製造方法を提供することを課題の一つとする。
ナトリウムイオン電池用又はカリウムイオン電池用の非水電解液であって、
(I)非水有機溶媒、
(II)イオン性塩である、溶質、
(III)有機塩素化合物、P-Cl結合を有するリン化合物、S(=O)2-Cl結合を有するスルホン化合物、S(=O)-Cl結合を有するスルフィン化合物、及びSi-Cl結合を有するケイ素化合物からなる群から選ばれる少なくとも1種
を含む、非水電解液。
前記(III)の濃度xが、塩素原子換算で0.01質量%≦x≦3.20質量%である、[1]に記載の非水電解液。
前記有機塩素化合物が、C-Cl結合を有する脂肪族炭化水素化合物、C-Cl結合を有する芳香族炭化水素化合物、下記式(1)で示される化合物、及び下記式(2)で示される化合物からなる群から選ばれる少なくとも1種である、[1]又は[2]に記載の非水電解液。
前記P-Cl結合を有するリン化合物が、三塩化リン、二塩化一フッ化リン、一塩化二フッ化リン、塩化ホスホリル、二塩化一フッ化ホスホリル、一塩化二フッ化ホスホリル、五塩化リン、四塩化一フッ化リン、三塩化二フッ化リン、二塩化三フッ化リン、一塩化四フッ化リン、六塩化リン酸塩、五塩化一フッ化リン酸塩、四塩化二フッ化リン酸塩、三塩化三フッ化リン酸塩、二塩化四フッ化リン酸塩、一塩化五フッ化リン酸塩、モノクロロリン酸塩、ジクロロリン酸塩、モノクロロモノフルオロリン酸塩、ビス(ジクロロホスホリル)イミド塩、ジクロロホスホリルイソシアネート、モノクロロモノフルオロホスホリルイソシアネート、下記式(A)で示される化合物、下記式(B)で示される化合物、及び下記式(C)で示される化合物からなる群から選ばれる少なくとも1種である、[1]又は[2]に記載の非水電解液。
前記S(=O)2-Cl結合を有するスルホン化合物が、塩化スルフリル、塩化フッ化スルフリル、クロロメタンスルホニルクロリド、メタンジスルホニルジクロリド、1,3-プロパンジスルホニルジクロリド、クロロスルホニルイソシアネート、クロロスルホン酸、クロロスルホン酸塩、ビス(クロロスルホニル)イミド塩、(ジクロロホスホリル)(クロロスルホニル)イミド塩、(ジフルオロホスホリル)(クロロスルホニル)イミド塩、及び下記式(D)で示される化合物、からなる群から選ばれる少なくとも1種である、[1]又は[2]に記載の非水電解液。
前記S(=O)-Cl結合を有するスルフィン化合物が、塩化スルフィニル、塩化フッ化スルフィニル、メチルスルフィニルクロリド、エチルスルフィニルクロリド、及びt-ブチルスルフィニルクロリドからなる群から選ばれる少なくとも1種である、[1]又は[2]に記載の非水電解液。
前記Si-Cl結合を有するケイ素化合物が、トリアルキルクロロシラン、ジアルキルジクロロシラン、アルキルトリクロロシラン、テトラクロロシラン、ジアルキルクロロヒドロシラン、アルキルジクロロヒドロシラン、及びアルキルクロロジヒドロシランからなる群から選ばれる少なくとも1種である、[1]又は[2]に記載の非水電解液。
前記(II)が、ナトリウムからなるカチオンと、ヘキサフルオロリン酸アニオン、ジフルオロリン酸アニオン、モノフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ジフルオロオキサラトホウ酸アニオン、テトラフルオロオキサラトリン酸アニオン、ジフルオロビスオキサラトリン酸アニオン、トリスオキサラトリン酸アニオン、トリフルオロメタンスルホン酸アニオン、フルオロスルホン酸アニオン、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドアニオン、ビス(ジフルオロホスホリル)イミドアニオン、(ジフルオロホスホリル)(フルオロスルホニル)イミドアニオン、及び(ジフルオロホスホリル)(トリフルオロメタンスルホニル)イミドアニオンからなる群から選ばれる少なくとも1種のアニオンの対からなるイオン性塩である、[1]~[7]のいずれか1項に記載の非水電解液。
前記(II)が、カリウムからなるカチオンと、ヘキサフルオロリン酸アニオン、ジフルオロリン酸アニオン、モノフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ジフルオロオキサラトホウ酸アニオン、テトラフルオロオキサラトリン酸アニオン、ジフルオロビスオキサラトリン酸アニオン、トリスオキサラトリン酸アニオン、トリフルオロメタンスルホン酸アニオン、フルオロスルホン酸アニオン、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドアニオン、ビス(ジフルオロホスホリル)イミドアニオン、(ジフルオロホスホリル)(フルオロスルホニル)イミドアニオン、及び(ジフルオロホスホリル)(トリフルオロメタンスルホニル)イミドアニオンからなる群から選ばれる少なくとも1種のアニオンの対からなるイオン性塩である、[1]~[7]のいずれか1項に記載の非水電解液。
前記(I)が、環状エステル、鎖状エステル、環状エーテル、及び鎖状エーテルからなる群から選ばれる少なくとも一つを含む、[1]~[9]のいずれか1項に記載の非水電解液。
[11]
前記環状エステルの一部又は全部が環状カーボネートである、[10]に記載の非水電解液。
[12]
前記鎖状エステルの一部又は全部が鎖状カーボネートである、[10]に記載の非水電解液。
前記(I)が、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、γ-ブチロラクトン、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、1,3-ジオキソラン、2-メチル-1,3-ジオキソラン、4-メチル-1,3-ジオキソラン、ジメトキシエタン、ジエトキシエタン、エトキシメトキシエタン、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、及びジプロピレングリコールジメチルエーテル、からなる群から選ばれる少なくとも一つを含む、[1]~[12]のいずれか1項に記載の非水電解液。
さらに、シクロヘキシルベンゼン、t-ブチルベンゼン、t-アミルベンゼン、フルオロベンゼン、ビニレンカーボネート、ビニレンカーボネートのオリゴマー(数平均分子量が170~5000)、ビニルエチレンカーボネート、フルオロエチレンカーボネート、1,6-ジイソシアナトヘキサン、エチニルエチレンカーボネート、trans-ジフルオロエチレンカーボネート、1,3-プロパンサルトン、1,3-プロペンサルトン、1,3,2-ジオキサチオラン-2,2-ジオキシド、4-プロピル-1,3,2-ジオキサチオラン-2,2-ジオキシド、メチレンメタンジスルホネート、1,2-エタンジスルホン酸無水物、トリス(トリメチルシリル)ボレート、スクシノニトリル、アジポニトリル、(エトキシ)ペンタフルオロシクロトリホスファゼン、メタンスルホニルフルオリド、テトラフルオロ(ピコリナト)ホスフェート、及び1,3-ジメチル-1,3-ジビニル-1,3-ジ(1,1,1,3,3,3-ヘキサフルオロイソプロピル)ジシロキサンからなる群から選ばれる少なくとも1つの添加剤を含有する、[1]~[13]のいずれか1項に記載の非水電解液。
少なくとも、正極と、負極と、[1]~[8]、[10]~[14]のいずれか1項に記載の非水電解液とを備える、非水ナトリウムイオン電池。
[16]
少なくとも、正極と、負極と、[1]~[7]、[9]~[14]のいずれか1項に記載の非水電解液とを備える、非水カリウムイオン電池。
[1]~[8]、[10]~[14]のいずれか1項に記載の非水電解液を準備する工程、及び
少なくとも正極と負極とを備えた空セルに前記非水電解液を充填する工程
を有する、非水ナトリウムイオン電池の製造方法。
[18]
[1]~[7]、[9]~[14]のいずれか1項に記載の非水電解液を準備する工程、及び
少なくとも正極と負極とを備えた空セルに前記非水電解液を充填する工程
を有する、非水カリウムイオン電池の製造方法。
本開示の実施形態に係る非水電解液は、ナトリウムイオン電池用又はカリウムイオン電池用の非水電解液であって、
(I)非水有機溶媒、
(II)イオン性塩である、溶質、
(III)有機塩素化合物、P-Cl結合を有するリン化合物、S(=O)2-Cl結合を有するスルホン化合物、S(=O)-Cl結合を有するスルフィン化合物、及びSi-Cl結合を有するケイ素化合物からなる群から選ばれる少なくとも1種を含む。
本開示の非水電解液に用いられる非水有機溶媒として、例えば、エステル類(カーボネート類を含む)、エーテル類、ラクトン類、ニトリル類、イミド類、及びスルホン類が挙げられる。
中でも、非水有機溶媒は、環状エステル、鎖状エステル、環状エーテル、及び鎖状エーテルからなる群から選ばれた少なくとも一つを含むことが好ましい。
鎖状エステルとしては、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルプロピルカーボネート、エチルプロピルカーボネート、メチルブチルカーボネート等の鎖状カーボネートの他、酢酸メチル、酢酸エチル、酢酸2,2-ジフルオロエチル、プロピオン酸メチル、プロピオン酸エチル、2-フルオロプロピオン酸メチル、2-フルオロプロピオン酸エチル、3,3,3-トリフルオロプロピオン酸メチル等が挙げられる。
鎖状エーテルとしては、ジメトキシエタン、ジエトキシエタン、ジエチルエーテル、ジブチルエーテル、ジイソプロピルエーテル、エトキシメトキシエタン、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル等が挙げられる。
上記非水有機溶媒における、環状エステル、鎖状エステル、環状エーテル、及び鎖状エーテルからなる群から選ばれた少なくとも一つの含有量(複数存在する場合は、その合計量)は、非水有機溶媒の総量に対して、好ましくは70~100体積%が好ましく、80~100体積%がより好ましい。
また、非水有機溶媒が鎖状エステルを含み、鎖状エステルの一部または全部が鎖状カーボネートであることが好ましい。
上記非水有機溶媒が、環状カーボネート及び鎖状カーボネートからなる群から選ばれる少なくとも1種を含むと、高温でのサイクル特性に優れる点で好ましい。また、上記非水有機溶媒が、環状エステル及び鎖状エステルからなる群から選ばれる少なくとも1種を含むと、低温での入出力特性に優れる点で好ましい。
上記非水有機溶媒における、環状カーボネート及び鎖状カーボネートからなる群から選ばれる少なくとも1種の含有量(複数存在する場合は、その合計量)は、非水有機溶媒の総量に対して、10~100体積%が好ましく、30~100体積%がより好ましい。
本開示の非水電解液に用いられる溶質として、例えば、ナトリウムイオン電池の場合ナトリウムイオン、カリウムイオン電池の場合カリウムイオンからなるカチオンと、ヘキサフルオロリン酸アニオン、ジフルオロリン酸アニオン、モノフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ヘキサフルオロヒ酸アニオン、ヘキサフルオロアンチモン酸アニオン、ジフルオロオキサラトホウ酸アニオン、テトラフルオロオキサラトリン酸アニオン、ジフルオロビスオキサラトリン酸アニオン、トリスオキサラトリン酸アニオン、トリフルオロメタンスルホン酸アニオン、フルオロスルホン酸アニオン、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(ペンタフルオロエタンスルホニル)イミドアニオン、(トリフルオロメタンスルホニル)(ペンタフルオロエタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドアニオン、(ペンタフルオロエタンスルホニル)(フルオロスルホニル)イミドアニオン、トリス(トリフルオロメタンスルホニル)メチドアニオン、ビス(ジフルオロホスホリル)イミドアニオン、(ジフルオロホスホリル)(フルオロスルホニル)イミドアニオン、及び(ジフルオロホスホリル)(トリフルオロメタンスルホニル)イミドアニオンからなる群から選ばれる少なくとも1種のアニオンの対からなるイオン性塩が挙げられる。
本開示の非水電解液に用いられる(III)成分は、有機塩素化合物、P-Cl結合を有するリン化合物、S(=O)2-Cl結合を有するスルホン化合物、S(=O)-Cl結合を有するスルフィン化合物、及びSi-Cl結合を有するケイ素化合物からなる群から選ばれる少なくとも1種である。これらは分解電位以上の電位での充電によって塩化物イオンを生成するものである。
上記有機塩素化合物は、C-Cl結合を有する脂肪族炭化水素化合物、及びC-Cl結合を有する芳香族炭化水素化合物、下記式(1)で示される化合物、及び下記式(2)で示される化合物からなる群から選ばれる少なくとも1種であることが好ましい。
Raが表す炭素数2~10のアルケニル基としては、ビニル基、アリル基等が挙げられる。
Raが表す炭素数2~10のアルキニル基としては、エチニル基、プロパルギル基等が挙げられる。
Raが表す炭素数6~15のアリール基としては、フェニル基、ナフチル基等が挙げられ、フェニル基が好ましい。
Raが表すアルコキシ基、アルケニルオキシ基、アルキニルオキシ基、及びアリールオキシ基におけるアルキル基、アルケニル基、アルキニル基、及びアリール基は、それぞれRaが表すアルキル基、アルケニル基、アルキニル基、及びアリール基と同様の基が挙げられ、好ましい例も同様である。
Raが表す各基が有していてもよい置換基としては、塩素原子、フッ素原子、エーテル基、カルボニル基、又はこれらの基を2種以上組み合わせてなる基が挙げられる。
Rxが表す各基が有していてもよい置換基としては、塩素原子、フッ素原子、エーテル基、カルボニル基、又はこれらの基を2種以上組み合わせてなる基が挙げられる。
上述の通り、複数あるRaの内、少なくとも1つはC-Cl結合を有する。
Rbが表す各基が有していてもよい置換基としては、塩素原子、フッ素原子、エーテル基、カルボニル基、又はこれらの基を2種以上組み合わせてなる基が挙げられる。
Ryが表す各基が有していてもよい置換基としては、塩素原子、フッ素原子、エーテル基、カルボニル基、又はこれらの基を2種以上組み合わせてなる基が挙げられる。
上述の通り、複数あるRbの内、少なくとも1つはC-Cl結合を有する。
中でもジクロロメタン、トリクロロメタン、1,1,2-トリクロロエタン、1,1,2,2-テトラクロロエタン、1,1,1,2-テトラクロロエタン、トリクロロエテン、テトラクロロエテン、アセチルクロリド、ジクロロアセチルクロリド、炭酸ビストリクロロメチル、ヘキサクロロ-2-プロパノン、オキサリルクロリド、クロロメチルホスホン酸ジフルオリド、クロロメチルホスホン酸ジメチル、クロロメチルスルホン酸フルオリド、2-クロロエタンスルホン酸フルオリド、クロロメチルスルホン酸メチル、フルオロスルホン酸クロロメチルが好ましい。
上記P-Cl結合を有するリン化合物としては、三塩化リン、二塩化一フッ化リン、一塩化二フッ化リン、塩化ホスホリル、二塩化一フッ化ホスホリル、一塩化二フッ化ホスホリル、五塩化リン、四塩化一フッ化リン、三塩化二フッ化リン、二塩化三フッ化リン、一塩化四フッ化リン、六塩化リン酸塩、五塩化一フッ化リン酸塩、四塩化二フッ化リン酸塩、三塩化三フッ化リン酸塩、二塩化四フッ化リン酸塩、一塩化五フッ化リン酸塩、モノクロロリン酸塩、ジクロロリン酸塩、モノクロロモノフルオロリン酸塩、ビス(ジクロロホスホリル)イミド塩、ジクロロホスホリルイソシアネート、モノクロロモノフルオロホスホリルイソシアネート、下記式(A)で示される化合物、下記式(B)で示される化合物、及び下記式(C)で示される化合物からなる群から選ばれる少なくとも1種が挙げられる。
R1~R3が表す炭素数2~10のアルケニル基としては、ビニル基、アリル基等が挙げられる。
R1~R3が表す炭素数2~10のアルキニル基としては、エチニル基、プロパルギル基等が挙げられる。
R1~R3が表す炭素数6~15のアリール基としては、フェニル基、ナフチル基等が挙げられ、フェニル基が好ましい。
R1~R3が表すアルコキシ基、アルケニルオキシ基、アルキニルオキシ基、及びアリールオキシ基におけるアルキル基、アルケニル基、アルキニル基、及びアリール基は、それぞれR1~R3が表すアルキル基、アルケニル基、アルキニル基、及びアリール基と同様の基が挙げられ、好ましい例も同様である。
R1~R3が表す各基が有していてもよい置換基としては、塩素原子、フッ素原子、エーテル基、カルボニル基、又はこれらの基を2種以上組み合わせてなる基が挙げられる。
中でも塩化ホスホリルや二塩化一フッ化ホスホリル、ジクロロリン酸塩、モノクロロモノフルオロリン酸塩、ビス(ジクロロホスホリル)イミド塩、ジクロロホスホリルイソシアネート、ジクロロリン酸メチルが好ましい。
上記S(=O)2-Cl結合を有するスルホン化合物としては、塩化スルフリル、塩化フッ化スルフリル、クロロメタンスルホニルクロリド、メタンジスルホニルジクロリド、1,3-プロパンジスルホニルジクロリド、クロロスルホニルイソシアネート、クロロスルホン酸、クロロスルホン酸塩、ビス(クロロスルホニル)イミド塩、(ジクロロホスホリル)(クロロスルホニル)イミド塩、(ジフルオロホスホリル)(クロロスルホニル)イミド塩、及び下記式(D)で示される化合物、からなる群から選ばれる少なくとも1種が挙げられる。
R4が表す各基が有していてもよい置換基としては、塩素原子、フッ素原子、アルキル基(好ましくは炭素数1~3のアルキル基)、クロロスルホニル基、エーテル基、カルボニル基、又はこれらの基を2種以上組み合わせてなる基等が挙げられる。
中でもメタンスルホニルクロリド、トリフルオロメタンスルホニルクロリド、トリクロロメタンスルホニルクロリド、塩化スルフリル、塩化フッ化スルフリル、クロロスルホン酸塩、クロロスルホン酸クロロメチル、ビス(クロロスルホニル)イミド塩、(ジクロロホスホリル)(クロロスルホニル)イミド塩、メタンジスルホニルジクロリド、1,3-プロパンジスルホニルジクロリドが好ましい。
非水ナトリウムイオン電池の場合、特に非水ナトリウムイオン電池中でのイオン伝導を助ける役割をするという観点から、リチウムイオン、ナトリウムイオン、カリウムイオン、テトラアルキルアンモニウムイオン、又はテトラアルキルホスホニウムイオンが好ましく、リチウムイオン、ナトリウムイオン、テトラアルキルアンモニウムイオン又はスピロ骨格を有するアンモニウムイオンであることがより好ましい。
非水カリウムイオン電池の場合、特に非水カリウムイオン電池中でのイオン伝導を助ける役割をするという観点から、リチウムイオン、ナトリウムイオン、カリウムイオン、テトラアルキルアンモニウムイオン、又はテトラアルキルホスホニウムイオンが好ましく、カリウムイオン、テトラアルキルアンモニウムイオン又はスピロ骨格を有するアンモニウムイオンであることがより好ましい。
テトラアルキルアンモニウムイオンにおけるアルキル基の炭素数は、1~6であることが好ましく、テトラアルキルホスホニウムイオンにおけるアルキル基の炭素数は、1~6であることが好ましい。
テトラアルキルアンモニウムイオンにおける4つのアルキル基は同一でも互いに異なっていてもよく、テトラアルキルホスホニウムイオンにおける4つのアルキル基は同一でも互いに異なっていてもよい。
スピロ骨格を有するアンモニウムイオンは、例えば、5-アゾニアスピロ[4.4]ノナンが好ましい。
上記S(=O)-Cl結合を有するスルフィン化合物としては、塩化スルフィニル、塩化フッ化スルフィニル、メチルスルフィニルクロリド、エチルスルフィニルクロリド、及びt-ブチルスルフィニルクロリドからなる群から選ばれる少なくとも1種が挙げられる。
上記Si-Cl結合を有するケイ素化合物としては、トリアルキルクロロシラン、ジアルキルジクロロシラン、アルキルトリクロロシラン、テトラクロロシラン、ジアルキルクロロヒドロシラン、アルキルジクロロヒドロシラン、及びアルキルクロロジヒドロシランからなる群から選ばれる少なくとも1種が挙げられる。
Si-Cl結合を有するケイ素化合物に含まれることのあるアルキル基としては、メチル基又はエチル基が好ましく、メチル基がより好ましい。
上記(III)の濃度xは、塩素原子換算で、0.05質量%≦x≦1.20質量%であることがさらに好ましい。
本開示の要旨を損なわない限りにおいて、本開示の非水電解液に一般に用いられる添加成分を任意の比率でさらに添加しても良い。具体例としては、シクロヘキシルベンゼン、シクロヘキシルフルオロベンゼン、ビフェニル、ジフルオロアニソール、t-ブチルベンゼン、t-アミルベンゼン、フルオロベンゼン、2-フルオロトルエン、2-フルオロビフェニル、ビニレンカーボネート、ビニレンカーボネートのオリゴマー(数平均分子量が170~5000)、ジメチルビニレンカーボネート、ビニルエチレンカーボネート、フルオロエチレンカーボネート、1,6-ジイソシアナトヘキサン、エチニルエチレンカーボネート、trans-ジフルオロエチレンカーボネート、無水マレイン酸、無水コハク酸、1,3-プロパンサルトン、1,3-プロペンサルトン、1,4-ブタンスルトン、1,3,2-ジオキサチオラン-2,2-ジオキシド、4-プロピル-1,3,2-ジオキサチオラン-2,2-ジオキシド、メチレンメタンジスルホネート、ジメチレンメタンジスルホネート、トリメチレンメタンジスルホネート、エチレンサルフェート、メタンスルホン酸メチル、ジフルオロビス(オキサラト)リン酸リチウム、ジフルオロビス(オキサラト)リン酸ナトリウム、ジフルオロビス(オキサラト)リン酸カリウム、ジフルオロオキサラトホウ酸リチウム、ジフルオロオキサラトホウ酸ナトリウム、ジフルオロオキサラトホウ酸カリウム、テトラフルオロオキサラトリン酸リチウム、テトラフルオロオキサラトリン酸ナトリウム、テトラフルオロオキサラトリン酸カリウム、トリス(オキサラト)リン酸リチウム、ヘキサフルオロイソプロパノール、トリフルオロエタノール、ジ(ヘキサフルオロイソプロピル)カーボネート、ジ(トリフルオロエチル)カーボネート、1,2-エタンジスルホン酸無水物、トリス(トリメチルシリル)ボレート、スクシノニトリル、アジポニトリル、(エトキシ)ペンタフルオロシクロトリホスファゼン、メタンスルホニルフルオリド、テトラフルオロ(ピコリナト)ホスフェート、1,3-ジメチル-1,3-ジビニル-1,3-ジ(1,1,1,3,3,3-ヘキサフルオロイソプロピル)ジシロキサン等の過充電防止効果、負極皮膜形成効果や正極保護効果を有する化合物が挙げられる。また、ポリマー電池と呼ばれる非水電解液電池に使用される場合のように非水電解液をゲル化剤や架橋ポリマーにより擬固体化して使用することも可能である。ヘキサフルオロイソプロパノール等のフッ素化されたアルコールは、その求核性の低さからヘキサフルオロリン酸塩を始めとする溶質と反応してフッ化水素を発生させる事は無く、例えば入出力特性を向上する添加剤として用いられる。
本開示の非水電解質電池は、非水ナトリウムイオン電池又は非水カリウムイオン電池である。
本開示の実施形態に係る非水ナトリウムイオン電池は、少なくとも、正極と、負極と、上記非水電解液とを含む。
また本開示の実施形態に係る非水カリウムイオン電池は、少なくとも、正極と、負極と、上記非水電解液とを含む。
より具体的には、本開示の非水電解液電池は、正極と、ナトリウム又はナトリウムの吸蔵放出の可能な負極材料からなる負極と、上記非水電解液と、集電体、セパレーター、容器等から成る。あるいは、本開示の非水電解液電池は、正極と、カリウム又はカリウムの吸蔵放出の可能な負極材料からなる負極と、上記非水電解液と、集電体、セパレーター、容器等から成る。
正極は正極活物質、集電体であるアルミニウム箔、導電材、結着剤から成り、正極活物質の種類は特に限定されるものでないが、ナトリウムイオンやカリウムイオンが可逆的に挿入-脱離可能な材料が用いられる。アルミニウム箔の材質としては、一般的にはアルミニウム純度の高い純アルミニウム1000系(例えばA1085や、A1N30等)や、強度を高める目的でマンガンを添加したアルミマンガン合金3000系(例えばA3003)等が用いられる。更には、同様に強度を高める目的でマグネシウムを添加したアルミマグネシウム合金5000系や、鉄を添加した8000系(1000~7000番台に該当しない合金)もよく用いられる。また、アルミニウム箔は厚さ数μm~数十μmのものが一般的に用いられている。
負極は負極活物質、集電体、導電材、結着剤から成り、負極活物質の種類は特に限定されるものでないが、ナトリウムイオンやカリウムイオンが可逆的に挿入-脱離可能な材料が用いられる。
正極、負極の集電体には、銅、アルミニウム、ステンレス鋼、ニッケル、チタン又はこれらの合金等を用いることができる。集電体の少なくとも一方の面に活物質層が形成される。
正極と負極の接触を防ぐためのセパレーターとしては、ポリオレフィン(例えば、ポリプロピレン、ポリエチレン)、紙、及びガラス繊維等で作られた不織布や多孔質シート、フィルムが使用される。これらは、電解液がしみ込んでイオンが透過し易いように、微多孔化されているものが好ましい。
外装体としては、例えば、コイン型、円筒型、角型等の金属缶や、ラミネート外装体を用いることができる。金属缶材料としては、例えば、ニッケルメッキを施した鉄鋼板、ステンレス鋼板、ニッケルメッキを施したステンレス鋼板、アルミニウム又はその合金、ニッケル、チタン等が挙げられる。ラミネート外装体としては、例えば、アルミニウムラミネートフィルム、SUS製ラミネートフィルム、シリカをコーティングしたポリプロピレンやポリエチレン等のラミネートフィルム等を用いることができる。
本開示は、前記非水電解液を準備する工程、及び少なくとも正極と負極とを備えた空セルに前記非水電解液を充填する工程を有する、非水ナトリウムイオン電池の製造方法にも関する。
また本開示は、前記非水電解液を準備する工程、及び少なくとも正極と負極とを備えた空セルに前記非水電解液を充填する工程を有する、非水カリウムイオン電池の製造方法にも関する。
[C-Cl結合を有する添加剤を含む電解液作製]
(電解液No.1~電解液No.57の作製)
非水溶媒としてプロピレンカーボネート(以下、「PC」とも記載する)、ジエチルカーボネート(以下、「DEC」とも記載する)の、体積比1:1の混合溶媒を用い、該溶媒中に、溶質のナトリウム塩としてNaPF6、C-Cl結合を有する添加剤を、表1及び表2に記載の濃度となるように溶解し、電解液No.1~電解液No.56を調製した。また、C-Cl結合を有する添加剤を用いなかったこと以外は電解液No.1と同様にして、電解液No.57を調製した。上記の調製は、液温を20℃~30℃の範囲に維持しながら行った。
(電解液No.58~電解液No.100の作製)
非水溶媒としてPCを用い、C-Cl結合を有する添加剤に代えて、P-Cl結合を有する添加剤を、表3及び表4に記載の濃度となるように溶解すること以外は、電解液No.1と同様に電解液No.58~電解液No.99を調製した。また、P-Cl結合を有する添加剤を用いなかったこと以外は電解液No.58と同様にして、電解液No.100を調製した。
(電解液No.101~電解液No.144の作製)
非水溶媒としてPC、エチレンカーボネート(以下「EC」とも記載する)、DECの、体積比1:1:2の混合溶媒を用い、C-Cl結合を有する添加剤に代えて、S(=O)2-Cl結合を有する添加剤を、表5及び表6に記載の濃度となるように溶解すること以外は、電解液No.1と同様に電解液No.101~電解液No.143を調製した。また、S(=O)2-Cl結合を有する添加剤を用いなかったこと以外は電解液No.101と同様にして、電解液No.144を調製した。
(電解液No.145~電解液No.159の作製)
非水溶媒としてPC、ジメチルカーボネート(以下「DMC」とも記載する)の、体積比3:7の混合溶媒を用い、C-Cl結合を有する添加剤に代えて、S(=O)-Cl結合を有する添加剤を、表7に記載の濃度となるように溶解すること以外は、電解液No.1と同様に電解液No.145~電解液No.158を調製した。また、S(=O)-Cl結合を有する添加剤を用いなかったこと以外は電解液No.145と同様にして、電解液No.159を調製した。
(電解液No.160~電解液No.168の作製)
非水溶媒としてジエチレングリコールジメチルエーテル(以下「DG」とも記載する)を用い、該溶媒中に、溶質としてナトリウムビス(フルオロスルホニル)イミド(以下「NaFSI」とも記載する)、Si-Cl結合を有する添加剤を、表8に記載の濃度となるように溶解し、電解液No.160~電解液No.167を調製した。また、Si-Cl結合を有する添加剤を用いなかったこと以外は電解液No.160と同様にして、電解液No.168を調製した。上記の調製は、液温を20℃~30℃の範囲に維持しながら行った。
(電解液No.169~電解液No.180の作製)
非水溶媒としてEC、DECの、体積比1:1の混合溶媒を用い、該溶媒中に、溶質のカリウム塩としてカリウムビス(フルオロスルホニル)イミド(以下「KFSI」とも記載する)、Cl含有添加剤(含塩素化合物)を、表9に記載の濃度となるように溶解し、電解液No.169~電解液No.179を調製した。また、Cl含有添加剤を用いなかったこと以外は電解液No.169と同様にして、電解液No.180を調製した。上記の調製は、液温を20℃~30℃の範囲に維持しながら行った。
[実施例1-1~実施例1-56及び比較例1-1]
試験用電解液として表1に記載の電解液、正極材料としてNaNi0.5Ti0.3Mn0.2O2、負極材料としてハードカーボン(クレハ社製、カーボトロンP)を用いて作製した試験用セルに対し、高温サイクル試験を行い、サイクル特性、サイクル試験中の抵抗増加率、ガス発生量をそれぞれ評価した。これらの評価結果を表10及び表11に示す。なお、試験用セルは以下のように作製した。
正極活物質としてNaNi0.5Ti0.3Mn0.2O2を90質量%と、導電剤として5質量%のアセチレンブラックと、結着剤として5質量%のポリフッ化ビニリデン(PVDF)とを混合し、さらに溶媒としてN-メチルピロリドンを前記正極活物質と、導電剤と、結着剤との総質量に対し、82質量%となるように添加し、スラリー溶液を調製した。このスラリー溶液を、正極集電体であるアルミニウム箔上に塗布して、150℃で12時間乾燥させることにより、集電体上に正極活物質層を形成した試験用正極を得た。
負極活物質としてハードカーボン粉末(クレハ社製、カーボトロンP)90質量%と、結着剤としてポリフッ化ビニリデン(PVDF)10質量%とを混合し、さらに溶媒としてN-メチルピロリドンを前記負極活物質と結着剤との総質量に対し50質量%となるように添加し、スラリー溶液を調製した。このスラリー溶液を、負極集電体である銅箔上に塗布して、150℃で12時間乾燥させることにより、集電体上に負極活物質層を形成した試験用負極を得た。
組み立てた上記の電池は、25℃の環境温度において充電上限電圧4.1V、放電下限電圧1.5Vとして、定電流定電圧法で、電流密度0.32mA/cm2、定電圧充電終止電流密度0.08mA/cm2で充放電を行った。これを充放電1サイクルとし、計3サイクルの充放電を行って電池を安定化させた。その後再び25℃の環境温度において充電上限電圧4.1Vとして、定電流定電圧法で、電流密度0.32mA/cm2、定電圧充電終止電流密度0.08mA/cm2で充電を行い、これを満充電状態とした。満充電状態のセルを電気化学アナライザー(ALSモデル604Eビー・エー・エス株式会社)で交流インピーダンス測定を行った。この時観測された円弧より算出した抵抗値を初期抵抗とした。その後、放電下限電圧1.5Vとして、定電流法で、電流密度0.32mA/cm2で放電を行った。
初期試験後のセルに対し、60℃の環境温度での充放電試験を実施し、サイクル特性を評価した。充電は4.1Vまで、放電は1.5Vまで行い、電流密度1.56mA/cm2で充放電サイクルを繰り返した。そして、60℃の環境温度での充放電試験における500サイクル目の放電容量維持率でセルの劣化の具合を評価した(高温サイクル特性評価)。「高温サイクル後放電容量維持率」は下記式で求めた。なお、60℃の環境温度での充放電試験における1サイクル目の放電容量を初放電容量とした。
<500サイクル目の放電容量維持率>
高温サイクル後放電容量維持率(%)=(500サイクル目の放電容量/初放電容量)×100
上記のサイクル試験後のセルに対し、25℃の環境温度において充電上限電圧4.1Vとして、定電流定電圧法で、電流密度0.32mA/cm2、定電圧充電終止電流密度0.08mA/cm2で充電を行い、満充電状態とした。満充電状態のセルを電気化学アナライザー(ALSモデル604Eビー・エー・エス株式会社)で交流インピーダンス測定を行った。この時観測された円弧より算出した抵抗値をサイクル試験後の抵抗とした。その後、放電下限電圧1.5Vとして、定電流法で、電流密度0.32mA/cm2で放電を行った。サイクル試験における抵抗の増加率でセルの劣化具合を評価した(抵抗増加率)。「高温サイクル時抵抗増加率」は下記式で求めた。
<抵抗増加率>
高温サイクル時抵抗増加率(%)=(サイクル試験後の抵抗/初期抵抗)×100
上記の高温サイクル特性評価の実施前後において、シリコンオイル(信越化学工業社製、シリコーンオイルKF54)を用いたアルキメデス法によりセルの容積を測定し、ガス発生量V(単位:cm3)(ガス発生量V=高温サイクル特性評価実施後のセルの容積V2-高温サイクル特性評価実施前のセルの容積V1)を求めた。このガス発生量Vに基づき、「高温サイクル時ガス発生量」を評価した。
また、実施例1-1~実施例1-18において、C-Cl結合を有する化合物を所定量(電解液全量に対して、0.06質量%~3.00質量%)添加することにより、高温サイクル特性の向上効果がより発揮されることを確認した。
NaFe0.4Mn0.3Ni0.3O2を正極活物質に用い、表3及び表4に記載の電解液を用いた以外は実施例1-1と同様にセルを作製し、高温サイクル試験を行い、サイクル特性、サイクル試験中の抵抗増加率、ガス発生量をそれぞれ評価した。これらの評価結果を表12及び13に示す。
また、実施例2-1~実施例2-18において、P-Cl結合を有する化合物を所定量添加することにより、高温サイクル特性の向上効果がより発揮されることを確認した。
NaNi1/3Ti1/3Mn1/3O2を正極活物質に用い、表5及び表6に記載の電解液を用いた以外は実施例1-1と同様にセルを作製し、高温サイクル試験を行い、サイクル特性、サイクル試験中の抵抗増加率、ガス発生量をそれぞれ評価した。これらの評価結果を表14及び表15に示す。
また、実施例3-1~実施例3-18において、S(=O)2-Cl結合を有する化合物を所定量添加することにより、高温サイクル特性の向上効果がより発揮されることを確認した。
Na2/3Ni1/3Ti1/6Mn1/2O2を正極活物質に用い、表7に記載の電解液を用いた以外は実施例1-1と同様にセルを作製し、高温サイクル試験を行い、サイクル特性、サイクル試験中の抵抗増加率、ガス発生量をそれぞれ評価した。これらの評価結果を表16に示す。
また、実施例4-1~実施例4-12において、S(=O)-Cl結合を有する化合物を所定量添加することにより、高温サイクル特性の向上効果がより発揮されることを確認した。
NaCrO2を正極活物質に用い、表8に記載の電解液を用いた以外は実施例1-1と同様にセルを作製し、充電上限電圧を3.3Vに変更して、初期充放電試験及び高温サイクル試験を行い、サイクル特性、サイクル試験中の抵抗増加率(充電上限電圧を3.3Vに変更)、ガス発生量をそれぞれ評価した。これらの評価結果を表17に示す。
また、実施例5-1~実施例5-6において、Si-Cl結合を有する化合物を所定量添加することにより、高温サイクル特性の向上効果がより発揮されることを確認した。
[実施例6-1~実施例6-11及び比較例6-1]
試験用電解液として表9に記載の電解液、正極材料としてK2Mn[Fe(CN)6]、負極材料として人造黒鉛を用いて作製した試験用セルに対し、高温サイクル試験を行い、サイクル特性、サイクル試験中の抵抗増加率、ガス発生量をそれぞれ評価した。これらの評価結果を表18に示す。なお、試験用セルは以下のように作製した。
正極活物質としてK2Mn[Fe(CN)6]を85質量%と、導電剤として8質量%のアセチレンブラックと、結着剤として7質量%のポリフッ化ビニリデン(PVDF)とを混合し、さらに溶媒としてN-メチルピロリドンを前記正極活物質と、導電剤と、結着剤との総質量に対し、82質量%となるように添加し、スラリー溶液を調製した。このスラリー溶液を、正極集電体であるアルミニウム箔上に塗布して、150℃で12時間乾燥させることにより、集電体上に正極活物質層を形成した試験用正極を得た。
負極活物質として人造黒鉛90質量%と、結着剤としてポリフッ化ビニリデン(PVDF)10質量%とを混合し、さらに溶媒としてN-メチルピロリドンを前記負極活物質と結着剤との総質量に対し50質量%となるように添加し、スラリー溶液を調製した。このスラリー溶液を、負極集電体である銅箔上に塗布して、150℃で12時間乾燥させることにより、集電体上に負極活物質層を形成した試験用負極を得た。
組み立てた上記の電池は、25℃の環境温度において充電上限電圧4.1V、放電下限電圧2.0Vとして、定電流定電圧法で、電流密度0.13mA/cm2、定電圧充電終止電流密度0.03mA/cm2で充放電を行った。これを充放電1サイクルとし、計3サイクルの充放電を行って電池を安定化させた。その後再び25℃の環境温度において充電上限電圧4.1Vとして、定電流定電圧法で、電流密度0.13mA/cm2、定電圧充電終止電流密度0.03mA/cm2で充電を行い、これを満充電状態とした。満充電状態のセルを電気化学アナライザー(ALSモデル604Eビー・エー・エス株式会社)で交流インピーダンス測定を行った。この時観測された円弧より算出した抵抗値を初期抵抗とした。その後、放電下限電圧2.0Vとして、定電流法で、電流密度0.13mA/cm2で放電を行った。
初期試験後のセルに対し、60℃の環境温度での充放電試験を実施し、サイクル特性を評価した。充電は4.1Vまで、放電は2.0Vまで行い、電流密度0.62mA/cm2で充放電サイクルを繰り返した。そして、60℃の環境温度での充放電試験における100サイクル目の放電容量維持率でセルの劣化の具合を評価した(高温サイクル特性評価)。「高温サイクル後放電容量維持率」は下記式で求めた。なお、60℃の環境温度での充放電試験における1サイクル目の放電容量を初放電容量とした。
<100サイクル目の放電容量維持率>
高温サイクル後放電容量維持率(%)=(100サイクル目の放電容量/初放電容量)×100
上記のサイクル試験後のセルに対し、25℃の環境温度において充電上限電圧4.1Vとして、定電流定電圧法で、電流密度0.13mA/cm2、定電圧充電終止電流密度0.03mA/cm2で充電を行い、満充電状態とした。満充電状態のセルを電気化学アナライザー(ALSモデル604Eビー・エー・エス株式会社)で交流インピーダンス測定を行った。この時観測された円弧より算出した抵抗値をサイクル試験後の抵抗とした。その後、放電下限電圧2.0Vとして、定電流法で、電流密度0.13mA/cm2で放電を行った。サイクル試験における抵抗の増加率でセルの劣化具合を評価した(抵抗増加率)。「高温サイクル時抵抗増加率」は下記式で求めた。
<抵抗増加率>
高温サイクル時抵抗増加率(%)=(サイクル試験後の抵抗/初期抵抗)×100
上記の高温サイクル特性評価の実施前後において、シリコンオイル(信越化学工業社製、シリコーンオイルKF54)を用いたアルキメデス法によりセルの容積を測定し、ガス発生量V(単位:cm3)(ガス発生量V=高温サイクル特性評価実施後のセルの容積V2-高温サイクル特性評価実施前のセルの容積V1)を求めた。このガス発生量Vに基づき、「高温サイクル時ガス発生量」を評価した。
また、実施例6-1~実施例6-6において、塩素含有化合物を所定量添加することにより、高温サイクル特性の向上効果がより発揮されることを確認した。
[添加剤含有電解液作製]
(電解液No.181~電解液No.192の作製)
非水溶媒としてPC、DECを体積比1:1で混合した混合溶媒を用い、該溶媒中に、溶質のナトリウム塩としてNaPF6、塩素含有化合物としてクロロスルホン酸ナトリウム、その他の添加剤(第2の化合物ともいう)としてフルオロエチレンカーボネートを、表19に記載の濃度となるように溶解し、電解液No.181を調製した。上記の調製は、液温を20~30℃の範囲に維持しながら行った。
また、その他の添加剤の種類及び濃度を表19に記載のものに変更すること以外は電解液No.181と同様に電解液No.182~電解液No.186を調製した。さらに、クロロスルホン酸ナトリウムを添加しなかったこと以外は、電解液No.181~電解液No.186と同様にして、電解液No.187~電解液No.192を調製した。
[添加剤含有電解液作製]
(電解液No.193~電解液No.198の作製)
非水溶媒としてEC、DECを体積比1:1で混合した混合溶媒を用い、該溶媒中に、溶質のカリウム塩としてKFSI、塩素含有化合物として塩化フッ化スルフリル、その他の添加剤としてフルオロエチレンカーボネートを、表20に記載の濃度となるように溶解し、電解液No.193を調製した。上記の調製は、液温を20~30℃の範囲に維持しながら行った。
また、その他の添加剤の種類を表20に記載のものに変更すること以外は電解液No.193と同様に電解液No.194、電解液No.195を調製した。さらに、塩化フッ化スルフリルを添加しなかったこと以外は、電解液No.193~電解液No.195と同様にして、電解液No.196~電解液No.198を調製した。
[実施例7-1~実施例7-6及び比較例7-1~比較例7-6]
非水電解液として、表19に記載の電解液を用いた以外は、実施例1-1と同様の性能評価を実施した。評価結果を表21に示す。
[実施例8-1~実施例8-3及び比較例8-1~比較例8-3]
非水電解液として、表20に記載の電解液を用いた以外は、実施例6-1と同様の性能評価を実施した。評価結果を表22に示す。
本出願は、2021年6月23日出願の日本特許出願(特願2021-104481)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (18)
- ナトリウムイオン電池用又はカリウムイオン電池用の非水電解液であって、
(I)非水有機溶媒、
(II)イオン性塩である、溶質、
(III)有機塩素化合物、P-Cl結合を有するリン化合物、S(=O)2-Cl結合を有するスルホン化合物、S(=O)-Cl結合を有するスルフィン化合物、及びSi-Cl結合を有するケイ素化合物からなる群から選ばれる少なくとも1種
を含む、非水電解液。 - 前記(III)の濃度xが、塩素原子換算で0.01質量%≦x≦3.20質量%である、請求項1に記載の非水電解液。
- 前記有機塩素化合物が、C-Cl結合を有する脂肪族炭化水素化合物、C-Cl結合を有する芳香族炭化水素化合物、下記式(1)で示される化合物、及び下記式(2)で示される化合物からなる群から選ばれる少なくとも1種である、請求項1又は2に記載の非水電解液。
(式中Raは、それぞれ独立に、フッ素原子、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数1~10のアルコキシ基、置換基を有していてもよい炭素数2~10のアルケニル基、置換基を有していてもよい炭素数2~10のアルケニルオキシ基、置換基を有していてもよい炭素数2~10のアルキニル基、置換基を有していてもよい炭素数2~10のアルキニルオキシ基、置換基を有していてもよい炭素数6~15のアリール基、置換基を有していてもよい炭素数6~15のアリールオキシ基、又は、N(Rx)2を表す。Rxは、それぞれ独立に、水素原子、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数2~10のアルケニル基、又は、置換基を有していてもよい炭素数2~10のアルキニル基を表す。複数あるRxは互いに同一でも互いに異なっていてもよい。複数あるRxは互いに結合していてもよい。複数あるRaの内、少なくとも1つはC-Cl結合を有し、Raは互いに同一でも互いに異なっていてもよい。複数あるRaは互いに結合していてもよい。)
(式中Rbは、それぞれ独立に、フッ素原子、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数1~10のアルコキシ基、置換基を有していてもよい炭素数2~10のアルケニル基、置換基を有していてもよい炭素数2~10のアルケニルオキシ基、置換基を有していてもよい炭素数2~10のアルキニル基、置換基を有していてもよい炭素数2~10のアルキニルオキシ基、置換基を有していてもよい炭素数6~15のアリール基、置換基を有していてもよい炭素数6~15のアリールオキシ基、又は、N(Ry)2を表す。Ryは、それぞれ独立に、水素原子、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数2~10のアルケニル基、又は、置換基を有していてもよい炭素数2~10のアルキニル基を表す。複数あるRyは互いに同一でも互いに異なっていてもよい。複数あるRyは互いに結合していてもよい。複数あるRbの内、少なくとも1つはC-Cl結合を有し、Rbは互いに同一でも互いに異なっていてもよい。複数あるRbは互いに結合していてもよい。) - 前記P-Cl結合を有するリン化合物が、三塩化リン、二塩化一フッ化リン、一塩化二フッ化リン、塩化ホスホリル、二塩化一フッ化ホスホリル、一塩化二フッ化ホスホリル、五塩化リン、四塩化一フッ化リン、三塩化二フッ化リン、二塩化三フッ化リン、一塩化四フッ化リン、六塩化リン酸塩、五塩化一フッ化リン酸塩、四塩化二フッ化リン酸塩、三塩化三フッ化リン酸塩、二塩化四フッ化リン酸塩、一塩化五フッ化リン酸塩、モノクロロリン酸塩、ジクロロリン酸塩、モノクロロモノフルオロリン酸塩、ビス(ジクロロホスホリル)イミド塩、ジクロロホスホリルイソシアネート、モノクロロモノフルオロホスホリルイソシアネート、下記式(A)で示される化合物、下記式(B)で示される化合物、及び下記式(C)で示される化合物からなる群から選ばれる少なくとも1種である、請求項1又は2に記載の非水電解液。
(式中R1は、それぞれ独立に、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数1~10のアルコキシ基、置換基を有していてもよい炭素数2~10のアルケニル基、置換基を有していてもよい炭素数2~10のアルケニルオキシ基、置換基を有していてもよい炭素数2~10のアルキニル基、置換基を有していてもよい炭素数2~10のアルキニルオキシ基、置換基を有していてもよい炭素数6~15のアリール基、又は置換基を有していてもよい炭素数6~15のアリールオキシ基を表す。複数あるR1は互いに同一でも互いに異なっていてもよい。R1は互いに結合していてもよい。)
(式中R2は、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数1~10のアルコキシ基、置換基を有していてもよい炭素数2~10のアルケニル基、置換基を有していてもよい炭素数2~10のアルケニルオキシ基、置換基を有していてもよい炭素数2~10のアルキニル基、置換基を有していてもよい炭素数2~10のアルキニルオキシ基、置換基を有していてもよい炭素数6~15のアリール基、又は置換基を有していてもよい炭素数6~15のアリールオキシ基を表す。)
(式中R3は、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数1~10のアルコキシ基、置換基を有していてもよい炭素数2~10のアルケニル基、置換基を有していてもよい炭素数2~10のアルケニルオキシ基、置換基を有していてもよい炭素数2~10のアルキニル基、置換基を有していてもよい炭素数2~10のアルキニルオキシ基、置換基を有していてもよい炭素数6~15のアリール基、又は置換基を有していてもよい炭素数6~15のアリールオキシ基を表す。) - 前記S(=O)2-Cl結合を有するスルホン化合物が、塩化スルフリル、塩化フッ化スルフリル、クロロメタンスルホニルクロリド、メタンジスルホニルジクロリド、1,3-プロパンジスルホニルジクロリド、クロロスルホニルイソシアネート、クロロスルホン酸、クロロスルホン酸塩、ビス(クロロスルホニル)イミド塩、(ジクロロホスホリル)(クロロスルホニル)イミド塩、(ジフルオロホスホリル)(クロロスルホニル)イミド塩、及び下記式(D)で示される化合物、からなる群から選ばれる少なくとも1種である、請求項1又は2に記載の非水電解液。
(式中R4は、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数1~10のアルコキシ基、置換基を有していてもよい炭素数2~10のアルケニル基、置換基を有していてもよい炭素数2~10のアルケニルオキシ基、置換基を有していてもよい炭素数2~10のアルキニル基、置換基を有していてもよい炭素数2~10のアルキニルオキシ基、置換基を有していてもよい炭素数6~15のアリール基、又は置換基を有していてもよい炭素数6~15のアリールオキシ基を表す。) - 前記S(=O)-Cl結合を有するスルフィン化合物が、塩化スルフィニル、塩化フッ化スルフィニル、メチルスルフィニルクロリド、エチルスルフィニルクロリド、及びt-ブチルスルフィニルクロリドからなる群から選ばれる少なくとも1種である、請求項1又は2に記載の非水電解液。
- 前記Si-Cl結合を有するケイ素化合物が、トリアルキルクロロシラン、ジアルキルジクロロシラン、アルキルトリクロロシラン、テトラクロロシラン、ジアルキルクロロヒドロシラン、アルキルジクロロヒドロシラン、及びアルキルクロロジヒドロシランからなる群から選ばれる少なくとも1種である、請求項1又は2に記載の非水電解液。
- 前記(II)が、ナトリウムからなるカチオンと、ヘキサフルオロリン酸アニオン、ジフルオロリン酸アニオン、モノフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ジフルオロオキサラトホウ酸アニオン、テトラフルオロオキサラトリン酸アニオン、ジフルオロビスオキサラトリン酸アニオン、トリスオキサラトリン酸アニオン、トリフルオロメタンスルホン酸アニオン、フルオロスルホン酸アニオン、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドアニオン、ビス(ジフルオロホスホリル)イミドアニオン、(ジフルオロホスホリル)(フルオロスルホニル)イミドアニオン、及び(ジフルオロホスホリル)(トリフルオロメタンスルホニル)イミドアニオンからなる群から選ばれる少なくとも1種のアニオンの対からなるイオン性塩である、請求項1又は2に記載の非水電解液。
- 前記(II)が、カリウムからなるカチオンと、ヘキサフルオロリン酸アニオン、ジフルオロリン酸アニオン、モノフルオロリン酸アニオン、テトラフルオロホウ酸アニオン、ジフルオロオキサラトホウ酸アニオン、テトラフルオロオキサラトリン酸アニオン、ジフルオロビスオキサラトリン酸アニオン、トリスオキサラトリン酸アニオン、トリフルオロメタンスルホン酸アニオン、フルオロスルホン酸アニオン、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、(トリフルオロメタンスルホニル)(フルオロスルホニル)イミドアニオン、ビス(ジフルオロホスホリル)イミドアニオン、(ジフルオロホスホリル)(フルオロスルホニル)イミドアニオン、及び(ジフルオロホスホリル)(トリフルオロメタンスルホニル)イミドアニオンからなる群から選ばれる少なくとも1種のアニオンの対からなるイオン性塩である、請求項1又は2に記載の非水電解液。
- 前記(I)が、環状エステル、鎖状エステル、環状エーテル、及び鎖状エーテルからなる群から選ばれる少なくとも一つを含む、請求項1又は2に記載の非水電解液。
- 前記環状エステルの一部又は全部が環状カーボネートである、請求項10に記載の非水電解液。
- 前記鎖状エステルの一部又は全部が鎖状カーボネートである、請求項10に記載の非水電解液。
- 前記(I)が、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、γ-ブチロラクトン、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、1,3-ジオキソラン、2-メチル-1,3-ジオキソラン、4-メチル-1,3-ジオキソラン、ジメトキシエタン、ジエトキシエタン、エトキシメトキシエタン、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、及びジプロピレングリコールジメチルエーテル、からなる群から選ばれる少なくとも一つを含む、請求項1又は2に記載の非水電解液。
- さらに、シクロヘキシルベンゼン、t-ブチルベンゼン、t-アミルベンゼン、フルオロベンゼン、ビニレンカーボネート、ビニレンカーボネートのオリゴマー(数平均分子量が170~5000)、ビニルエチレンカーボネート、フルオロエチレンカーボネート、1,6-ジイソシアナトヘキサン、エチニルエチレンカーボネート、trans-ジフルオロエチレンカーボネート、1,3-プロパンサルトン、1,3-プロペンサルトン、1,3,2-ジオキサチオラン-2,2-ジオキシド、4-プロピル-1,3,2-ジオキサチオラン-2,2-ジオキシド、メチレンメタンジスルホネート、1,2-エタンジスルホン酸無水物、トリス(トリメチルシリル)ボレート、スクシノニトリル、アジポニトリル、(エトキシ)ペンタフルオロシクロトリホスファゼン、メタンスルホニルフルオリド、テトラフルオロ(ピコリナト)ホスフェート、及び1,3-ジメチル-1,3-ジビニル-1,3-ジ(1,1,1,3,3,3-ヘキサフルオロイソプロピル)ジシロキサンからなる群から選ばれる少なくとも1つの添加剤を含有する、請求項1又は2に記載の非水電解液。
- 少なくとも、正極と、負極と、請求項1又は2に記載の非水電解液とを備える、非水ナトリウムイオン電池。
- 少なくとも、正極と、負極と、請求項1又は2に記載の非水電解液とを備える、非水カリウムイオン電池。
- 請求項1又は2に記載の非水電解液を準備する工程、及び
少なくとも正極と負極とを備えた空セルに前記非水電解液を充填する工程
を有する、非水ナトリウムイオン電池の製造方法。 - 請求項1又は2に記載の非水電解液を準備する工程、及び
少なくとも正極と負極とを備えた空セルに前記非水電解液を充填する工程
を有する、非水カリウムイオン電池の製造方法。
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