WO2016072158A1 - Procédé de purification de solution d'électrolyte et procédé de production de solution d'électrolyte - Google Patents
Procédé de purification de solution d'électrolyte et procédé de production de solution d'électrolyte Download PDFInfo
- Publication number
- WO2016072158A1 WO2016072158A1 PCT/JP2015/076382 JP2015076382W WO2016072158A1 WO 2016072158 A1 WO2016072158 A1 WO 2016072158A1 JP 2015076382 W JP2015076382 W JP 2015076382W WO 2016072158 A1 WO2016072158 A1 WO 2016072158A1
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- WO
- WIPO (PCT)
- Prior art keywords
- chloride
- electrolyte solution
- acid
- purifying
- agent
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 92
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 119
- 238000000746 purification Methods 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 84
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 73
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000243 solution Substances 0.000 claims abstract description 43
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 7
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 176
- 239000002253 acid Substances 0.000 claims description 114
- 235000006408 oxalic acid Nutrition 0.000 claims description 59
- -1 carboxylic acid chlorides Chemical class 0.000 claims description 58
- 230000002829 reductive effect Effects 0.000 claims description 35
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 25
- 239000012346 acetyl chloride Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 21
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 21
- 239000012025 fluorinating agent Substances 0.000 claims description 19
- 239000012629 purifying agent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 17
- 239000003125 aqueous solvent Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 238000003682 fluorination reaction Methods 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 10
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000002841 Lewis acid Substances 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 claims description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000003949 imides Chemical class 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 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 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229940006487 lithium cation Drugs 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 150000004010 onium ions Chemical class 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 3
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 239000012085 test solution Substances 0.000 description 86
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 238000009835 boiling Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 17
- 239000011737 fluorine Substances 0.000 description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 229910013870 LiPF 6 Inorganic materials 0.000 description 11
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 239000003456 ion exchange resin Substances 0.000 description 8
- 229920003303 ion-exchange polymer Polymers 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- LSJNBGSOIVSBBR-UHFFFAOYSA-N thionyl fluoride Chemical compound FS(F)=O LSJNBGSOIVSBBR-UHFFFAOYSA-N 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 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 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000004255 ion exchange chromatography Methods 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- AOMUALOCHQKUCD-UHFFFAOYSA-N dodecyl 4-chloro-3-[[3-(4-methoxyphenyl)-3-oxopropanoyl]amino]benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=C(Cl)C(NC(=O)CC(=O)C=2C=CC(OC)=CC=2)=C1 AOMUALOCHQKUCD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 3
- 238000013101 initial test Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 3
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910010941 LiFSI Inorganic materials 0.000 description 2
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- DDKMFOUTRRODRE-UHFFFAOYSA-N chloromethanone Chemical compound Cl[C]=O DDKMFOUTRRODRE-UHFFFAOYSA-N 0.000 description 2
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 231100001231 less toxic Toxicity 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GKDCWKGUOZVDFX-UHFFFAOYSA-N 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)butane-2,3-diol Chemical compound FC(F)(F)C(C(F)(F)F)(O)C(O)(C(F)(F)F)C(F)(F)F GKDCWKGUOZVDFX-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- CMQUGOHGJUTDGZ-UHFFFAOYSA-N 3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propanoic acid Chemical compound OC(=O)C(O)(C(F)(F)F)C(F)(F)F CMQUGOHGJUTDGZ-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QHEDSQMUHIMDOL-UHFFFAOYSA-J hafnium(4+);tetrafluoride Chemical compound F[Hf](F)(F)F QHEDSQMUHIMDOL-UHFFFAOYSA-J 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for purifying an electrolyte solution used as an electrolytic solution for electrochemical devices such as lithium ion batteries, sodium ion batteries, lithium air batteries, lithium sulfur batteries, and lithium ion capacitors.
- non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, and lithium ion capacitors have been actively developed.
- Metal salts (Li, Na, etc.) of ionic complexes in which Lewis acid and fluorine ions are bonded such as hexafluorophosphate anion, tetrafluoroborate anion, hexafluoroarsenate anion, have high solubility and high ion dissociation
- hexafluorophosphate anion such as hexafluorophosphate anion, tetrafluoroborate anion, hexafluoroarsenate anion
- hexafluoroarsenate anion have high solubility and high ion dissociation
- it is used as a supporting electrolyte for electrochemical devices from the viewpoint of a wide potential window.
- lithium hexafluorophosphate (hereinafter LiPF 6 ) is particularly widely used because it is less toxic than lithium hexafluoroarsenate and has higher solubility than lithium tetrafluoroborate.
- LiPF 6 also has a major drawback that it has low thermal stability and decomposes into lithium fluoride (hereinafter LiF) and phosphorus pentafluoride (hereinafter PF 5 ) by heating.
- LiF is deposited on the electrode surface and becomes a resistance component, thereby reducing the performance of lithium-based electrochemical devices such as lithium ion batteries.
- PF 5 accelerates the decomposition of the electrolyte solvent due to its strong Lewis acidity.
- an ionic complex containing fluorine may react with moisture in the air or liquid to generate hydrogen fluoride.
- excessive hydrogen fluoride may remain or hydrogen fluoride may be by-produced.
- hydrogen fluoride in the electrolyte causes dissolution of the electrode material and corrosion of the current collector, which in turn causes deterioration of the cycle characteristics of the battery, and further decreases in battery characteristics such as charge / discharge capacity and storage stability. Therefore, the lower the content of hydrogen fluoride, the better.
- the concentration of hydrogen fluoride in the electrolytic solution is less than 30 ppm by mass (Patent Document 3).
- hydrogen fluoride when removing hydrogen fluoride in the electrolyte under reduced pressure, hydrogen fluoride has a high boiling point of 19.54 ° C. due to the influence of hydrogen bonds, so it takes time to remove hydrogen fluoride. The concentration of hydrogen fluoride could not be lowered sufficiently.
- the present invention has been made in view of the above circumstances, and removes hydrogen fluoride in an electrolyte solution used as an electrolyte solution for an electrochemical device to a low concentration in a short time compared to the conventional method. It is an object of the present invention to provide a method for purifying an electrolyte solution that can be used. Furthermore, it is more preferable that oxalic acid remaining when producing an ionic complex in which a part or all of the fluorine of LiPF 6 is replaced with oxalic acid can be removed at the same time.
- the present inventor conducted extensive research to solve the above problems, and added a chloride purification agent to make hydrogen fluoride into hydrogen chloride, and then fluorinated purification agent and unreacted purification agent.
- a chloride purification agent to make hydrogen fluoride into hydrogen chloride, and then fluorinated purification agent and unreacted purification agent.
- the present invention provides the following method for purifying an electrolyte solution.
- the first aspect of the present invention is a step of adding thionyl chloride as a purification agent to an electrolyte solution containing at least hydrogen fluoride as an impurity and having an electrolyte dissolved in a nonaqueous solvent, and reacting the impurity with the purification agent. And removing the impurities by removing hydrogen chloride as a reaction product, the fluorinated purification agent, and the unreacted purification agent, and an electrolyte solution comprising: This is a purification method.
- an electrolyte solution containing at least hydrogen fluoride as an impurity and having an electrolyte dissolved in a non-aqueous solvent includes a carboxylic acid chloride, a sulfonate acid chloride, a sulfinate acid chloride, a silicon chloride, Adding a purification agent consisting of one or a mixture selected from the group consisting of carboxylic acid anhydrides and reacting the impurities with the purification agent while extracting the reaction product out of the reaction system; And a step of removing the impurities by removing hydrogen chloride and the fluorinated purification agent, which are substances, and the unreacted purification agent, and a method for purifying an electrolyte solution.
- a third aspect of the present invention is a method for producing an electrolyte solution, which includes a purification step using the method for purifying an electrolyte solution according to the first or second aspect.
- the purification method of the present invention hydrogen fluoride in a solution used as an electrolytic solution of an electrochemical device is used, thionyl chloride is used as a purification agent, or a reaction product is removed from the system during the reaction with the purification agent. By removing it, it is possible to remove it to a low concentration in a simpler process and in a shorter time than before. Further, since the specific purification agent reacts with both hydrogen fluoride and oxalic acid, hydrogen fluoride and oxalic acid can be removed simultaneously by removing the reaction product and the unreacted purification agent.
- thionyl chloride is added as a purification agent to an electrolyte solution containing at least hydrogen fluoride as an impurity and in which the electrolyte is dissolved in a nonaqueous solvent, and the impurity is reacted with the purification agent.
- a removal step of removing the impurities by removing hydrogen chloride as a reaction product, the fluorinated purification agent, and the unreacted purification agent is a method for purifying an electrolyte solution.
- the electrolyte solution may contain oxalic acid as an impurity.
- fluorinated refining agent refers to thionyl fluoride, thionyl monochloride monochloride and the like.
- reaction product of the refining agent and oxalic acid refers to sulfur dioxide, carbon monoxide, carbon dioxide, etc. produced by the reaction of the refining agent and oxalic acid.
- the reaction product becomes a gas and quickly exits the reaction system and can participate in the reaction. Therefore, the reverse reaction of the reaction formula does not proceed, the reaction rate of the normal reaction that is a reaction between hydrogen fluoride and thionyl chloride is increased, and the concentration of hydrogen fluoride can be rapidly reduced to a low concentration.
- reaction products and unreacted thionyl chloride can be removed simultaneously with removal of hydrogen chloride, a separate step such as filtration is unnecessary, which is suitable for industrial purification. .
- thionyl chloride is a liquid at normal temperature and pressure, it is liquid when added to the electrolyte solution before purification, and therefore, it is easier to add than when adding a gaseous purification agent.
- the electrolyte contained in the solution is preferably a salt, and the cation of the salt is preferably composed of one of lithium cation, sodium cation, potassium cation, quaternary alkyl ammonium cation, or a mixture thereof. This is because these cations can be used as cations of salts contained in the electrolyte for non-aqueous electrolyte batteries.
- the salt anion is one of a hexafluorophosphate anion, a tetrafluoroborate anion, a bis (fluorosulfonyl) imide anion, a bis (trifluoromethanesulfonyl) imide anion, a bis (difluorophosphoryl) imide anion, or a mixture thereof. It is preferable to become. This is because these anions can be used as anions of salts contained in the electrolyte for non-aqueous electrolyte batteries.
- the salt is lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, lithium bis (fluorosulfonyl) imide, bis (fluorosulfonyl) ) Sodium imide, potassium bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide lithium, sodium bis (trifluoromethanesulfonyl) imide, potassium bis (trifluoromethanesulfonyl) imide, lithium bis (difluorophosphoryl) imide, bis (difluoro) One of phosphoryl) imide sodium, potassium bis (difluorophosphoryl) imide, difluoroionic complex (2a), (2b), (2c) It is preferably made of a mixture thereof.
- each element constituting the general formula (2) is as follows.
- the lithium salt of the difluoroionic complex (2a) is referred to as (2a-Li).
- A Li, Na, K or quaternary alkyl ammonium
- A Li, Na, K or quaternary alkyl ammonium
- A Li, Na, K or quaternary alkyl ammonium
- A Li, Na, K or quaternary alkyl ammonium
- non-aqueous solvent for the electrolyte solution the same non-aqueous solvent used in the synthesis method of the third embodiment described later can be used.
- the reaction time between the impurities and the purifying agent can be appropriately selected within the range of 0.1 to 72 hours depending on the reaction rate, but occupying the apparatus for a long time leads to an increase in production cost. Is preferably 12 hours or shorter, and more preferably 6 hours or shorter. Furthermore, in order to advance the reaction of the entire system, it is preferable to stir the solution during the reaction.
- the purification agent is preferably used in a range of 10 moles or less relative to the number of moles of free acid. Furthermore, it is preferable that the free acid and the purifying agent are in a molar ratio range of 1: 0.1 to 1:10, and in particular, the free acid and the purifying agent are in a molar ratio range of 1: 1 to 1: 5. It is preferable.
- the addition of the purification agent, stirring, and the subsequent removal of the reaction product and the unreacted purification agent are preferably performed at a temperature of ⁇ 60 ° C. to 150 ° C., more preferably ⁇ 20 ° C. to 120 ° C. If the temperature is lower than ⁇ 60 ° C., the stirring may be insufficient due to an increase in viscosity or the reaction rate may be decreased. If the temperature is higher than 150 ° C., the dissolved electrolyte may be decomposed. In particular, the temperature at which the reaction product and the unreacted purification agent are removed is preferably ⁇ 20 ° C. to 120 ° C., which can be easily heated and cooled.
- each process in the first embodiment of the present invention at a temperature lower than the boiling point of the purifying agent or the solvent so as not to evaporate a large amount of the purifying agent or the solvent.
- the addition of a purifying agent, stirring, and the subsequent removal of the reaction product and unreacted purifying agent are preferably performed at 50 ° C. or lower so that the electrolyte contained in the solution does not decompose.
- the reaction product and the unreacted purification agent are removed by a method using a vapor pressure difference. Specifically, a method of degassing under reduced pressure or an inert gas introduced into the solution is used. It is removed by the method of kicking out with it.
- Vacuum pump, aspirator, etc. can be used for decompression. Depressurization is performed by keeping the reactor in a sealed state and then maintaining the system at a pressure lower than atmospheric pressure. At this time, a part of the nonaqueous solvent is also distilled off, so that the concentration of the electrolyte is concentrated. Since the pressure in the system varies depending on the temperature and vapor pressure of the liquid to be purified, it cannot be generally stated. However, it is preferable to maintain the vacuum in the tank at 80 kPa or less in absolute pressure. If the holding pressure exceeds 80 kPa, the reaction product in the electrolyte solution, the unreacted purification agent, etc.
- the absolute pressure is preferably 20 kPa or more.
- the introduction of the inert gas into the solution is performed by bubbling the solution with nitrogen gas, helium gas, neon gas, argon gas, krypton gas, or xenon gas. Note that the decompression of the reaction system and the introduction of the inert gas into the solution may be performed simultaneously.
- a carboxylic acid chloride, a sulfonic acid chloride, a sulfinic acid chloride, a silicon chloride is added to an electrolyte solution containing at least hydrogen fluoride as an impurity and having an electrolyte dissolved in a nonaqueous solvent.
- a purification step of an electrolyte solution comprising: a removal step of removing the impurities by removing hydrogen chloride and the fluorinated purification agent which are reaction products, and the unreacted purification agent. Is the method.
- the same solution as in the first embodiment can be used.
- the reaction between the hydrogen fluoride in the solution and the purifying agent, or the reaction between hydrogen fluoride and oxalic acid and the purifying agent is carried out while extracting the reaction product out of the system.
- Hydrogen fluoride and oxalic acid can be removed by reaction decomposition.
- the method of extracting the produced reaction product out of the system is to reduce the pressure of the reaction system or to introduce an inert gas into the solution. Depressurization and introduction of inert gas can be performed in the same manner as described above. This is because the reaction between hydrogen fluoride and the refining agent is reversible, so the generated hydrogen chloride and the fluorinated purifying agent are continuously removed from the system by reducing the pressure or introducing an inert gas.
- reaction between oxalic acid and the refining agent is an irreversible reaction in which carbon monoxide and carbon dioxide are generated and discharged out of the system, but they are slowed down even if accelerated by reduced pressure or introduction of inert gas. It will never be done.
- the reaction is conducted while extracting the reaction product out of the system, whereby the fluorination reaction of thionyl chloride is accelerated and the removal of hydrogen fluoride can proceed. .
- the purification agent carboxylic acid chloride, sulfonate acid chloride, sulfinate acid chloride, silicon chloride, carboxylic acid anhydride and the like can be used.
- the purification agents include oxalyl chloride, methyl chloroformate, ethyl chloroformate, acetyl chloride, trifluoroacetic acid chloride, trifluoromethanesulfonic acid chloride, methanesulfonic acid chloride, thionyl chloride, trimethylsilyl chloride, acetic anhydride, trifluoroacetic anhydride.
- Carboxyl chloride, sulfonate chloride, sulfinate chloride and silicon chloride react with hydrogen fluoride to produce carboxylic acid fluoride, sulfonic acid fluoride, sulfinic acid fluoride, silicon fluoride and chloride, respectively.
- Produce hydrogen Since each fluoride has a small atomic weight of fluorine, it has a lower boiling point than chloride and is easily removed under reduced pressure or a bubbling environment. Further, since the boiling point of hydrogen chloride is as low as ⁇ 85 ° C., it is easily removed. Similarly, since carboxylic acid anhydride and carboxylic acid are obtained by reacting with hydrogen fluoride, carboxylic acid anhydride is removed by volatilization under reduced pressure or bubbling environment.
- acetyl chloride (boiling point 51 ° C.) reacts with hydrogen fluoride
- hydrogen chloride (boiling point ⁇ 85 ° C.)
- acetyl fluoride (boiling point 20 ° C.) are produced according to the following reaction formula, both of which are under reduced pressure or bubbling environment. Removed below.
- fluorinated purification agent refers to acetyl fluoride and the like.
- the purification agent is oxalyl chloride, methyl chloroformate, ethyl chloroformate, acetyl chloride, trifluoroacetic acid chloride, trifluoromethanesulfonic acid chloride, methanesulfonic acid chloride, thionyl chloride, it decomposes not only hydrogen fluoride but also oxalic acid And can be removed.
- reaction product of the purification agent and oxalic acid refers to acetic acid, carbon monoxide, carbon dioxide, etc. produced by the reaction of the purification agent and oxalic acid.
- the reaction product is reacted while being extracted out of the system, the reaction between hydrogen fluoride and the purifying agent can be accelerated, and hydrogen fluoride can be quickly removed to a low concentration. it can.
- reaction process and the removal process method and conditions in the second embodiment are the same as those in the first embodiment.
- the third embodiment of the present invention is a method for producing an electrolyte solution, comprising a purification step using the electrolyte solution purification method of the first or second embodiment.
- an electrolyte solution containing an ionic complex containing fluorine such as LiPF 6
- excess hydrogen fluoride may remain or hydrogen fluoride may be produced as a by-product, and the ionic complex containing fluorine is air.
- an electrolyte solution containing an ionic complex containing fluorine such as after synthesizing an ionic complex containing fluorine, it may generate hydrogen fluoride by reacting with moisture in the liquid or in the liquid.
- an electrolyte solution with less impurities such as hydrogen fluoride can be obtained.
- the 6-coordinated ionic complex (1) represented by the general formula (1) is fluorinated with a fluorinating agent in a non-aqueous solvent to produce the difluoroionic complex (2) represented by the general formula (2).
- the electrolyte solution of the first or second embodiment is purified.
- a hexacoordinate ionic complex in which three bidentate ligands represented by the following general formula (1) are coordinated hereinafter referred to as a six-coordinate ionic complex
- a difluoroionic complex represented by the following general formula (2) hereinafter sometimes referred to as difluoroionic complex (2)
- a + is any one selected from the group consisting of metal ions, protons, and onium ions, and serves to assist ion conduction in the nonaqueous electrolyte battery.
- metal ions protons, and onium ions
- lithium ion, sodium ion, potassium ion, or quaternary alkyl ammonium ion is preferable.
- the quaternary alkylammonium ion is not particularly limited, and examples thereof include trimethylpropylammonium and 1-butyl-1-methylpyrrolidinium.
- M is any one selected from the group consisting of P, As and Sb.
- F is a fluorine atom.
- O is an oxygen atom.
- Y is a carbon atom or a sulfur atom.
- Q is 1 when Y is a carbon atom.
- Q is 1 or 2 when Y is a sulfur atom.
- W is a hydrocarbon group which may have a heteroatom having 1 to 10 carbon atoms or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used), or- N (R 1 ) — is represented.
- R 1 represents a hydrogen atom, an alkali metal, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom which may have a halogen atom.
- R 1 can take a branched chain or a cyclic structure.
- Z is a carbon atom.
- each element of the anion portion of the hexacoordinate ionic complex (1) and the difluoroionic complex (2) is at least one combination selected from (a), (b), and (c).
- a fluorinating agent having a molar ratio of 1.5 to 50 moles to the 6-coordinated ionic complex (1) is added.
- the difluoroionic complex (2) is obtained by selective fluorination with use.
- the amount of the fluorinating agent used is preferably 1.8 to 40 mol times, more preferably 2.0 to 20 mol times.
- an ionic fluorinating agent that generates fluoride ions when added to a non-aqueous solvent can be used.
- an ionic fluorinating agent that generates fluoride ions when added to a non-aqueous solvent.
- an acid or a Lewis acid may be added in addition to the fluorinating agent.
- an acid or a Lewis acid By adding an acid or a Lewis acid, it is possible to increase the proton concentration in the reaction solution and improve the reaction rate when introducing fluorine using a fluorinating agent.
- sulfuric acid, fluorosulfuric acid, hydrogen chloride, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, nitric acid, p-toluenesulfonic acid can be used as an acid (protic acid or Bronsted acid) other than the fluorinating agent.
- boron trifluoride, phosphorus pentafluoride, aluminum trichloride, niobium pentachloride, trifluoromethanesulfonic acid metal salt (cations are Li, Na, K, La, Ce, Pr, Nd Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) can be used.
- trifluoromethanesulfonic acid, methanesulfonic acid, or trifluoroacetic acid because the effect of improving the reaction rate is great.
- the equivalent of the acid other than the fluorinating agent or the Lewis acid is preferably 0.001 to 2.0 molar equivalents relative to the hexacoordinate ionic complex (1). If the amount of the acid other than the fluorinating agent or the Lewis acid is too small, the effect of improving the reaction rate is small. If the amount is too large, not only the cost increases but also the decomposition of the product proceeds.
- an acid or Lewis acid By adding an acid or Lewis acid, it is possible to use other than the above acidic fluorinating agent.
- potassium fluoride Sodium fluoride, lithium fluoride, cesium fluoride, calcium fluoride, nickel fluoride, cobalt fluoride, iron fluoride, zinc fluoride, manganese fluoride, and ammonium fluoride are preferable.
- lithium fluoride sodium fluoride, potassium fluoride, cesium fluoride, cal fluoride Um, nickel fluoride, iron fluoride, zinc fluoride, ammonium fluoride is preferred.
- the non-aqueous solvent used in the synthesis method described above dissolves the 6-coordinate ionic complex (1) as a raw material even in a very small amount, and does not cause a reaction with a compound in the system.
- Those having a relative dielectric constant of 2 or more are preferable.
- a non-aqueous solvent having no solubility it is not preferable because fluorination becomes very slow. If there is even a slight solubility, the reaction proceeds because the solubility of the target difluoroionic complex (2) is high.
- carbonate esters, esters, ketones, lactones, ethers, nitriles, amides, sulfones and the like can be used, and not only a single solvent but also two or more kinds of mixed solvents may be used.
- non-aqueous solvent examples include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, acetone, ethyl Methyl ketone, diethyl ketone, ⁇ -butyrolactone, ⁇ -valerolactone, tetrahydrofuran, tetrahydropyran, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, propionitrile, N, N -Dimethylformamide, dimethyl sulfoxide, sulfolane and the like, among which a solvent having a boiling point of 120 ° C or lower is preferable,
- the reaction temperature when introducing fluorine using a fluorinating agent is ⁇ 60 ° C. to 150 ° C., preferably ⁇ 20 to 120 ° C. Fluorine introduction does not proceed sufficiently at temperatures lower than -60 ° C, and decomposition of the 6-coordinate ionic complex (1) or difluoroionic complex (2) as a product may occur at temperatures above 150 ° C. There is sex. The range of ⁇ 20 to 120 ° C. is optimal in order to obtain a sufficient fluorine introduction rate and not cause decomposition.
- the reaction time can be appropriately selected according to the reaction rate. However, since occupying the apparatus for a long period leads to an increase in production cost, it is preferable to set it to 72 hours or less in practice. Furthermore, in order to advance the reaction of the entire system, it is preferable to stir the solution during the reaction.
- a pressure reducing operation in order to reduce the residual free acid concentration, and if necessary, remove the precipitate by filtration.
- a vacuum pump, an aspirator, etc. can be used for pressure reduction operation.
- the depressurization operation is carried out by keeping the reactor in a sealed state and then maintaining the system at a pressure below atmospheric pressure. Since the pressure in the system varies depending on the temperature and vapor pressure of the liquid to be purified, it cannot be generally stated. However, it is preferable to maintain the vacuum in the tank at 80 kPa or less in absolute pressure.
- the absolute pressure is preferably 20 kPa or more.
- the ligand of the six-coordinated ionic complex (1) and the difluoroionic complex (2) is oxalic acid
- a pressure reduction operation is performed after fluorination, and a part of the solvent is distilled off to difluoro It is preferable to separate the oxalic acid deposited when the ionic complex (2) is concentrated by filtration.
- the raw materials and products were handled in a nitrogen atmosphere with a dew point of ⁇ 50 ° C. or lower.
- the glass reactor and fluororesin reactor used were those dried at 150 ° C. for 12 hours or more and then cooled to room temperature under a nitrogen stream having a dew point of ⁇ 50 ° C. or less.
- test solution used in the de-free acid treatment test shown in Table 1 was prepared as a solution containing at least hydrogen fluoride as an impurity and dissolved in an electrolyte.
- the free acid value was expressed as a value based on the salt (for example, (2a-Li) in the test solution A) by converting the molar concentration of the acid into the mass of HF.
- the conversion rate to a difluoroionic complex (2a-Li) in which two molecules of oxalic acid are coordinated is 71.0% and the selectivity is 95.4%.
- the residual chlorine concentration and the residual free acid concentration are difluoroion ions. And less than 100 ppm by mass and 2000 ppm by mass, respectively, based on the sex complex (2a-Li).
- the amount of hydrogen fluoride added was 2.0 molar equivalents, 0.02 molar equivalent of trifluoromethanesulfonic acid (hereinafter TfOH) was added as an acid for accelerating the reaction, and the mixture was stirred at 0 ° C. for 24 hours.
- TfOH trifluoromethanesulfonic acid
- the conversion rate to the difluoroionic complex (2a-Li) was 94.2% and the selectivity was 95.2%. It was confirmed that the reaction rate was improved by proceeding the fluorination reaction in the presence of TfOH. It was.
- Test solution B Test solution A was concentrated to a salt concentration of about 50% by mass, and the precipitated solid was removed by filtration. While stirring at a temperature of 25 ° C., 6 mass times of chloroform was added to the mass of the obtained concentrated liquid to precipitate a solid. The precipitated (2a-Li) was collected by filtration. The free acid concentration contained in (2a-Li) recovered here was less than 20 mass ppm based on (2a-Li). This (2a-Li) was dissolved in EMC to prepare a 25% by mass EMC solution. Oxalic acid (0.11 g, 1.3 mmol) was added to 100 g of this EMC solution to prepare Test Solution B containing 2,000 ppm by mass of oxalic acid in terms of HF based on (2a-Li).
- Test solution C Test solution A was concentrated to a salt concentration of about 50% by mass, and the precipitated solid was removed by filtration. While stirring at a temperature of 25 ° C., 6 mass times of chloroform was added to the mass of the obtained concentrated liquid to precipitate a solid. The precipitated (2a-Li) was collected by filtration. The free acid concentration contained in (2a-Li) recovered here was less than 20 mass ppm based on (2a-Li). This (2a-Li) was dissolved in EMC to prepare a 25% by mass EMC solution. HF (0.05 g, 2.5 mmol) was added to 100 g of this EMC solution to prepare Test Solution C containing 2000 mass ppm of HF based on (2a-Li).
- Test solution D Test solution A (100 g) was concentrated under reduced pressure (50 ° C., 1.3 kPa) to remove EMC. Dimethyl carbonate (hereinafter DMC) (70 g) was added to the remaining solid residue (30 g) to prepare a (2a-Li) / DMC solution having a salt concentration of about 25% by mass, and the free acid concentration was measured (2a-Li ) And 1750 mass ppm.
- DMC Dimethyl carbonate
- Test Solution E By changing EMC to DMC in the procedure for preparing Test Solution C described above, Test Solution E containing 2000 mass ppm of HF based on (2a-Li) was obtained.
- Test Solution G By changing EMC to DEC in the above-described procedure for preparing Test Solution C, Test Solution G containing 2000 mass ppm of HF based on (2a-Li) was obtained.
- Test solution H A test solution containing 500 mass ppm of HF and 1500 mass ppm of oxalic acid in terms of HF based on (2a-Li) by changing DMC to tetrahydrofuran (hereinafter THF) in the procedure for preparing test solution D described above. H was obtained.
- Test Solution I By changing EMC to THF in the procedure for preparing Test Solution C described above, Test Solution I containing 2000 ppm by mass of HF based on (2a-Li) was obtained.
- Test Solution K By changing EMC to AcOEt in the procedure for preparing Test Solution C described above, Test Solution K containing 2,000 ppm by mass of HF based on (2a-Li) was obtained.
- Test solution L By changing DMC to acetonitrile (hereinafter referred to as CH 3 CN) in the procedure for preparing test solution D described above, HF is contained at 500 ppm by mass based on (2a-Li), and oxalic acid is contained at 1500 ppm by mass in terms of HF. Test liquid L was obtained.
- Test solution M By changing EMC to CH 3 CN in the procedure for preparing test solution C described above, test solution M containing 2000 mass ppm of HF based on (2a-Li) was obtained.
- the conversion rate and selectivity were determined by F and P-NMR, the residual chlorine concentration was determined by silver nitrate titration, and the residual free acid concentration was determined by free acid titration.
- the conversion rate to the difluoroionic complex (2a-Na) is 94.8%, the selectivity is 96.0%, and the residual chlorine concentration and the residual free acid concentration are the same as those of the difluoroionic complex (2a-Na).
- the standards were less than 100 mass ppm and 2000 mass ppm, respectively.
- the obtained (2a-Na) / EMC solution was adjusted to a salt concentration of about 25% by mass to obtain Test Solution N.
- the molar ratio of the fluoride anion to the oxalate anion was 1: 2. From this, it was found that 2000 mass ppm of free acid was derived from HF at 400 mass ppm and oxalic acid at 1600 mass ppm (converted to HF).
- Test solution O 500 g of the ion exchange resin was weighed and immersed in a 0.1 N aqueous sodium hydroxide solution (2.5 kg), and stirred at 25 ° C. for 6 hours. The ion exchange resin was collected by filtration and washed thoroughly with pure water until the pH of the washing solution was 8 or less. Thereafter, moisture was removed by drying under reduced pressure (120 ° C., 1.3 kPa) for 12 hours. Test solution A was concentrated to a salt concentration of about 50% by mass, and the precipitated solid was removed by filtration. While stirring at a temperature of 25 ° C., 6 mass times of chloroform was added to the mass of the obtained concentrated liquid to precipitate a solid.
- the precipitated (2a-Li) was collected by filtration.
- the free acid concentration contained in (2a-Li) recovered here was less than 20 mass ppm based on (2a-Li).
- This (2a-Li) 25 g, 99.4 mmol was dissolved in EMC (275 mL), 150 g of the dried ion exchange resin was added thereto, and the mixture was stirred at 25 ° C. for 6 hours. Thereafter, by removing the ion exchange resin by filtration, a (2a-Na) / EMC solution in which cations were exchanged from Li + to Na + was obtained.
- the ratio of Na + / Li + was 99.3.
- Test solution P LiPF 6 (25 g) was dissolved in EMC (75 g), and then HF (0.05 g, 2.5 mmol) was added to prepare a test solution P containing 2000 mass ppm of HF based on LiPF 6 .
- Test Solution Q After dissolving NaPF 6 (25 g) in EMC (75 g), HF (0.05 g, 2.5 mmol) was added to prepare Test Solution Q containing 2000 mass ppm of HF based on NaPF 6 .
- Test solution R LiBF 4 (25 g) was dissolved in EMC (75 g), HF (0.05 g, 2.5 mmol) was added, and a test solution R containing 2000 ppm by mass of HF based on LiBF 4 was obtained.
- Test solution S LiFSI (25 g) was dissolved in EMC (75 g), and then HF (0.05 g, 2.5 mmol) was added to prepare test solution S containing 2000 mass ppm of HF based on LiFSI.
- Test solution T LiDFPI (25 g) was dissolved in EMC (75 g), and then HF (0.05 g, 2.5 mmol) was added to prepare test solution T containing 2000 mass ppm of HF based on LiDFPI.
- each test solution is shown in Table 1.
- Table 1 PF 6 represents a hexafluorophosphate anion
- BF 4 represents a tetrafluoroborate anion
- FSI represents a bis (fluorosulfonyl) imide anion
- DFPI represents a bis (difluorophosphoryl) imide anion.
- each test solution containing an ionic complex should be based on the ionic complex, since an ionic complex is often contained in the electrolytic solution by several% to several tens of%. It is necessary to make the hydrogen fluoride concentration about 1000 ppm by mass or less.
- Example 1-1 To test solution A (100 g), thionyl chloride (0.36 g, 3.0 mmol, 1.2 eq. With respect to 2000 mass ppm of free acid converted to HF) was added as a purification agent, and the mixture was stirred at a temperature of 25 ° C. for 6 hours. Went. Thereby, hydrogen fluoride and thionyl chloride were converted into highly volatile hydrogen chloride and thionyl fluoride by the reaction. Thereafter, the reaction product was removed by reducing the pressure at a temperature of 20 to 40 ° C. and an absolute pressure of 50 to 80 kPa. At the same time, 25 g of EMC was distilled off to concentrate the ionic complex. As a result of measuring the free acid concentration, the value in terms of HF based on (2a-Li) was 200 ppm by mass.
- Example 1-2 Except for changing the temperature from 25 ° C. to 40 ° C., the same procedure as in Example 1-1 was performed. As a result, the free acid concentration was less than 100 mass ppm.
- Example 1-3 The procedure was the same as in Example 1-1, except that the temperature was changed from 25 ° C. to 40 ° C., the stirring time was changed from 6 hours to 3 hours, and dry nitrogen gas (10 mL / min) was continuously blown into the solution during the stirring. As a result of the treatment, the free acid concentration was less than 100 ppm by mass.
- Example 1-4 Thionyl chloride (0.36 g, 3.0 mmol, 1.2 eq. With respect to 2000 mass ppm of free acid converted to HF) was added to test solution A (100 g), and the pressure was 50 to 80 kPa at 40 ° C. and absolute pressure. The mixture was depressurized to 3 hours and stirred. The pressure was restored to atmospheric pressure with nitrogen, and 5 g of EMC was added to restore the initial test solution weight to 100 g. Thereafter, concentration was performed under reduced pressure at a temperature of 20 to 40 ° C. and an absolute pressure of 50 to 80 kPa, and 25 g of EMC was distilled off. As a result of measuring the free acid concentration, the value in terms of HF based on (2a-Li) was less than 100 mass ppm.
- Example 1-5 The test solution B was used and the treatment was performed in the same procedure as in Example 1-2, except that the stirring time was changed from 6 hours to 3 hours. As a result, the free acid concentration was less than 100 ppm by mass.
- Example 1-6 The treatment was performed in the same procedure as in Example 1-2 except that the test solution C was used and the stirring time was changed from 6 hours to 3 hours. As a result, the free acid concentration was 600 ppm by mass.
- Example 1-7 As a result of processing in the same procedure as Example 1-6 except that the addition amount of thionyl chloride was changed to 0.59 g, 5.0 mmol (2.0 eq. Relative to 2000 mass ppm of free acid in terms of HF), The free acid concentration was 200 ppm by mass.
- Example 1-8 As a result of performing the same procedure as in Example 1-4 except that the amount of thionyl chloride added was changed to 0.59 g and 5.0 mmol using Test Solution C, the free acid concentration was less than 100 ppm by mass. became.
- test solution A 100 g was stirred at a temperature of 40 ° C. for 3 hours while continuously blowing dry nitrogen gas (10 mL / min) into the solution. Thereafter, vacuum concentration was performed at a temperature of 20 to 40 ° C., and 25 g of EMC was distilled off. As a result of measuring the free acid concentration, it was 2000 mass ppm.
- Test solution A 100 g was stirred at a temperature of 40 ° C. for 3 hours while keeping the pressure in the container at a reduced pressure (50 to 80 kPa). Thereafter, vacuum concentration was performed at a temperature of 20 to 40 ° C., and 25 g of EMC was distilled off. As a result of measuring the free acid concentration, the value in terms of HF based on (2a-Li) was 1900 mass ppm.
- Test solution C 100 g containing hydrogen fluoride but containing almost no oxalic acid was stirred at a temperature of 40 ° C. for 3 hours while keeping the pressure in the container at a reduced pressure (50 to 80 kPa). Thereafter, vacuum concentration was performed at a temperature of 20 to 40 ° C., and 25 g of EMC was distilled off. As a result of measuring the free acid concentration, the value in terms of HF based on (2a-Li) was 1700 ppm by mass.
- Example 2-1 To test solution D (100 g), thionyl chloride (0.36 g, 3.0 mmol, 1.2 eq. With respect to 2000 mass ppm of free acid converted to HF) was added, and the pressure was reduced to 40 ° C. and pressure 50 to 80 kPa. For 3 hours. The pressure was returned to atmospheric pressure with nitrogen, and DMC corresponding to the weight reduced by distillation during the operation was added to return the initial test solution weight to 100 g. Thereafter, concentration under reduced pressure was performed at a temperature of 20 to 40 ° C., and 25 g of DMC was distilled off. As a result of measuring the free acid concentration, the value in terms of HF based on (2a-Li) was less than 100 mass ppm.
- Example 2-2 To test solution E (100 g), thionyl chloride (0.59 g, 5.0 mmol, 2.0 eq. With respect to 2000 mass ppm of free acid converted to HF) was added, and the pressure was reduced to 40 ° C. and pressure 50 to 80 kPa. For 3 hours. The pressure was returned to atmospheric pressure with nitrogen, and DMC corresponding to the weight reduced by distillation during the operation was added to return the initial test solution weight to 100 g. Thereafter, concentration under reduced pressure was performed at a temperature of 20 to 40 ° C., and 25 g of DMC was distilled off. As a result of measuring the free acid concentration, the value in terms of HF based on (2a-Li) was less than 100 mass ppm.
- Example 2-3 Except that the test solution used was changed to F and DMC was changed to DEC, the results were processed in the same procedure as in Example 2-1. As a result, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass. It was.
- Example 2-4 As a result of processing in the same procedure as in Example 2-2 except that the test solution used was changed to G and DMC was changed to DEC, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass. It was.
- Example 2-5 Except that the test solution used was changed to H and DMC was changed to THF, the same procedure as in Example 2-1 was performed. As a result, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass. It was.
- Example 2-6 Except that the test solution used was changed to I and DMC was changed to THF, the same procedure as in Example 2-2 was performed. As a result, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass. It was.
- Example 2-7 As a result of performing the same procedure as in Example 2-1, except that the test solution to be used was J and DMC was changed to AcOEt, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass. It was.
- Example 2-8 As a result of processing in the same procedure as Example 2-2 except that the test solution used was changed to K and DMC was changed to AcOEt, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass. It was.
- Example 2-9 As a result of processing in the same procedure as in Example 2-1, except that the test solution used was changed to L and DMC was changed to CH 3 CN, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass. It became.
- Example 2-10 Except that the test solution used was changed to M and DMC was changed to CH 3 CN, the treatment was performed in the same procedure as in Example 2-2. As a result, the free acid concentration (the same HF equivalent value as above) was 100 ppm by mass. became.
- Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-5, and Examples 2-1 to 2-10 are shown in Table 2.
- SOCl 2 represents thionyl chloride and AcCl represents acetyl chloride.
- Example 1-1 The treatment with 1.2 molar equivalents of thionyl chloride at 25 ° C. for 6 hours reduced the free acid to 200 mass ppm (Example 1-1), and the temperature was further raised to 40 ° C. to reduce the free acid to less than 100 mass ppm. (Example 1-2). Further, the treatment with thionyl chloride was carried out under reduced pressure, or nitrogen was introduced to improve the rate of liberated acid, and the free acid became less than 100 ppm by mass at 40 ° C. for 3 hours (Example 1 3, 1-4).
- the free acid concentration is the same 2000 mass ppm, but when the main component is oxalic acid, the residual free acid concentration is reduced to less than 100 ppm under conditions of 1.2 molar equivalents of thionyl chloride and 3 hours at 40 ° C.
- the main component having a free acid concentration of 2000 mass ppm is HF
- the free acid is only reduced to 600 mass ppm under the conditions of 1.2 molar equivalents of thionyl chloride at 40 ° C. for 3 hours.
- Example 1-6 By increasing thionyl chloride to 2.0 molar equivalents, the free acid can be increased to 200 ppm by mass (Example 1-7). Further, by using 2.0 molar equivalents of thionyl chloride and treating under reduced pressure, the free acid can be increased to 100 masses. It could be reduced to less than ppm (Example 1-8).
- Example 3-1 As a result of carrying out the treatment in the same procedure as in Example 1-4 except that the test solution to be used was changed to N, the free acid concentration (the same HF equivalent value as above) was less than 100 ppm by mass.
- Example 3-2 As a result of carrying out the treatment by the same procedure as in Example 1-8 except that the test solution to be used was changed to O, the free acid concentration (the same HF equivalent value as described above) was less than 100 mass ppm.
- Example 3-3 As a result of performing the treatment in the same procedure as in Example 1-8 except that the test solution used was changed to P, the free acid concentration (the same HF equivalent value as described above) was less than 100 mass ppm.
- Example 3-4 As a result of carrying out the treatment by the same procedure as in Example 1-8 except that the test solution used was changed to Q, the free acid concentration (the same HF equivalent value as described above) was less than 100 mass ppm.
- Example 3-5 As a result of performing the treatment in the same procedure as in Example 1-8 except that the test solution used was changed to R, the free acid concentration (the same HF equivalent value as described above) was less than 100 mass ppm.
- Example 3-6 As a result of performing the same procedure as in Example 1-8 except that the test solution used was changed to S, the free acid concentration (the same HF equivalent value as described above) was less than 100 ppm by mass.
- Example 3-7 As a result of performing the treatment in the same procedure as in Example 1-8 except that the test solution used was changed to T, the free acid concentration (the same HF equivalent value as described above) was less than 100 mass ppm.
- Example 4-1 Treatment with the same procedure as in Example 1-4 except that acetyl chloride (0.24 g, 3.0 mmol, 1.2 eq. Relative to the free acid) was used instead of thionyl chloride.
- acetyl chloride (0.24 g, 3.0 mmol, 1.2 eq. Relative to the free acid) was used instead of thionyl chloride.
- the same HF conversion value as above was less than 100 mass ppm.
- Example 4-2 Treatment with the same procedure as in Example 1-8 except that acetyl chloride (0.39 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride.
- acetyl chloride (0.39 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride.
- the same HF conversion value as above was less than 100 mass ppm.
- Example 4-3 Treatment with the same procedure as in Example 1-4 except that oxalyl chloride (0.38 g, 3.0 mmol, 1.2 eq. With respect to the free acid) was used instead of thionyl chloride.
- oxalyl chloride (0.38 g, 3.0 mmol, 1.2 eq. With respect to the free acid) was used instead of thionyl chloride.
- the same HF conversion value as above was less than 100 mass ppm.
- Example 4-4 Treatment with the same procedure as in Example 1-8 except that oxalyl chloride (0.63 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride.
- oxalyl chloride (0.63 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride.
- the same HF equivalent value as above was 150 ppm by mass.
- Example 4-5 Treatment with the same procedure as in Example 1-4 except that methyl chloroformate (0.28 g, 3.0 mmol, 1.2 eq. Relative to the free acid) was used instead of thionyl chloride.
- the concentration (the same HF equivalent value as described above) was less than 100 ppm by mass.
- Example 4-6 Treatment with the same procedure as in Example 1-8 except that methyl chloroformate (0.47 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride.
- the concentration (the same HF equivalent value as described above) was 100 mass ppm.
- Example 4-7 As a result of treatment in the same procedure as Example 1-4, except that trifluoromethanesulfonic acid chloride (0.51 g, 3.0 mmol, 1.2 eq. Relative to the free acid) was used instead of thionyl chloride,
- the free acid concentration (the same HF equivalent value as described above) was less than 100 ppm by mass.
- Example 4-8 As a result of treatment in the same procedure as Example 1-8, except that trifluoromethanesulfonic acid chloride (0.84 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride, The free acid concentration (same HF equivalent value as above) was 100 mass ppm.
- Example 4-9 As a result of treatment in the same procedure as in Example 1-4, except that methanesulfonic acid chloride (0.34 g, 3.0 mmol, 1.2 eq. With respect to the free acid) was used instead of thionyl chloride, the result was free.
- the acid concentration (the same HF equivalent value as described above) was less than 100 ppm by mass.
- Example 4-10 As a result of treatment in the same procedure as in Example 1-8, except that methanesulfonic acid chloride (0.57 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride, the result was free.
- the acid concentration (the same HF equivalent value as described above) was 100 mass ppm.
- Example 4-11 The treatment with the same procedure as in Example 1-4 except that trimethylsilyl chloride (0.33 g, 3.0 mmol, 1.2 eq. With respect to the free acid) was used instead of thionyl chloride. (The same HF equivalent value as described above) was 1000 ppm by mass.
- Example 4-12 Treatment with the same procedure as in Example 1-8 except that trimethylsilyl chloride (0.54 g, 5.0 mmol, 2.0 eq. Relative to the free acid) was used instead of thionyl chloride. (The same HF equivalent value as described above) was 100 mass ppm.
- Examples 4-1 to 4-12 are shown in Table 4.
- AcCl represents acetyl chloride
- (COCl) 2 represents oxalyl chloride
- ClCO 2 Me represents methyl chloroformate
- TfCl represents trifluoromethanesulfonic acid chloride
- MsCl represents methanesulfonic acid chloride
- TMSCl trimethylsilyl chloride.
- the residual free acid concentration after generation can be reduced to 100 mass ppm by reducing the pressure during the reaction with the purification agent, and the pressure reduction is reduced during the reaction with the purification agent.
- the residual free acid concentration could be greatly reduced as compared with the case where the test was not performed (Comparison between Examples 4-1 and 4-2 and Comparative Examples 1-4 and 1-5).
- the concentration of free acid after treatment was less than 100 ppm by mass when using AcCl, whereas 100 to 150 mass by using (COCl) 2 , ClCO 2 Me, TfCl, MsCl, and TMSCl. It was ppm, and a slight decrease in the effect was confirmed.
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Abstract
La présente invention concerne un procédé de purification d'une solution d'électrolyte est caractérisé par : une étape dans laquelle un agent de purification est ajouté dans une solution qui est obtenue par dissolution d'un électrolyte dans un solvant non aqueux et contient au moins du fluorure d'hydrogène en tant qu'impureté, de sorte que l'impureté réagisse avec l'agent de purification ; et une étape dans laquelle l'impureté est éliminée par retrait du produit de réaction et de l'agent de purification n'ayant pas réagi. Le chlorure de thionyle est utilisé en tant qu'agent de purification. De plus, un chlorure d'acide carboxylique, un chlorure d'acide sulfonique, un chlorure d'acide sulfinique, le chlorure de silicium ou un anhydride d'acide carboxylique peut être utilisé en tant qu'agent de purification, et dans ce cas, le produit de réaction est extrait du système de réaction pendant la réaction entre le fluorure d'hydrogène et l'agent de purification. Selon ce procédé de purification, le fluorure d'hydrogène dans une solution d'électrolyte peut être éliminé à une concentration faible par des procédés simples en un temps plus court par rapport à des procédés conventionnels.
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CN110911755A (zh) * | 2019-10-24 | 2020-03-24 | 东莞东阳光科研发有限公司 | 一种锂盐的除酸方法、非水电解液和电池 |
CN113165875A (zh) * | 2018-11-16 | 2021-07-23 | 麻省固能控股有限公司 | 纯化的双(氟磺酰基)亚胺锂(LiFSI)产物、纯化粗制LiFSI的方法以及纯化的LiFSI产物的用途 |
CN114684856A (zh) * | 2022-03-07 | 2022-07-01 | 中船(邯郸)派瑞特种气体股份有限公司 | 一种去除六氟化钨中氟化氢的方法及装置 |
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JP2018536645A (ja) | 2015-10-28 | 2018-12-13 | 味の素株式会社 | 免疫賦活剤 |
JP2021057100A (ja) * | 2018-01-24 | 2021-04-08 | セントラル硝子株式会社 | 非水電解液電池用電解液、及びこれを用いた非水電解液電池 |
CN116282084A (zh) * | 2023-03-22 | 2023-06-23 | 哈工大机器人集团(杭州湾)国际创新研究院 | 一种在全卤有机化合物中制备六氟磷酸钠的方法 |
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CN113165875A (zh) * | 2018-11-16 | 2021-07-23 | 麻省固能控股有限公司 | 纯化的双(氟磺酰基)亚胺锂(LiFSI)产物、纯化粗制LiFSI的方法以及纯化的LiFSI产物的用途 |
CN110911755A (zh) * | 2019-10-24 | 2020-03-24 | 东莞东阳光科研发有限公司 | 一种锂盐的除酸方法、非水电解液和电池 |
CN114684856A (zh) * | 2022-03-07 | 2022-07-01 | 中船(邯郸)派瑞特种气体股份有限公司 | 一种去除六氟化钨中氟化氢的方法及装置 |
CN114684856B (zh) * | 2022-03-07 | 2024-01-23 | 中船(邯郸)派瑞特种气体股份有限公司 | 一种去除六氟化钨中氟化氢的方法及装置 |
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