TW201420552A - 製備雙（氟磺醯基）醯亞胺鋰或鈉的方法 - Google Patents
製備雙（氟磺醯基）醯亞胺鋰或鈉的方法 Download PDFInfo
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- TW201420552A TW201420552A TW103103873A TW103103873A TW201420552A TW 201420552 A TW201420552 A TW 201420552A TW 103103873 A TW103103873 A TW 103103873A TW 103103873 A TW103103873 A TW 103103873A TW 201420552 A TW201420552 A TW 201420552A
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- Prior art keywords
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- formula
- reaction
- lithium
- salt
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 150000003949 imides Chemical class 0.000 title abstract 2
- 239000011734 sodium Substances 0.000 title description 15
- 229910052708 sodium Inorganic materials 0.000 title description 10
- 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 title description 9
- -1 sulphonato Chemical class 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 229910001414 potassium ion Inorganic materials 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 229910001417 caesium ion Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 239000002253 acid Substances 0.000 abstract description 17
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 15
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000003682 fluorination reaction Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 229910010941 LiFSI Inorganic materials 0.000 description 8
- 125000001309 chloro group Chemical group Cl* 0.000 description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 8
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000004060 quinone imines Chemical class 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000012025 fluorinating agent Substances 0.000 description 6
- 230000000269 nucleophilic effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 6
- QYMKJDBPTYZRRF-UHFFFAOYSA-N FS(=O)(=O)[Ru]S(=O)(=O)F Chemical compound FS(=O)(=O)[Ru]S(=O)(=O)F QYMKJDBPTYZRRF-UHFFFAOYSA-N 0.000 description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 229910021201 NaFSI Inorganic materials 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 4
- ZPWMKTLKAVZWCB-UHFFFAOYSA-N sulfo carbamimidate Chemical compound NC(=N)OS(O)(=O)=O ZPWMKTLKAVZWCB-UHFFFAOYSA-N 0.000 description 4
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 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 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000012320 chlorinating reagent Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- XJTOEJFGOWXJHG-UHFFFAOYSA-N O=S(Cl)([Ru]S(Cl)(=O)=O)=O Chemical class O=S(Cl)([Ru]S(Cl)(=O)=O)=O XJTOEJFGOWXJHG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 2
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 2
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 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 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Chemical class 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- CNCOVVWFWVPEMA-UHFFFAOYSA-N sulfanyl hydrogen sulfate Chemical compound OS(=O)(=O)OS CNCOVVWFWVPEMA-UHFFFAOYSA-N 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YECOTGLJPABYBJ-UHFFFAOYSA-N FC(S(=O)(=O)C=1C(=C2C(C(=O)NC2=O)=CC1)S(=O)(=O)C(F)(F)F)(F)F.[Li] Chemical compound FC(S(=O)(=O)C=1C(=C2C(C(=O)NC2=O)=CC1)S(=O)(=O)C(F)(F)F)(F)F.[Li] YECOTGLJPABYBJ-UHFFFAOYSA-N 0.000 description 1
- DMPGTQROCHKGLL-UHFFFAOYSA-N FS(=O)(=O)C=1C(=C2C(C(=O)NC2=O)=CC1)S(=O)(=O)F.[Li] Chemical compound FS(=O)(=O)C=1C(=C2C(C(=O)NC2=O)=CC1)S(=O)(=O)F.[Li] DMPGTQROCHKGLL-UHFFFAOYSA-N 0.000 description 1
- OTDLRHDNXVYKPY-UHFFFAOYSA-N FS(=O)(=O)[Ru]S(=O)(=O)F.[Li] Chemical compound FS(=O)(=O)[Ru]S(=O)(=O)F.[Li] OTDLRHDNXVYKPY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HWCRBSLBZOJSOW-UHFFFAOYSA-N N-ethylethanamine trihydrofluoride Chemical compound F.F.F.C(C)NCC HWCRBSLBZOJSOW-UHFFFAOYSA-N 0.000 description 1
- ZRYIENGIGBAWCV-UHFFFAOYSA-N N=S(=O)(S(=O)(=O)Cl)S(=O)(=O)Cl Chemical class N=S(=O)(S(=O)(=O)Cl)S(=O)(=O)Cl ZRYIENGIGBAWCV-UHFFFAOYSA-N 0.000 description 1
- SHWCXIHZDQOSLX-UHFFFAOYSA-N NC(C(C(C(N)=O)=C1S(F)(=O)=O)=CC=C1S(F)(=O)=O)=O Chemical compound NC(C(C(C(N)=O)=C1S(F)(=O)=O)=CC=C1S(F)(=O)=O)=O SHWCXIHZDQOSLX-UHFFFAOYSA-N 0.000 description 1
- RRVPRGMPOKICMG-UHFFFAOYSA-N OP(=O)(S(=O)(=O)F)S(=O)(=O)F Chemical compound OP(=O)(S(=O)(=O)F)S(=O)(=O)F RRVPRGMPOKICMG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WXIUBYCJAAEOFL-UHFFFAOYSA-N [S].ClOCl Chemical compound [S].ClOCl WXIUBYCJAAEOFL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- DRWMGJONTCWKES-UHFFFAOYSA-N chloroform;hydrochloride Chemical compound Cl.ClC(Cl)Cl DRWMGJONTCWKES-UHFFFAOYSA-N 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PKNLWLCURZNADF-UHFFFAOYSA-N hex-5-enoyl chloride Chemical compound ClC(=O)CCCC=C PKNLWLCURZNADF-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- XXZNFWHGOMHWCO-UHFFFAOYSA-N n,n-diethylthiohydroxylamine Chemical compound CCN(S)CC XXZNFWHGOMHWCO-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YALHCTUQSQRCSX-UHFFFAOYSA-N sulfane sulfuric acid Chemical compound S.OS(O)(=O)=O YALHCTUQSQRCSX-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- QTJXVIKNLHZIKL-UHFFFAOYSA-N sulfur difluoride Chemical compound FSF QTJXVIKNLHZIKL-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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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- 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
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Abstract
本發明係關於製備式(III)之雙(磺酸根基)醯亞胺鹽的方法：(III) (SO3-)-N--(SO3-)3C+其中C+代表一價陽離子，該方法包括下式(I)之醯胺基硫酸與式(II)之鹵基磺酸的反應：(I) (OH)-SO2-NH2 (II) (OH)-SO2-X 其中X代表鹵原子，且該方法包括與和陽離子C+形成之鹽的鹼之反應。本發明亦關於製備式(V)之雙(氟磺醯基)醯亞胺酸的方法：(V) F-(SO2)-NH-(SO2)-F 及關於製備式(VII)之雙(氟磺醯基)醯亞胺鋰鹽之方法：(VII) F-(SO2)-N--(SO2)-F Li+。
Description
本發明有關製備雙(氟磺醯基)醯亞胺鋰或鈉鹽的方法，以及製備用於雙(氟磺醯基)醯亞胺鋰或鈉的製備中之中間產物的方法，及如此製得之雙(氟磺醯基)醯亞胺鋰或鈉於電解質及鋰離子或鈉離子型電池組的製造中之用途。
鋰離子或鈉離子電池組至少包含負極、正極、隔板及電解質。電解質係由溶解於溶劑中之鋰或鈉鹽所組成，該溶劑通常為有機碳酸酯之混合物，以在黏性及介電常數之間具有良好折衷。
最廣泛使用的鹽類包括六氟磷酸鋰(LiPF6)，其具有許多所需要的特質，但展現出分解成氫氟酸氣體形式的缺點。此存在安全問題，特別是在私人交通工具即將使用鋰離子電池組的情況下。
已發展其他鹽，諸如LiTFSI(雙(三氟甲磺醯基)醯亞胺)鋰及LiFSI(雙(氟磺醯基)醯亞胺鋰)。該等
鹽展現出少許或無自發性分解，且水解方面比LiPF6更安定。然而，LiTFSI展現出對於鋁集電器具有腐蝕性，在LiFSI實例中無此情況。因此，LiFSI顯示出為LiPF6的可能替代物。
存在數種製造雙(氟磺醯基)醯亞胺鋰的已知合成途徑。該等途徑之一係由全氟磺酸與脲之反應所組成：此方面詳見文件WO 2010/113483。從該反應獲得之產物隨後分解於水中，且雙(氟磺醯基)醯亞胺係呈與四丁基銨之鹽的形式沉澱。然而，由於該合成途徑的整體產率非常低，其大規模生產不可行。
其他途徑包括令二氟硫化物與氨反應：此方面詳見文件WO 2010/113835。然而，該方法亦形成許多副產物，其需要昂貴之純化階段。
此外，文獻WO 2009/123328大致描述磺醯基醯亞胺化合物之製造。該文件特別描述介於醯胺基硫酸與亞硫醯氯之間的反應，然後與氯磺酸反應，以形成雙(氯磺醯基)醯亞胺，隨後對其進行氟化階段。然而，雙(氯磺醯基)醯亞胺為不安定化合物，其無法承受純化作用。為此，存在之雜質保留至氟化階段結束時，且使分離更加困難。
因此，真正需要發展使得能以較簡單方式及/或具有更佳產率獲得LiFSI或NaFSI的方法。
本發明首先係關於製備式(III)之雙(磺酸根基)醯亞胺鹽的方法：(III)(SO3 -)-N--(SO3 -)3C+其中C+代表一價陽離子，該方法包括下式(I)之醯胺基硫酸與式(II)之鹵基磺酸的反應：(I)(OH)-SO2-NH2 (II)(OH)-SO2-X其中X代表鹵原子，且該方法包括與和陽離子C+形成之鹽的鹼之反應。在C+為質子H+之情況下，基質為水。
根據一具體實例，X代表氯原子。
根據一具體實例，C+代表質子H+、鉀離子K+、鈉離子Na+、鋰離子Li+或銫離子Cs+，較佳為質子H+、Na+離子及鉀離子K+。
根據一具體實例，該方法包括式(I)之醯胺基硫酸與式(II)之鹵基磺酸於包含C+陽離子之非親核鹼存在下的反應，該非親核鹼較佳為碳酸鉀K2CO3或碳酸鈉Na2CO3。
根據另一具體實例，該方法包括式(I)之醯胺基硫酸與式(II)之鹵基磺酸於第一鹼存在下的反應，以提供式(IV)之雙(磺醯基)醯亞胺：(IV)(OH)-SO2-NH-SO2-(OH)然後式(IV)之雙(磺醯基)醯亞胺與和C+陽離子形成之鹽的第二鹼之反應，以製得式(III)之雙(磺酸根基)醯亞胺鹽。
根據一具體實例，該第一鹼為三乙胺，且第二鹼係選自氫氧化鉀、氫氧化鈉及碳酸鉀。
根據另一替代具體實例，該方法包括式(I)之醯胺基硫酸與式(II)之鹵基磺酸於氯化劑(諸如亞硫醯氯)存在下的反應，以在水解之後提供式(IV)之雙(磺醯基)醯亞胺。
根據一具體實例，該方法包括式(III)之雙(磺酸根基)醯亞胺鹽的純化階段，較佳係藉由從水或從極性溶劑(諸如醇)再結晶來進行。
本發明另一主旨為製備式(V)之雙(氟磺醯基)醯亞胺酸的方法：(V)F-(SO2)-NH-(SO2)-F包括如上述式(III)之雙(磺酸根基)醯亞胺鹽的製備，然後氟化該雙(磺酸根基)醯亞胺鹽。
根據一具體實例，該雙(磺酸根基)醯亞胺鹽之氟化反應包括雙(磺酸根基)醯亞胺鹽與氟化劑之反應，該氟化劑較佳係選自氟化氫、三氟化二乙胺基硫及四氟化硫。
根據另一具體實例，該雙(磺酸根基)醯亞胺鹽之氟化反應包括：(a)利用較佳係選自亞硫醯氯、五氯化磷、磷醯氯及草醯氯之氯化劑將該雙(磺酸根基)醯亞胺鹽氯化，以製得式(VI)之雙(氯磺醯基)醯亞胺鹽：(VI)Cl-(SO2)-N-(SO2)-Cl C+和然後(b)利用氟化劑將式(VI)之雙(氯磺醯基)醯亞胺鹽氟化，以製得式(V)之雙(氟磺醯基)醯亞胺
酸，該氟化劑較佳係選自氟化氫、三氟化二乙胺基硫、四氟化硫及氟化鹽，特別是氟化鋅。
本發明另一主旨為製備式(V)之雙(氟磺醯基)醯亞胺鋰或鈉鹽的方法：(VII)F-(SO2)-N--(SO2)-F M+其中M代表Li或Na，包括如上述式(V)之雙(氟磺醯基)醯亞胺酸的製備，然後使該雙(氟磺醯基)醯亞胺酸與鋰或鈉鹼反應。
本發明之非常特別的主旨為製備式(VII)之雙(氟磺醯基)醯亞胺鋰鹽之方法。
根據一具體實例，該鋰或鈉鹼係選自氫氧化鋰、氫氧化鈉、碳酸鋰或碳酸鈉。
本發明另一主旨係製造電解質之方法，其包括如上述式(VII)之雙(氟磺醯基)醯亞胺鹽的製備及將該雙(氟磺醯基)醯亞胺鹽溶解於溶劑中。
本發明另一主旨係製造電池組或電池組電池之方法，其包括如上述之電解質的製造，且將該電解質插於陽極與陰極之間。
本發明另一主旨係式(III)雙(磺酸根基)醯亞胺鹽：(III)(SO3 -)-N--(SO3 -)3C+其中C+代表一價陽離子。
根據一具體實例，C+代表H+離子或Na+離子或Li+離子或Cs+離子或K+離子，且較佳地為H+離子或Na+離子或
K+離子。
本發明另一主旨係式(VI)之雙(氯磺醯基)醯亞胺化合物(鹽或酸)。該化合物可在氟化階段(b)之前分離。
本發明使得可能克服當前技術的缺點。更特別的是提供可以更簡單之方式及/或較佳產率製得LiFSI或NaFSI之方法。
其係藉由發展雙(磺酸根基)醯亞胺及陽離子之三鹽的製備方法而完成，包括醯胺基硫酸與鹵基磺酸之反應且添加至少一種包含上述陽離子之鹽的鹼。
該雙(磺酸根基)醯亞胺三鹽可隨後用以製備雙(氟磺醯基)醯亞胺，使得可能製得LiFSI或NaFSI，此獲致比當前技術所提供之合成途律更佳之產率。
相較於文件WO 2009/123328，本發明方法包括雙(氯磺醯基)醯亞胺鹽(VI)之分離，因此使得可移除雜質，諸如在第一階段期間形成的殘留之氯磺酸衍生物。
本發明另一主旨為高純度雙(氟磺醯基)醯亞胺鋰或鈉。
現更詳細描述本發明且不對以下描述強加限制：本發明提供根據以下分成三部分之一般反應式之雙(氟磺醯基)醯亞胺鋰鹽的製備：1)(OH)-SO2-NH2+(OH)-SO2-X → (SO3 -)-N-(SO3 -)3C+
2)(SO3 -)-N--(SO3 -)3C+ → F-(SO2)-NH-(SO2)-F
3)F-(SO2)-NH-(SO2)-F → F-(SO2)-N--(SO2)-F M+
考慮兩種備擇形式作為該第一部分。第一備擇形式對應於下列反應式：(OH)-SO2-NH2+(OH)-SO2-X+zCxBy → (SO3 -)-N--(SO3 -)3C++z’By’Hx’+CX
在前述反應式中，(OH)-SO2-NH2為醯胺基硫酸，其化學式稱為(I)；(OH)-SO2-X為鹵基磺酸(X代表鹵原子)，其化學式稱為(II)；及CxBy為非親核鹼(即，無法藉由永久地添加至(OH)-SO2-X)而干擾反應的有機鹼，C+代表該鹼所形成的一價陽離子，及x、y、z、x’、y’及z’為整數或分數，使得乘積zx及乘積z’x’等於4。
三鹽(SO3 -)-N--(SO3 -)3C+之化學式稱為(III)。
較佳地，X代表氯。
C+代表例如鉀離子K+。CxBy代表例如碳酸鉀K2CO3。在該情況下，C代表鉀K，B代表CO3，x具有值2，y具有值1，z具有值2，x’具有值2，y’具有值1及z’具有值2。
或者，C+可代表例如鈉離子Na+，銫離子Cs+，鋰離子Li+或H+離子。
上述反應可例如在0至150℃(較佳為0至50℃，更佳為10至40℃，特別是15至30℃)之溫度下，且在大
氣壓力至高達15巴之壓力下進行。胺磺酸較佳為限量反應物，及鹵基磺酸(OH)-SO2-X可過量使用(1至3當量)。
第二備擇形式對應於下列反應式：(OH)-SO2-NH2+(OH)-SO2-X+B’ → (OH)-SO2-NH-SO2-(OH)+B’H+ X-
(OH)-SO2-NH-SO2-(OH)+z CxBy → (SO3 -)-N--(SO3 -)3C++z’By’Hx’
該反應式中，(OH)-SO2-NH-SO2-(OH)為雙(磺醯基)醯亞胺，其化學式稱為(IV)；X仍代表鹵原子；B’為親核或非親核鹼；CxBy為親核或非親核鹼，C+代表從該鹼形成之一價陽離子，及x、y、z、x’、y’及z’為整數或分數，使得乘積zx及乘積z’x’等於3。在上述反應式中，這兩階段為連續階段，且式(IV)之雙(磺醯基)醯亞胺未予分離。
在C+為質子H+之情況下，第二備擇形式只包括第一階段。
較佳地，X代表氯。
C+代表例如鉀離子K+。
CxBy代表例如氫氧化鉀(KOH)、氫氧化鈉(NaOH)或碳酸鉀(K2CO3)。
B’代表例如三乙胺(NEt3)。
上述反應式可例如在0至150℃(較佳為0至50℃，更佳為10至40℃，特別是15至30℃)之溫度下，且在
大氣壓力至15巴之壓力下進行。胺磺酸較佳為限量反應物，及鹵基磺酸(OH)-SO2-X可過量使用(1至3當量)。鹼B’亦用作反應溶劑，及鹼CxBy係過量添加直到獲得8至14之鹼性pH為止。
結束第一部分時，式(III)之化合物(三鹽或酸)較佳係經純化。此係因為三鹽(III)或酸較不溶於水，然而在反應期間形成的雜質在鹼性條件下非常容易溶解於水。純化作用亦可從其他極性溶劑(諸如醇)進行。
考慮兩種備擇形式作為該第二部分。該第一備擇形式包含氯化反應及然後氟化反應，然而該第二備擇形式包含直接氟化反應。
第一備擇形式對應於下列反應式：(SO3 -)-N--(SO3 -)3C++xA1 → Cl-(SO2)-N--(SO2)-Cl C++A2
Cl-(SO2)-N--(SO2)-Cl C++3HF → F-(SO2)-NH-(SO2)-F+2HCl+CF
該反應式中，F-(SO2)-NH-(SO2)-F為雙(氟磺醯基)醯亞胺酸，其化學式稱為(V)；A1代表氯化劑；A2通常代表氯化反應的一或多種產物；C+仍代表上述之一價陽離子；x為整數或分數；及Cl-(SO2)-N--(SO2)-Cl C+為雙(氯磺醯基)醯亞胺鹽，其化學式稱為(VI)。
A1可例如為亞硫醯氯SOCl2(x=1)，該情況下，若
C+為鉀離子，A2代表2KCl+2SO2。
A1亦可為五氯化磷(PCl5)、磷醯氯(POCl3)或草醯氯。
氯化反應可例如為在0至150℃之溫度下及在大氣壓力至高達15巴之壓力下進行。氯化劑較佳係過量使用，且通常作為溶劑。反應之溫度有利地在溶劑之沸點附近。例如，在亞硫醯氯之情況下，沸點在76℃附近，反應溫度因此為例如60至90℃，或從70至80℃。
至於氟化反應，後者可例如在0至350℃(較佳為0至50℃，更佳為10至40℃，特別是15至30℃)之溫度下，且在大氣壓力至15巴之壓力下進行。
亦可能使用其他氟化劑代替HF，諸如三氟化二乙胺基硫(DAST)或四氟化硫(SF4)，或者式CxFy之氟化物鹽，其中x及y為正整數且C為陽離子。例如，如文件WO 2009/123328中所述，CxFy可為氟化鋅ZnF2。
第二備擇形式對應於例如下列反應式：(SO3 -)-N--(SO3 -)3C++5HF → F-(SO2)-NH-(SO2)-F+2H2O+3CF
該反應式中，C+仍代表上述一價陽離子，例如K+。
該反應可例如在0至350℃(較佳為0至50℃，更佳為10至40℃，特別是15至30℃)之溫度下，且在大氣壓力至高達15巴之壓力下進行。氟化氫通常係過量使用。該反應在無溶劑之情況下進行。
可能使用其他氟化劑(諸如三氟化二乙胺基硫
(DAST)或四氟化硫(SF4))代替氟化氫。
由於此等氟化劑比氟化氫更具反應性，在相同壓力及溫度範圍內，其可以比氟化氫較少過量來使用。
雙(氟磺醯基)醯亞胺酸隨後經純化；在反應結束時，由於雜質不可溶或只稍微溶解於有機溶劑，故酸係使用有機溶劑自殘留固體萃取出。該有機溶劑較佳為碳酸二甲酯。
該第三部分對應於下列反應式：F-(SO2)-NH-(SO2)-F+MB → F-(SO2)-N--(SO2)-F M++BH
F-(SO2)-N--(SO2)-F M+為LiFSI或NaFSI，其化學式稱為(VII)。MB為鋰或鈉鹼，即呈從鋰陽離子Li+或鈉陽離子Na+及從陰離子B-形成之鹽形式的鹼。該鹼可例如為氫氧化鋰、氫氧化鈉、碳酸鋰或碳酸鈉。
該反應可例如在25℃至80℃之溫度下進行。鋰或鈉鹼係以1至1.5當量之比例使用，較佳係於水中，或亦於極性溶劑(諸如醇)中。
根據本發明，雙(氟磺醯基)醯亞胺鋰或鈉(MFSI)之純度較佳為至少等於99.5重量%，有利地為至少等於99.9重量%。
存在雙(磺酸根基)醯亞胺鹽中之雜質(如LiCl、LiF及FSO3Li或NaCl、NaF及FSO3Na)各較佳代表至多
1000ppm，且有利地至多為500ppm。
不論製備方法為何，FSO3Li較佳地代表至多5ppm。
根據本發明任何具體實例，雙(氟磺醯基)醯亞胺鋰或鈉(MFSI)較佳不含水分亦不含由週期表第11至15族及4至6族之陽離子(諸如Zn、Cu、Sn、Pb、Bi)的鹽所組成的雜質。由於該等雜質的電化學活性，其對於Li或Na離子電池組之容量具有負面影響。
如上述製備之MFSI可藉由溶解於適當溶劑中而用於電解質之製備。
例如，如文件J.Electrochemical Society(2011,158,A74-82)所述，LiFSI可1mol/l之濃度溶解於5：2：3(體積比)之碳酸乙二酯(EC)、碳酸二甲酯(DMC)及碳酸乙基甲酯(EMC)的混合物；此種電解質展現出非常良好之傳導性、良好之循環安定性及鋁之高於4.2V。
該電解質可藉由以本身為人習知之方式定位在陰極及陽極之間而隨後用於電池組或電池組電池的製造。
下列實施例說明但不限制本發明。
反應係在無溶劑下於乾燥圓底玻璃燒瓶中進行。將1.1ml之氯磺酸添加至1.61g之胺磺酸並攪拌之。然後，添加2ml之三乙胺。使反應混合物攪拌1天。藉由添加20ml之水來停止反應。然後，添加2.79g之氫氧化鉀。最終產物沉澱且藉由過濾收集，並以2×30ml之CH2Cl2清洗之。
將15.3g之三鹽添加至250ml之圓底燒瓶。隨後逐滴添加60ml之草醯氯，然後添加1ml之二甲基甲醯胺。該反應介質在回流下攪拌3小時，且該溶液變成黃色。在反應結束時，過濾該溶液，且製得白色固體(w=19.0g)，其包含經氯化之化合物及氯化鉀。
19.0g之雙(氯磺醯基)醯亞胺鉀及氯化鉀的混合物添加至800ml之熱壓器中。隨後在周圍溫度下添加20g之氟化氫。將該反應介質攪拌3小時。隨後藉由空氣流移除所放出之過量氟化氫及氯化氫。然後獲得金黃色的固體。
Claims (3)
- 一種雙(氟磺醯基)醯亞胺鋰或鈉，其純度至少等於99.5重量%，較佳係至少等於99.9重量%。
- 一種式(VI)之雙(氯磺醯基)醯亞胺鹽，(VI)Cl-(SO2)-N--(SO2)-Cl C+其中C+代表一價陽離子。
- 如申請專利範圍第2項之鹽，其中C+代表Na+離子或Li+離子或Cs+離子或K+離子，較佳為K+離子。
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| FR1252642A FR2975684B1 (fr) | 2011-05-24 | 2012-03-23 | Procede de preparation de bis(fluorosulfonyl)imidure de lithium ou sodium |
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| CN101654229B (zh) | 2009-09-04 | 2013-01-02 | 华中科技大学 | 一种制备含氟磺酰(磷酰)亚胺及其碱金属盐的方法 |
| EP2476666A4 (en) | 2009-09-04 | 2013-01-23 | Asahi Glass Co Ltd | METHOD FOR THE PRODUCTION OF BIS (SULFONYL) IMID AMMONIA SALTS, BIS (SULPHONYL) IMID AND BIS (SULFONYL) IMID LITHIUM SALTS |
| JP2011082033A (ja) | 2009-10-07 | 2011-04-21 | Mitsubishi Chemicals Corp | 非水系電解液二次電池モジュール |
| CN102405189B (zh) | 2009-11-27 | 2014-07-09 | 株式会社日本触媒 | 氟磺酰亚胺盐以及氟磺酰亚胺盐的制备方法 |
| PL2578533T3 (pl) | 2010-05-28 | 2019-07-31 | Nippon Shokubai Co., Ltd. | Sól metalu alkalicznego fluorosulfonyloimidu i sposób jej wytwarzania |
| US8828346B2 (en) * | 2011-03-08 | 2014-09-09 | Trinapco, Inc. | Method of making fluorosulfonylamine |
| FR2975694B1 (fr) * | 2011-05-24 | 2013-08-02 | Arkema France | Procede de preparation de bis(fluorosulfonyl)imidure de lithium |
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- 2011-05-24 FR FR1154490A patent/FR2975694B1/fr active Active
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