CN107973822A - A kind of phosphorus nitrile compounds and its synthetic method and application - Google Patents
A kind of phosphorus nitrile compounds and its synthetic method and application Download PDFInfo
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- CN107973822A CN107973822A CN201610936342.3A CN201610936342A CN107973822A CN 107973822 A CN107973822 A CN 107973822A CN 201610936342 A CN201610936342 A CN 201610936342A CN 107973822 A CN107973822 A CN 107973822A
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- China
- Prior art keywords
- carbonate
- electrolyte
- lithium
- compound
- formula
- Prior art date
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- -1 phosphorus nitrile compounds Chemical class 0.000 title claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 5
- 239000011574 phosphorus Substances 0.000 title claims abstract description 5
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical group 0.000 claims abstract description 32
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 20
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 19
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- PWORGPNOUCYYCW-UHFFFAOYSA-N [SH2]=N.[Cl] Chemical class [SH2]=N.[Cl] PWORGPNOUCYYCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N N,N-Diethylethanamine Substances CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000013538 functional additive Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 6
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 150000008053 sultones Chemical class 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- XJGIGXYFHBOWDQ-UHFFFAOYSA-N B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] Chemical class B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] XJGIGXYFHBOWDQ-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910005948 SO2Cl Inorganic materials 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- IDGCBXSROJHVOG-UHFFFAOYSA-N [Li].[SH2]=N.[F] Chemical compound [Li].[SH2]=N.[F] IDGCBXSROJHVOG-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 11
- 229910001290 LiPF6 Inorganic materials 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of phosphonitrile class compounds and methods and application, belong to technical field of electrolyte.The phosphorus nitrile compounds are containing the double oroalkane sulfonyl imines of phosphonitrile, shown in general structure such as formula (I), the compound structure is novel, synthetic method is simple and practicable, for having preferable anti-flammability in electrolyte, the battery formed using the electrolyte containing the compound shows excellent cycle performance, fire resistance and high-temperature behavior.
Description
Technical field
The present invention relates to the technical field of electrolyte of lithium ion battery, and in particular to a kind of electrolyte is fire-retardant with phosphonitrile class
Agent, synthetic method and its application.
Background technology
Lithium ion battery have the advantages that, high voltage higher than energy, recycle often, storage time it is long, not only exist
On portable electric appts, as mobile phone, DV and laptop computer are used widely, and it is widely used in
In terms of the large and medium-sized electrical equipment such as electric automobile, energy storage, electric bicycle and electric tool.With lithium ion battery market
Constantly expand, safety problem has become major obstacle of the lithium battery applications on electric car, due to the electrolysis of lithium ion battery
Liquid is usually to be made of organic solvent, and these solvents are mostly combustibles, if battery improper use, it is possible to cause and emit
Cigarette, on fire, burning, or even explosion, for these hidden danger, researcher, which takes certain methods, improves lithium battery.Mesh
Before, flame-retardant additive is added into electrolyte and has become one of main method of solution lithium ion battery security.It is common
Fire retardant has the compounds such as phosphate, phosphite ester, halogenated phosphate, halogenated acid phosphate and halo ether compound, such as,
Patent CN103779608 makes electrolyte have good fire resistance by adding tributyl phosphate TBP.Although these are fire-retardant
The flame retardant effect of agent is preferable, but phosphate to graphite cathode destroy it is larger, while can reduce electrolyte ionic conductivity and
Invertibity of battery etc..Therefore, at present there is an urgent need to a kind of good flame retardation effect, self stability is good, and can effectively improve electricity
The fire retardant of the high safety of the chemical property in pond.
The content of the invention
In view of the above-mentioned problems, on the one hand technical scheme provides a kind of phosphorus nitrile compounds, its structure such as formula (I)
It is shown：
Wherein, R1-R5It is each independently bromine or fluorine；Each R6It independently is fluorine or C1-C9Perfluoroalkyl.
In certain embodiments, R1-R5For fluorine.
In certain embodiments, each R6It independently is F, CF3, CF3CF2, CF3CF2CF2Or CF3CF2CF2CF2。
In certain embodiments, R1-R5For fluorine；R6For F；I.e. the compounds of this invention is compound shown in formula (II)：
In certain embodiments, R1-R5For fluorine；R6For CF3；I.e. the compounds of this invention is compound shown in formula (IV)：
Another aspect of the present invention is to provide the electrolyte prepared using formula (I) compound.
In certain embodiments, the electrolyte that formula (I) compound is prepared, it is characterised in that further include non-aqueous organic
Solvent, electrolyte lithium salt and other functional additives.
In certain embodiments, the electrolyte that formula (I) compound is prepared, it is characterised in that in the electrolyte, formula
(I) compound accounts for 3~15%.
In certain embodiments, in the electrolyte that formula (I) compound is prepared, the weight hundred shared by formula (I) compound
Divide than being 5%.
In certain embodiments, the non-aqueous organic solvent includes cyclic carbonate and linear carbonate, in the electrolytic solution
Account for 75~90%；The linear carbonate for dimethyl carbonate (DMC), diethyl carbonate (DEC),
Methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl acetate (EA), methyl acetate (MA), one kind in butyl acetate or
Numerous compositions.
In certain embodiments, the non-aqueous organic solvent accounts for 75% in the electrolytic solution.
In certain embodiments, in the non-aqueous organic solvent, cyclic carbonate is ethylene carbonate (EC), carbonic acid third
One kind or its combination in enester (PC)；Linear carbonate is dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate
Two or more combination in ester (EMC).
In certain embodiments, the non-aqueous organic solvent is ethylene carbonate (EC), dimethyl carbonate (DMC), carbon
Sour methyl ethyl ester (EMC) and the combination of propene carbonate (PC).
In certain embodiments, ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and carbonic acid third
The mass ratio of enester (PC) is 3：4：2：1.
In certain embodiments, the percentage by weight of the electrolyte lithium salt in the electrolytic solution is 5%~20%, described
Lithium salts be selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4), di-oxalate lithium borate
(LiBOB), double fluorine sulfimide lithiums (LiFSI), bis trifluoromethyl sulfimide lithium (LiTFSI) and double fluorine Lithium bis (oxalate) borates
(LiODFB) one or more combinations in.
In certain embodiments, the electrolyte lithium salt is lithium hexafluoro phosphate (LiPF6)。
In certain embodiments, the percentage by weight of the electrolyte lithium salt in the electrolytic solution be preferably 10%~
20%.
In certain embodiments, the percentage by weight of the electrolyte lithium salt in the electrolytic solution is preferably 15%.
In certain embodiments, lithium hexafluoro phosphate LiPF6Percentage by weight be preferably 15%.
In certain embodiments, other described functional additives account for 3 in the electrolytic solution~
8%；Other described functional additives are selected from vinylene carbonate (VC), ethylene sulfite (ES), fluoro ethylene carbonate
Ester (FEC), vinylethylene carbonate (VEC), biphenyl (BP), cyclohexyl benzene (CHB), tert-butyl benzene (TBB), succinonitrile (SN),
Glutaronitrile (GN), adiponitrile (AND), the third sultone of 1,3- (PS), Isosorbide-5-Nitrae-fourth sultone (BS), glycol sulfite (GS), third
Four or more combination in alkenyl -1,3- sultones (PES).
In certain embodiments, other described functional additives are vinylene carbonate (VC), cyclohexyl benzene
(CHB), the combination of succinonitrile (SN) and the third sultone of 1,3- (PS).
In certain embodiments, vinylene carbonate (VC), in the third sulphur of cyclohexyl benzene (CHB), succinonitrile (SN) and 1,3-
Shared percentage by weight is respectively 1.0%, 1.0%, 2.0% and 1.0% to ester (PS) in the electrolytic solution.
The third aspect of the present invention provides the preparation method of compound shown in formula (II)：
Its step includes：
(1) by sulfamic acid, thionyl chloride, chlorosulfonic acid heating reaction, double chlorine sulfimides are obtained；
(2) in organic solvent, double chlorine sulfimides and hexachlorocyclotriph,sphazene are reacted, obtains double chlorine sulfimide bases five
Three phosphonitrile of chlorine ring；
(3) under phase transfer catalyst effect, double three phosphonitriles of chlorine sulfimide base pentachloro- ring is fluorinated, obtain formula
(II) compound, distilation is up to sterling；
Specifically reaction equation is：
The fourth aspect of the present invention provides the preparation method of compound shown in formula (III)：
Its step includes：
A) at -60 DEG C, by R6SO2Cl is added dropwise to dissolved with excessive NH3Triethylamine solution in, react at room temperature 6h after heat back
Stream, (C is obtained after extraction, drying2H5)3NH(R6SO2)2N solution；
B) by gained (C2H5)3NH(R6SO2)2N solution enrichings sulfuric acid is acidified；
C) in organic solvent, product after acidifying and three phosphonitrile of hexafluoro ring, cyclopentene heating are reacted, vacuum distillation obtains
Formula (III) compound.
Specifically reaction equation is：
Wherein, each R6With implication as described in the present invention.
A kind of formula (I) compound provided by the invention, structure is novel, and synthesis is simple, and lithium ion is added to as fire retardant
In battery electrolyte, electrolyte flame-retardant and security can not only be improved, moreover it is possible to improve cycle performance and the high temperature storage of battery
Sustainability energy.
Term defines
The invention is intended to cover all replacement, modification and equivalent technical solutions, they are included in claim such as and determine
In the scope of the invention of justice.Those skilled in the art will appreciate that many and similar or equivalent method of the present invention and material
Material can be used in the practice present invention.The present invention is not limited to method of the present invention and material.Combined document, patent
With one or more of similar material it is different from the application or in the case of contradicting (term defined in including but not limited to,
Term application, described technology etc.), it is subject to the application.
It will further be appreciated that some features of the present invention, are clearly visible, are carried out in multiple independent embodiments
Description, but can also be provided in combination in single embodiment.Conversely, the various features of the present invention, for brevity,
It is described, but can also be provided individually or with any appropriate sub-portfolio in single embodiment.
Unless otherwise stated, all scientific and technical terminologies used in the present invention have with those skilled in the art of the invention's
It is generally understood that identical implication.All patents of the present invention and public publication are integrally incorporated this hair by reference
It is bright.
Unless otherwise stated, following definition used in the present invention should be applied.For purposes of the present invention, chemical element
With periodic table of elements CAS editions, and 1994 the 75th edition《Handbook of Chemistry and Physics》Unanimously.In addition, organic chemistry General Principle can
With reference to " Organic Chemistry ", Thomas Sorrell, University Science Books, Sausalito:
1999, and " March's Advanced Organic Chemistry " by Michael B.Smith and Jerry
March,John Wiley&Sons,New York:Description in 2007, entire contents are incorporated by reference into the present invention.
Term "comprising" or " comprising " are open language, that is, include the content specified by the present invention, but be not precluded from it
Content in terms of him.
In each several part of this specification, the substituent that the present invention discloses compound is disclosed according to radical species or scope.It is special
Do not point out, the present invention includes each independent sub-combinations thereof of each member of these radical species and scope.For example, term
“C1-C9Alkyl " refers in particular to individually disclosed methyl, ethyl, C3Alkyl, C4Alkyl, C5Alkyl, C6Alkyl, C7Alkyl, C8Alkyl and
C9Alkyl.
In each several part of the present invention, connect substituent is described.When the structure clearly needs linking group, for this
Markush variable cited by group is interpreted as linking group.If for example, the structure needs linking group and is directed to be somebody's turn to do
The Markush group definition of variable lists " alkyl ", then it should be understood that being somebody's turn to do the alkylidene group that " alkyl " represents connection.
Embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferable to carry out
Formula.It should be pointed out that for those skilled in the art on the basis of this innovation and creation design, some deformations for making and
Improve, belong to protection scope of the present invention.Raw material used can be obtained by commercial sources in embodiment.
The synthesis of formula (II) compound：
(1)N2Under protection, sulfamic acid (60g), thionyl chloride (198.5g), 120 DEG C of heating are added in four-hole boiling flask
6h is reacted, is cooled, adds chlorosulfonic acid (72.0g), 120 DEG C of the reaction was continued 12h, revolving removes thionyl chloride, obtains double chlorine
Sulfimide crude product.
(2) it is added dropwise in the anhydrous tetrahydrofuran solution containing hexachlorocyclotriph,sphazene (268.6g), is reacted at room temperature
6h, obtains double three phosphonitrile solution of chlorine sulfimide base pentachloro- ring.
(3) potassium fluoride (323.2g) and 4 bromide (5.0g) are added, 50 DEG C of heating reaction 6h, cold filtration, obtains
To five fluorine ring of double fluorine sulfimide bases, three phosphonitrile solution.
(4) the first 40 DEG C of decompressions (8mmHg) of obtained five fluorine ring of double fluorine sulfimide bases, three phosphonitrile solution are distilled off molten
Agent and impurity, rear 75 DEG C of decompressions (8mmHg) distillation obtain target product formula (II) compound (137.6g), and yield 54.3% is pure
Degree 99.8%.
GC-MS measure and nuclear-magnetism fluorine spectrum measure are carried out to five fluorine ring of the double fluorine sulfimide bases of products therefrom, three phosphonitrile, obtained
Following result：
GC-MS, m/z：410.9[M+1]+；
19F-NMR (acetone-D6, CCl3F, 600MHz)：δ1=51.4ppm (s), δ2=-49.5ppm (s), δ3=-
63.1ppm (d), δ4=-65.4ppm (d), δ5=-67.9ppm (d), δ6=-70.2ppm (d).
The synthesis of formula (IV) compound：
A) toward addition triethylamine (50.0g) in three-necked flask, -60 DEG C is cooled to, is passed through excessive NH3, it is added dropwise under low temperature
(183.2g)CF3SO2After Cl, 6h is reacted at room temperature, is heated to reflux 30min, volume ratio 1:1 methylene chloride/water extracts, organic phase
With anhydrous MgSO4It is dry, obtain (C2H5)3NH(CF3SO2)2N solution；
B) by gained (C2H5)3NH(CF3SO2)2Concentrated sulfuric acid acidifying is added dropwise in N solution, adjusts pH=2, and first air-distillation removes
Solvent, rear 118 DEG C of decompressions (5mmHg) distillation obtain double (trimethyl fluoride sulfonyl) imines (99.8g), yield 72%；
C) toward three phosphonitrile (106.0g) of addition hexafluoro ring and cyclopentene (24.2g) in acetonitrile solvent, by the double (fluoroforms of gained
Base sulphonyl) imines is added dropwise wherein, 45 DEG C of heating reaction 4h, first it is distilled off solvent and impurity for 60 DEG C, latter 130 DEG C
(5mmHg) is evaporated under reduced pressure, and obtains formula (IV) compound (147.3g), yield 81.3%, purity 99.7%.
GC-MS measure is carried out to five fluorine ring of double (trimethyl fluoride sulfonyl) imido grpups of products therefrom, three phosphonitrile and nuclear-magnetism fluorine spectrum is surveyed
It is fixed, obtain following result：
GC-MS, m/z：510.8[M+1]+；
19F-NMR (acetone-D6, CCl3F, 600MHz)：δ1=-78.9ppm (s), δ2=-49.7ppm (s), δ3=-
63.5ppm (d), δ4=-65.8ppm (d), δ5=-68.5ppm (d), δ6=-70.8ppm (d).
Comparative example 1：
In glove box of the moisture less than 10ppm, by organic solvent according to ethylene carbonate (EC)：Dimethyl carbonate
(DMC)：Methyl ethyl carbonate (EMC)：Propene carbonate (PC)=3：4：2：1 mass ratio is uniformly mixed that (organic solvent accounts for electricity
The percentage for solving liquid gross weight is 80%), to add 15% electrolyte lithium salt (LiPF6), then sequentially add 1% carbonic acid it is sub-
Vinyl acetate (VC), 1% cyclohexyl benzene (CHB), 2% succinonitrile (SN) and 1% 1,3-propane sultone (PS), are fully stirred
Mix uniformly mixed, that is, obtain the electrolyte of comparative example 1.
Comparative example 2：
In glove box of the moisture less than 10ppm, by organic solvent according to ethylene carbonate (EC)：Dimethyl carbonate
(DMC)：Methyl ethyl carbonate (EMC)：Propene carbonate (PC)=3：4：2：1 mass ratio is uniformly mixed that (organic solvent accounts for electricity
The percentage for solving liquid gross weight is 75%), to add 15% electrolyte lithium salt (LiPF6), then sequentially add 1% carbonic acid it is sub-
Vinyl acetate (VC), 1% cyclohexyl benzene (CHB), 2% succinonitrile (SN), 1% 1,3-propane sultone (PS) and 5% 6
Three phosphonitrile of fluorine ring, is thoroughly mixed the electrolyte for uniformly, that is, obtaining comparative example 2.
Comparative example 3：
In glove box of the moisture less than 10ppm, by organic solvent according to ethylene carbonate (EC)：Dimethyl carbonate
(DMC)：Methyl ethyl carbonate (EMC)：Propene carbonate (PC)=3：4：2：1 mass ratio is uniformly mixed that (organic solvent accounts for electricity
The percentage for solving liquid gross weight is 75%), to add 15% electrolyte lithium salt (LiPF6), then sequentially add 1% carbonic acid it is sub-
Vinyl acetate (VC), 1% cyclohexyl benzene (CHB), 2% succinonitrile (SN), 1% 1,3-propane sultone (PS) and 5% 5
Three phosphonitrile of fluorine ethoxy basic ring, is thoroughly mixed the electrolyte for uniformly, that is, obtaining comparative example 3.
Comparative example 4：
By organic solvent according to ethylene carbonate (EC) in glove box of the moisture less than 10ppm：Dimethyl carbonate
(DMC)：Methyl ethyl carbonate (EMC)：Propene carbonate (PC)=3：4：2：1 mass ratio is uniformly mixed that (organic solvent accounts for electricity
The percentage for solving liquid gross weight is 75%), to add 15% electrolyte lithium salt (LiPF6), then sequentially add 1% carbonic acid it is sub-
Vinyl acetate (VC), 1% cyclohexyl benzene (CHB), 2% succinonitrile (SN), 1% 1,3-propane sultone (PS) and 5% 5
Three phosphonitrile lithium trifluoromethanesulp,onylimide of fluorine ring, is thoroughly mixed the electrolyte for uniformly, that is, obtaining comparative example 4.
Embodiment 1：
By organic solvent according to ethylene carbonate (EC) in glove box of the moisture less than 10ppm：Dimethyl carbonate
(DMC)：Methyl ethyl carbonate (EMC)：Propene carbonate (PC)=3：4：2：1 mass ratio is uniformly mixed that (organic solvent accounts for electricity
The percentage for solving liquid gross weight is 75%), to add 15% electrolyte lithium salt (LiPF6), then sequentially add 1% carbonic acid it is sub-
Vinyl acetate (VC), 1% cyclohexyl benzene (CHB), 2% succinonitrile (SN), 1% 1,3-propane sultone (PS) and 5% formula
(II) compound, is thoroughly mixed the electrolyte for uniformly, that is, obtaining embodiment 1.
Embodiment 2：
By organic solvent according to ethylene carbonate (EC) in glove box of the moisture less than 10ppm：Dimethyl carbonate (DMC：
Methyl ethyl carbonate (EMC)：Propene carbonate (PC)=3：4：2：1 mass ratio is uniformly mixed that (it is total that organic solvent accounts for electrolyte
The percentage of weight is 75%), to add 15% electrolyte lithium salt (LiPF6), then sequentially add 1% vinylene carbonate
(VC), 1% cyclohexyl benzene (CHB), 2% succinonitrile (SN), 1% 1,3-propane sultone (PS) and 5% formula (IV) are changed
Compound, is thoroughly mixed the electrolyte for uniformly, that is, obtaining embodiment 2.
The mass fraction of each component, see the table below one in comparative example 1~4 and embodiment 1~2：
Table one
Gained electrolyte is subjected to following experiment test：
The 1st, the electrolyte that comparative example 1~4 and embodiment 1~2 are prepared is injected into the power of same batch and same model
In battery, the cycle performance test experiments that battery carries out 1C in 0~4.2V under normal temperature environment are tested, obtain normal temperature circulation 1000 times
Rear capacity retention ratio and the front and rear cell thickness expansion rate of circulation.
2nd, the electrolyte that comparative example 1~4 and embodiment 1~2 are prepared is done into combustion testing, obtains comparative example and embodiment electricity
Solve the flammability results of liquid.
The 3rd, the electrolyte that comparative example 1~4 and embodiment 1~2 are prepared is injected into the power of same batch and same model
In battery, the capacity retention ratio and cell expansion rate of their batteries after 85 DEG C of high-temperature storage 7 days are tested.
Test result such as following table two above：
Table two
As seen from the above table, the 1C of embodiment 1 and embodiment 2,1000 discharge capacitances be substantially better than comparative example 1~
4, and cell thickness expansion rate is relatively low, and self-extinguishing time is significantly shorter than comparative example, and flame retardant effect is obvious.In 85 DEG C of storages of high temperature
After 7 days, embodiment 1 and 2 thickness swelling of embodiment are significant lower, and capacity retention ratio is higher, and performance is more stable.In conclusion
The battery prepared with the application method electrolyte, has superior cycle life, excellent anti-flammability and can show at high temperature
Go out excellent battery performance.
Claims (9)
- A kind of 1. phosphorus nitrile compounds shown in formula (I)：Wherein, R1-R5It is each independently bromine or fluorine；Each R6It independently is fluorine or C1-C9Perfluoroalkyl.
- 2. compound according to claim 1, wherein, each R6It independently is F, CF3, CF3CF2, CF3CF2CF2Or CF3CF2CF2CF2。
- 3. a kind of electrolyte, including non-aqueous organic solvent, electrolyte lithium salt and other functional additives, it is characterised in that also Including the compound described in claim 1 or 2.
- 4. electrolyte according to claim 3, it is characterised in that in the electrolyte, the weight shared by formula (I) compound Percentage is 3~15%.
- 5. electrolyte according to claim 3, it is characterised in that the non-aqueous organic solvent includes cyclic carbonate and chain Shape carbonic ester, accounts for 75%~90% in the electrolytic solution；The linear carbonate for dimethyl carbonate, One or more combinations in diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl acetate, methyl acetate, butyl acetate Thing；The cyclic carbonate is ethylene carbonate, one kind in propene carbonate or its combination.
- 6. electrolyte according to claim 3, it is characterised in that the weight hundred of the electrolyte lithium salt in the electrolytic solution Point ratio is 5%~20%, and the lithium salts is selected from lithium hexafluoro phosphate, lithium perchlorate, LiBF4, di-oxalate lithium borate, double One or more combinations in fluorine sulfimide lithium, bis trifluoromethyl sulfimide lithium and double fluorine Lithium bis (oxalate) borates.
- 7. electrolyte according to claim 3, it is characterised in that other described functional additives institute in the electrolytic solution The percentage by weight accounted for is 3~8%；Other described functional additives are selected from vinylene carbonate, ethylene sulfite, fluorine For ethylene carbonate, vinylethylene carbonate, biphenyl, cyclohexyl benzene, tert-butyl benzene, succinonitrile, glutaronitrile, adiponitrile, 1,3- Four or more combination in third sultone, 1,4- fourths sultone, glycol sulfite, acrylic -1,3- sultones.
- 8. the preparation method of compound shown in a kind of formula (II),Its step includes：(1) by sulfamic acid, thionyl chloride, chlorosulfonic acid heating reaction, double chlorine sulfimides are obtained；(2) in organic solvent, double chlorine sulfimides and hexachlorocyclotriph,sphazene are reacted, obtains double chlorine sulfimide base pentachloro- rings Three phosphonitriles；(3) under phase transfer catalyst effect, double three phosphonitriles of chlorine sulfimide base pentachloro- ring are fluorinated, obtain formula (II) change Compound, distilation is up to sterling；Specifically reaction equation is：
- 9. the preparation method of compound shown in a kind of formula (III),Its step includes：A) at -60 DEG C, by R6SO2Cl is added dropwise to dissolved with excessive NH3Triethylamine solution in, react at room temperature 6h after be heated to reflux, extract Take, obtain (C after drying2H5)3NH(R6SO2)2N solution；B) by gained (C2H5)3NH(R6SO2)2N solution enrichings sulfuric acid is acidified；C) in organic solvent, product after acidifying and three phosphonitrile of hexafluoro ring, cyclopentene heating are reacted, vacuum distillation obtains formula (III) compound；Specifically reaction equation is：
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