CN106976853A - A kind of preparation method of difluorophosphate - Google Patents
A kind of preparation method of difluorophosphate Download PDFInfo
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- CN106976853A CN106976853A CN201710252954.5A CN201710252954A CN106976853A CN 106976853 A CN106976853 A CN 106976853A CN 201710252954 A CN201710252954 A CN 201710252954A CN 106976853 A CN106976853 A CN 106976853A
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- Prior art keywords
- substituted
- alkyl
- unsubstituted
- reaction
- aryl
- Prior art date
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- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- 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 abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 42
- -1 C25 alkynes Chemical class 0.000 claims description 37
- 229910052736 halogen Inorganic materials 0.000 claims description 33
- 150000002367 halogens Chemical class 0.000 claims description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 28
- 239000000047 product Substances 0.000 description 21
- 239000012043 crude product Substances 0.000 description 18
- 150000004673 fluoride salts Chemical class 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000000725 suspension Substances 0.000 description 18
- 150000005686 dimethyl carbonates Chemical class 0.000 description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 238000010828 elution Methods 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- YSNLHLJYEBEKMC-UHFFFAOYSA-N P(O)(=O)(F)F.[Li] Chemical compound P(O)(=O)(F)F.[Li] YSNLHLJYEBEKMC-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- MSGYRGHIEBLFLX-UHFFFAOYSA-N F[P]F Chemical compound F[P]F MSGYRGHIEBLFLX-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000005017 substituted alkenyl group Chemical group 0.000 description 2
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004361 3,4,5-trifluorophenyl group Chemical group [H]C1=C(F)C(F)=C(F)C([H])=C1* 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- QTZBTBLHYPSFMG-UHFFFAOYSA-N 5-chloro-3-methylpyridin-2-amine Chemical compound CC1=CC(Cl)=CN=C1N QTZBTBLHYPSFMG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910004562 P2O3F4 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QCJJGGWWBPBHLS-UHFFFAOYSA-N [Li].P(O)(O)(=O)F Chemical compound [Li].P(O)(O)(=O)F QCJJGGWWBPBHLS-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 150000005682 diethyl carbonates Chemical class 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a kind of preparation method of difluorophosphate, including：By the compound reaction shown in lithium hexafluoro phosphate and formula (I), difluorophosphate is obtained.Compound reaction shown in lithium hexafluoro phosphate and formula (I) can be obtained yield and the high difluorophosphate of purity by the present invention.And the product separating-purifying prepared by the synthetic method of the present invention is easy, and technique is simple；It is adapted to large-scale production.
Description
Technical field
The present invention relates to energy-storage battery technical field, more particularly to a kind of preparation method of difluorophosphate.
Background technology
At present, the energy density of lithium ion battery is higher, is widely used in small-sized electronic product.Recently,
People expect that lithium ion battery is applied in electric automobile, energy storage device as electrokinetic cell.Therefore, lithium ion battery requires tool
There are high power capacity, long-life, high power forthright and the performance such as security.Electrolyte is commonly used in commercial li-ion battery：Solvent is carbonic acid
The isothrausmatic carbonic ester of vinyl acetate, propene carbonate, and the chain such as diethyl carbonate, dimethyl carbonate carbonic ester, solute is
LiPF6、LiBF4、LiClO4、LiCF3SO3、LiAsF6、LiCF3(CF2)3SO3Etc. the non-aqueous electrolyte prepared.Different groups
Into electrolyte can largely cause the difference on battery performance.The decomposition and side reaction of particularly electrolyte can significantly
Influence the problems such as battery life, self discharge.Therefore, it is above-mentioned to improve battery by attempting addition various additives in the electrolytic solution
The problem of existing.
Prior art discloses contain monofluorophosphoric acid lithium (Li2PO3) or diphosphonic acid lithium (LiPO F2F2) additive electrolysis
Liquid, the wherein additive can react with lithium and form diaphragm on negative or positive electrode surface, can effectively suppress electrolyte
Decomposed with caused by the contact of electrode material, so as to suppress self discharge and improve cycle life.It discloses from P2O3F4With gold
Category salt or ammonia react to manufacture diphosphonic acid lithium (LiPO2F2) method.But, the raw material P used in this method2O3F4Price is held high
It is expensive, and side reaction product needs separation and purification, so being used as electrolysis additive LiPO2F2Manufacture method is not suitable for work
Industry metaplasia is produced.
US2008-305402 and US2008/102376 are disclosed with a kind of carbonate compound from LiPF6Middle manufacture
LiPO2F2；EP-A-2065339 and W02008/111367 disclose how a kind of halide, the LiPF outside fluoride6With
Water manufactures LiPF6And LiPO2F2Mixture.The salt mixture of generation be dissolved in non-proton solvent and be used as lithium from
The electrolyte of sub- battery.However, above method is technically difficult, low yield and technique is more complicated and reactant impurity
More, purification difficulty is big, therefore is not suitable for extensive manufacture.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of difluorophosphate, this hair
The preparation method yield of the difluorophosphate of bright offer is high, purity is high, technique is simple.
The invention provides a kind of preparation method of difluorophosphate, including：
By the compound reaction shown in lithium hexafluoro phosphate and formula (I), difluorophosphate is obtained；
Wherein, n=1~200；
X1~X2One or more in hydroxyl and halogen；
R1~R4The independent alkyl selected from C1~C50, C1~C50 cycloalkyl, C2~C50 alkenyl, C2~C50
The aryl of alkynyl, C6~C50.
It is preferred that, the X1~X2Independently selected from-OH ,-F or-Cl；The R1~R4Do not take independently selected from substitution or
C1~the C25 in generation alkyl, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C1~C25 cycloalkyl, take
Generation or unsubstituted C2~C25 alkenyl, substituted or unsubstituted C2~C25 alkynyl.
It is preferred that, the X1~X2Independently selected from-OH or-F；The R1~R4Independently selected from substituted or unsubstituted
C1~C20 alkyl, substituted or unsubstituted C6~C20 aryl, substituted or unsubstituted C1~C20 cycloalkyl, substitution or
The alkynyl of unsubstituted C2~C20 alkenyl, substituted or unsubstituted C2~C20.
It is preferred that, the substituent of the substitution alkyl is selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde
One or more in base, C1~C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；The substituted cycloalkyl
Substituent be selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C20 alkyl, C1~C20 ring
One or more in alkyl and C6~C20 aryl；The substituent of the substituted alkenyl be selected from halogen, hydroxyl, amino, nitro,
One or more in cyano group, carboxyl, ether, aldehyde radical, C1~C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；
The substituent of the substituted alkynyl is selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C20 alkane
One or more in base, C1~C20 cycloalkyl and C6~C20 aryl；The substituent of the substituted aryl is selected from substituent
In cycloalkyl selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C20 alkyl and C1~C20
One or more.
It is preferred that, the compound shown in the formula (I) has following structure：
Wherein, q=2~100.
It is preferred that, the reaction temperature is 0~80 DEG C；The reaction time is 1~12h.
It is preferred that, the mol ratio of silica group is 1 in the compound shown in the lithium hexafluoro phosphate and formula (I)：(2~4).
It is preferred that, the solvent of the reaction is carbonates, carboxylic acid esters, alcohols or ethers；The lithium hexafluoro phosphate exists
Concentration in solvent is 1~10mol/L.
It is preferred that, it is described reaction in the environment of inert gas carry out, the inert gas be selected from nitrogen, helium, argon gas,
One kind in neon and xenon.
It is preferred that, filtering is also included after the reaction, product is obtained with eluent solvent, drying；The drying temperature is 80
~150 DEG C.
Compared with prior art, the invention provides a kind of preparation method of difluorophosphate, including：By lithium hexafluoro phosphate
Compound reaction with shown in formula (I), obtains difluorophosphate.The present invention is by the compound shown in lithium hexafluoro phosphate and formula (I)
Reaction can obtain yield and the high difluorophosphate of purity.The compound that the present invention is selected carries-Si-X keys, can make reaction
It is positive under faster speed to carry out, and reduce the generation of side reaction so that reaction can quickly carry out and obtain high receipts
Rate.And the product separating-purifying prepared by the synthetic method of the present invention is easy, and technique is simple；It is adapted to extensive raw
Production.
Brief description of the drawings
The nuclear-magnetism figure for the difluorophosphate that Fig. 1 prepares for the present invention.
Embodiment
By the compound reaction shown in lithium hexafluoro phosphate and formula (I), difluorophosphate is obtained；
Wherein, n=1~200；It is preferred that, the integer of n=1~100；The integer of preferred n=1~50；
X1~X2One or more in hydroxyl and halogen；The halogen is preferably fluorine, chlorine, bromine or iodine；More
It is preferred that, the X1~X2One or more in hydroxyl, fluorine, chlorine, bromine；Most preferably, the X1~X2It is independent
One or more of the ground in hydroxyl, fluorine or chlorine；Most most preferably, the X1~X2One in hydroxyl and fluorine
Plant or several.
R1~R4The independent alkyl selected from C1~C50, C1~C50 cycloalkyl, C2~C50 alkenyl, C2~C50
The aryl of alkynyl, C6~C50.
The R1~R4Preferably independently selected from substituted or unsubstituted C1~C25 alkyl, substituted or unsubstituted C6~
C25 aryl, substituted or unsubstituted C1~C25 cycloalkyl, substituted or unsubstituted C2~C25 alkenyl, substitution do not take
C2~the C25 in generation alkynyl；The R1~R4Alkyl more preferably independently selected from substituted or unsubstituted C1~C20, substitution or
Unsubstituted C6~C20 aryl, substituted or unsubstituted C1~C20 cycloalkyl, substituted or unsubstituted C2~C20 alkene
The alkynyl of base, substituted or unsubstituted C2~C20.The R1~R4Most preferably independently selected from substituted or unsubstituted C1~C15
Alkyl, substituted or unsubstituted C6~C15 aryl, substituted or unsubstituted C1~C15 cycloalkyl, substituted or unsubstituted
The alkynyl of C2~C15 alkenyl, substituted or unsubstituted C2~C15.
Wherein, in substituted or unsubstituted C1~C15 alkyl, R1~R4The most be preferably methyl, ethyl, propyl group or
Butyl.
In the present invention, the alkyl is preferably straight chained alkyl, branched alkyl, the direct-connected alkane of at least one substituent substitution
Base or the branched alkyl of at least one substituent substitution；Wherein, one kind in halogen and cyano group of the substituent independence or
Several, the number of substituent is preferably 1~5 on the alkyl, more preferably 2,3 or 4.
The aryl is preferably the aryl of unsubstituted aryl or the substitution of at least one substituent；Wherein, the substituent is only
Vertical selection halogen and/or cyano group；The number of substituent is preferably 1~5 on the aryl, more preferably 2,3 or 4.
The above-mentioned R of the present invention1~R4Group in：
It is described substitution alkyl substituent be preferably selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical,
One or more in C1~C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；Be more preferably selected from halogen, hydroxyl,
In amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C15 alkyl, C1~C15 cycloalkyl and C6~C15 aryl
It is one or more.The halogen is preferably fluorine, chlorine.
In a part of embodiment of the present invention, unsubstituted alkyl preferably can be：
Methyl, ethyl, n-propyl, 1- Methylethyls, normal-butyl, 1- methyl-propyls, 2- methyl-propyls, 1,1- dimethyl second
Base, n-pentyl, 1- methyl butyls, 1- ethyl propyls, 2- methyl butyls, 3- methyl butyls, 2,2- dimethyl propyls, 1,1- diformazans
Base propyl group, 1,2- dimethyl propyls, n-hexyl, 1- methyl amyls, 1- ethyl-butyls, 2- methyl amyls, 3- methyl amyls, 2-
Ethyl-butyl, 2,2- dimethylbutyls, 2,3- dimethylbutyls, 1,1- dimethylbutyls, 1,2- dimethylbutyls, 1,2,2- tri-
Methyl-propyl, 1- Ethyl-2-Methyls propyl group, 1- ethyl -1- methyl-propyls, n-octyl or positive decyl.
In a part of embodiment of the present invention, the alkyl being substituted with aryl preferably can be：
Phenyl methyl, diphenyl methyl, trityl group, 1- phenylethyls, 2- phenylethyls, (1- fluorophenyls) methyl,
(2- fluorophenyls) methyl, (3- fluorophenyls) methyl or (1,2- difluorophenyl) methyl.
In a part of embodiment of the present invention, the alkyl being optionally substituted by halogen preferably can be：
Methyl fluoride, difluoromethyl, trifluoromethyl, 1- fluoro ethyls, 2- fluoro ethyls, the fluoro ethyls of 1,1- bis-, the fluoro ethyls of 1,2- bis-,
2,2- bis- fluoro ethyls, 1,1,2- trifluoroethyl, chloromethyl, dichloromethyl, trichloromethyl, 1- chloroethyls, 2- chloroethyls, 1,1- bis-
Chloroethyl, 1,2- Dichloroethyls, 2,2- Dichloroethyls or 1,1,2- trichloroethyl.
In the present invention, the substituent of the substituted cycloalkyl be preferably selected from halogen, hydroxyl, amino, nitro, cyano group,
One or more in carboxyl, ether, aldehyde radical, C1~C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；It is more excellent
Choosing selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C15 alkyl, C1~C15 cycloalkyl and
One or more in C6~C15 aryl.The halogen is preferably fluorine, chlorine.
The substituent of the substituted alkenyl be selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~
One or more in C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；It is more preferably selected from halogen, hydroxyl, ammonia
One in base, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C15 alkyl, C1~C15 cycloalkyl and C6~C15 aryl
Plant or a variety of.The halogen is preferably fluorine, chlorine.
The substituent of the substituted alkynyl be selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~
One or more in C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；It is more preferably selected from halogen, hydroxyl, ammonia
One in base, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C15 alkyl, C1~C15 cycloalkyl and C6~C15 aryl
Plant or a variety of.The halogen is preferably fluorine, chlorine.
The substituent of the substituted aryl be selected from substituent be selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether,
One or more in the cycloalkyl of aldehyde radical, C1~C20 alkyl and C1~C20.It is more preferably selected from halogen, hydroxyl, amino, nitre
Base, cyano group, carboxyl, ether, aldehyde radical, C1~C15 alkyl, C1~C15 cycloalkyl and one kind or many in C6~C15 aryl
Kind.It is most preferably selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C12 alkyl, C1~C12
One or more in cycloalkyl and C6~C12 aryl.
The halogen is preferably fluorine, chlorine.When substituent is multiple, substituent can be with identical or different.
The present invention is not particularly limited for aryl, can be that monocyclic aryl can be polyaromatic；The present invention is for ring
Particular number be not particularly limited, when ring for it is multiple when, can also be condensed.
In a part of embodiment of the present invention, unsubstituted aryl preferably can be：
Phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2,3- 3,5-dimethylphenyls, 2,4- 3,5-dimethylphenyls,
2,5- 3,5-dimethylphenyls, 2,6- 3,5-dimethylphenyls, 2,3,4- trimethylphenyls, 2,3,5- trimethylphenyls, 2,3,6- trimethyls
Phenyl, 2,4,5- trimethylphenyls, 2,3,6- trimethylphenyls, 2,5,6- trimethylphenyls, 3,4,5- trimethylphenyl 1- naphthalenes
Base or 2- naphthyls.
In a part of embodiment of the present invention, unsubstituted aryl preferably can be：
2- phenyls, 3- phenyls or 4- phenyls.
In a part of embodiment of the present invention, preferably can be by the aryl that halogen atom replaces：
2- fluorophenyls, 3- fluorophenyls, 4- fluorophenyls, 2,3- difluorophenyls, 2,4- difluorophenyls, 2,5- difluorophenyls, 2,
6- difluorophenyls, 2,3,4- trifluorophenyls, 2,3,5- trifluorophenyls, 2,3,6- trifluorophenyls, 2,4,5- trifluorophenyls, 2,4,6-
Trifluorophenyl, 2,5,6- trifluorophenyls, 3,4,5- trifluorophenyls or pentafluorophenyl group.
In the present invention, the compound shown in the formula (I) preferably has following structure：
Wherein, it is preferred that q=2~100；Preferred q=2~50；The viscosity of hydroxy silicon oil is excellent in the formula (I-1)
Elect as less than 1000cs.
The present invention is not particularly limited for the molecular weight of above-claimed cpd, can be 100~5000；Preferably 150~
2000；Most preferably 150~1000.
The present invention for above-claimed cpd source without limiting, can be to be commercially available, can also be conventional according to this area
Method prepare, the present invention to this and is not limited.
The present invention reacts the compound shown in lithium hexafluoro phosphate and formula (I), obtains difluorophosphate.
The present invention preferably specifically reacts the compound shown in lithium hexafluoro phosphate and formula (I) in a solvent, obtains difluoro
Lithium phosphate.
In the present invention, the mol ratio of silica group is 1 in the lithium hexafluoro phosphate and compound shown in formula (I)：(2
~4)；More preferably 1：(2~3).
The reaction temperature is preferably 0~80 DEG C；More preferably 20~70 DEG C；Most preferably 30~60 DEG C.The reaction
Time is preferably 1~12h；More preferably 2~6h.
The solvent is preferably carbonates, carboxylic acid esters, alcohols or ethers；Above-mentioned solvent is that can dissolve hexafluorophosphoric acid
The solvent of lithium but insoluble difluorophosphate.Including but not limited to methyl ethyl carbonate, ethylene carbonate, fluorinated ethylene carbonate,
Propene carbonate (Pc), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate.
The concentration of the lithium hexafluoro phosphate in a solvent is preferably 1~10mol/L；More preferably 1~8mol/L；Most preferably
For 1~5mol/L；The most it is preferably 1~3mol/L.
In the present invention, the reaction is carried out preferably in closed container, and the reaction is entered in the environment of inert gas
OK, the one kind of the inert gas in nitrogen, helium, argon gas, neon and xenon.
It is of the present invention reaction be preferably stirring reaction, the present invention for stirring reaction concrete mode without limit,
It is well known to those skilled in the art.
It is preferably cooling, filtering, addition eluent solvent, filtering, vacuum drying after reaction of the present invention, obtains difluoro phosphorus
Sour lithium.
The cooling is preferably to be cooled to 25~35 DEG C.The present invention is for the filter type without restriction, this area
Known to technical staff.
Solvent refluxing elution is added after filtering, now solvent is above-mentioned reaction dissolvent.
Specific instrument and parameter of the invention for being dried under reduced pressure is without limiting, and well known to a person skilled in the art i.e.
Can.It is preferred that, the temperature that is dried under reduced pressure is 80~150 DEG C；More preferably 90~130 DEG C.The time of the drying be 3~
24h；More preferably 4~12h.
Difluorophosphate is identified present invention preferably employs following manner：
Using ion-chromatographic determination yield, it is specially：
In the chromatography of ions, as chromatographic column, using the ICS-3000 of DIONEX companies, and according to the conventional of manufacturer's recommended
The analysis condition of known metal ion/inorganic anion is analyzed.In gas chromatography, as chromatographic column, GL is used
The TC-1 (internal diameter 0.32mm × 0.25 μm of 30m × thickness) of Science companies, is opened with 5 DEG C per minute of programming rate from 40 DEG C
Begin to heat up, be measured.
The F obtained according to the method described above-Anion concentration, and obtain by acid-base titration the concentration of Bronsted acid, it is assumed that
The Bronsted acid is entirely HF, will be by above-mentioned F-Residual concentration conduct obtained from anion concentration subtracts the concentration of above-mentioned Bronsted acid
F-Anion concentration.
Reaction solution is analyzed using the chromatography of ions, acid-base titration, F is carried out-The analysis of anion concentration.Can be with
The lower limit of the quantitative values of trust is 1.0 × 10-2mol·kg-1。
Using31P-NMR and19F-NMR is analyzed and identified to obtained solid, NMR be using deuterated DMSO as solvent, with
Carried out on the basis of TMS.
In order to further illustrate the present invention, the preparation method of the difluorophosphate provided with reference to embodiments the present invention
It is described in detail.
Embodiment 1
By the compound and 400mL carbon that 152g lithium hexafluoro phosphates and 180g viscosity are formula (I-1) structure less than 1000cs
Dimethyl phthalate is added in the closed vessel of dry inert gas shielding, and is mixed into suspension, and 60 DEG C are reacted 6h, instead
Be cooled to room temperature after should terminating, be filtered to remove unreacted complete fluoride salt and solvent, obtain the crude product insoluble in solvent, then to its
Middle addition dimethyl carbonate is fully eluted, and after filtering while hot, is obtained product and is dried under reduced pressure 6h at 100 DEG C, obtain white powder, press
Nuclear-magnetism identification is carried out according to mode of the present invention, as a result as shown in figure 1, the difluorophosphate that Fig. 1 prepares for the present invention
Nuclear-magnetism figure；As seen from the figure the position of displacement 79 have typical difluorophosphoric acid with it is bimodal, be identified as difluorophosphate.
Yield and purity are calculated according to mode of the present invention, is as a result yield 95.8%, purity 99.5%.
Embodiment 2
By 1mol lithium hexafluoro phosphates and 2.2mol, the compound and 400mL methyl ethyl carbonates of formula (I-2) structure are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 50 DEG C of reaction 4h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add methyl ethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and is dried under reduced pressure 6h at 100 DEG C, obtain white powder, be identified as difluorophosphoric acid
Lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 97.1%, purity 99.9%.
Embodiment 3
By 1mol lithium hexafluoro phosphates and 2.2mol, the compound and 400mL diethyl carbonates of formula (I-2) structure are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 60 DEG C of reaction 2h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add diethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and is dried under reduced pressure 6h at 100 DEG C, obtain white powder, be identified as difluorophosphoric acid
Lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 98.5%, purity 99.4%.
Embodiment 4
By 1mol lithium hexafluoro phosphates and 1.1mol, the compound and 400mL dimethyl carbonates of formula (I-3) structure are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 60 DEG C of reaction 2h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add dimethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and 6h is dried under reduced pressure at 100 DEG C, weigh obtained white powder, be identified as difluoro
Lithium phosphate.Yield and purity are calculated according to mode of the present invention, is as a result yield 95.5%, purity 99.9%.
Embodiment 5
By 1mol lithium hexafluoro phosphates and 0.73mol, the compound and 400mL dimethyl carbonates of formula (I-4) structure are added to
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 60 DEG C of reaction 4h, reaction is cooled to after terminating
Room temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then adds carbonic acid diformazan thereto
Ester is fully eluted, after filtering while hot, obtains product and 6h is dried under reduced pressure at 100 DEG C, weigh obtained white powder, be identified as two
Lithium fluophosphate.Yield and purity are calculated according to mode of the present invention, is as a result yield 96.7%, purity 99.0%.
Embodiment 6
By 1mol lithium hexafluoro phosphates and 0.55mol, the compound and 400mL dimethyl carbonates of formula (I-5) structure are added to
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 60 DEG C of reaction 4h, reaction is cooled to after terminating
Room temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then adds carbonic acid diformazan thereto
Ester is fully eluted, after filtering while hot, obtains product and 6h is dried under reduced pressure at 100 DEG C, weigh obtained white powder, be identified as two
Lithium fluophosphate.Yield and purity are calculated according to mode of the present invention, is as a result yield 93.5%, purity 99.5%.
Embodiment 7
By 152g lithium hexafluoro phosphates and 180g, viscosity is less than the compound and 400mL carbonic acid of 1000cs formula (I-1) structure
Dimethyl ester is added in the closed vessel of dry inert gas shielding, and is mixed into suspension, 50 DEG C of reaction 6h, reaction
Room temperature is cooled to after end, unreacted complete fluoride salt and solvent is filtered to remove, obtains the crude product insoluble in solvent, then thereto
Add dimethyl carbonate fully to elute, after filtering while hot, obtain product and 6h is dried under reduced pressure at 100 DEG C, weigh obtained white powder
End, is identified as difluorophosphate.Yield and purity are calculated according to mode of the present invention, is as a result yield 85.6%, it is pure
Degree 99.4%.
Embodiment 8
By 1mol lithium hexafluoro phosphates and 1.1mol, the compound and 400mL dimethyl carbonates of formula (I-3) structure are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 70 DEG C of reaction 2h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add dimethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluorophosphoric acid
Lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 87.9%, purity 99.2%.
Embodiment 9
By 1mol lithium hexafluoro phosphates and 0.73mol, the compound and 400mL fluorinated ethylene carbonates of formula (I-4) structure add
Enter into the closed vessel of dry inert gas shielding, and be mixed into suspension, 60 DEG C of reaction 4h, reaction is dropped after terminating
Warm to room temperature, be filtered to remove unreacted complete fluoride salt and solvent, obtain the crude product insoluble in solvent, then add fluoro thereto
Ethylene carbonate is fully eluted, and after filtering while hot, is obtained product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified
For difluorophosphate.Yield and purity are calculated according to mode of the present invention, is as a result yield 91.2%, purity 99.8%.
Embodiment 10
By 152g lithium hexafluoro phosphates and 200g, viscosity is less than the compound and 400mL carbonic acid of 1000cs formula (I-1) structure
Propylene is added in the closed vessel of dry inert gas shielding, and is mixed into suspension, 60 DEG C of reaction 8h, reaction
Room temperature is cooled to after end, unreacted complete fluoride salt and solvent is filtered to remove, obtains the crude product insoluble in solvent, then thereto
Add fluorinated ethylene carbonate fully to elute, after filtering while hot, obtain product and be dried under reduced pressure 6h at 100 DEG C, obtained white powder
End, is identified as difluorophosphate.Yield and purity are calculated according to mode of the present invention, is as a result yield 93.5%, it is pure
Degree 99.3%.
Embodiment 11
By 1mol lithium hexafluoro phosphates and 0.55mol, the compound and 400mL dimethyl carbonates of formula (I-5) structure are added to
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 30 DEG C of reaction 6h, reaction is cooled to after terminating
Room temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then adds carbonic acid diformazan thereto
Ester is fully eluted, and after filtering while hot, is obtained product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluoro phosphorus
Sour lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 92.7%, purity 99.1%.
Embodiment 12
By 1mol lithium hexafluoro phosphates and 0.55mol, the compound and 400mL dimethyl carbonates of formula (I-5) structure are added to
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 20 DEG C of reaction 6h, reaction is cooled to after terminating
Room temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then adds carbonic acid diformazan thereto
Ester is fully eluted, and after filtering while hot, is obtained product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluoro phosphorus
Sour lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 87.7%, purity 99.2%.
Embodiment 13
1mol lithium hexafluoro phosphates and 2.2mol, the compound of formula (I-6) structure and 400mL dimethyl carbonates are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 50 DEG C of reaction 6h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add dimethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluorophosphoric acid
Lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 93.1%, purity 99.1%.
Embodiment 14
1mol lithium hexafluoro phosphates and 0.8mol, the compound of formula (I-7) structure and 400mL dimethyl carbonates are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 60 DEG C of reaction 4h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add dimethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluorophosphoric acid
Lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 91.2%, purity 99.3%.
Embodiment 15
1mol lithium hexafluoro phosphates and 1.1mol, the compound of formula (I-8) structure and 400mL dimethyl carbonates are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 50 DEG C of reaction 6h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add dimethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluorophosphoric acid
Lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 90.2%, purity 99.3%.
Embodiment 16
1mol lithium hexafluoro phosphates and 2.2mol, the compound of formula (I-9) structure and 400mL dimethyl carbonates are added to dry
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 50 DEG C of reaction 5h, reaction is cooled to room after terminating
Temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then add dimethyl carbonate thereto
Fully elution, after filtering while hot, obtains product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluorophosphoric acid
Lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 92.1%, purity 99.0%.
Embodiment 17
1mol lithium hexafluoro phosphates and 1.1mol, the compound of formula (I-10) structure and 400mL dimethyl carbonates are added to
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 50 DEG C of reaction 5h, reaction is cooled to after terminating
Room temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then adds carbonic acid diformazan thereto
Ester is fully eluted, and after filtering while hot, is obtained product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluoro phosphorus
Sour lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 89.2%, purity 99.3%.
Embodiment 18
1mol lithium hexafluoro phosphates and 0.8mol, the compound of formula (I-10) structure and 400mL dimethyl carbonates are added to
In the closed vessel of dry inert gas shielding, and suspension is mixed into, 60 DEG C of reaction 6h, reaction is cooled to after terminating
Room temperature, is filtered to remove unreacted complete fluoride salt and solvent, obtains the crude product insoluble in solvent, then adds carbonic acid diformazan thereto
Ester is fully eluted, and after filtering while hot, is obtained product and is dried under reduced pressure 6h at 100 DEG C, obtained white powder is identified as difluoro phosphorus
Sour lithium.Yield and purity are calculated according to mode of the present invention, is as a result yield 90.5.2%, purity 99.0%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of difluorophosphate, it is characterised in that including：
By the compound reaction shown in lithium hexafluoro phosphate and formula (I), difluorophosphate is obtained；
Wherein, n=1~200；
X1~X2One or more in hydroxyl and halogen；
R1~R4The independent alkyl selected from C1~C50, C1~C50 cycloalkyl, C2~C50 alkenyl, C2~C50 alkynyl,
C6~C50 aryl.
2. preparation method according to claim 1, it is characterised in that the X1~X2Independently selected from-OH ,-F or-Cl；Institute
State R1~R4Alkyl, substituted or unsubstituted C6~C25 aryl independently selected from substituted or unsubstituted C1~C25, substitution or
Unsubstituted C1~C25 cycloalkyl, substituted or unsubstituted C2~C25 alkenyl, substituted or unsubstituted C2~C25 alkynes
Base.
3. preparation method according to claim 2, it is characterised in that the X1~X2Independently selected from-OH or-F；The R1
~R4Alkyl, substituted or unsubstituted C6~C20 aryl independently selected from substituted or unsubstituted C1~C20, substitution or not
Substituted C1~C20 cycloalkyl, substituted or unsubstituted C2~C20 alkenyl, substituted or unsubstituted C2~C20 alkynes
Base.
4. the preparation method according to Claims 2 or 3, it is characterised in that the substituent of the substitution alkyl is selected from halogen, hydroxyl
In base, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl
One or more；The substituent of the substituted cycloalkyl be selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether,
One or more in aldehyde radical, C1~C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；The substituted alkenyl
Substituent is selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~C20 alkyl, C1~C20 cycloalkanes
One or more in base and C6~C20 aryl；The substituent of the substituted alkynyl is selected from halogen, hydroxyl, amino, nitro, cyanogen
One or more in base, carboxyl, ether, aldehyde radical, C1~C20 alkyl, C1~C20 cycloalkyl and C6~C20 aryl；Institute
State substituted aryl substituent be selected from substituent be selected from halogen, hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical, C1~
One or more in C20 alkyl and C1~C20 cycloalkyl.
5. preparation method according to claim 1, it is characterised in that the compound shown in the formula (I) has following structure：
Wherein, q=2~100.
6. preparation method according to claim 1, it is characterised in that the reaction temperature is 0~80 DEG C；The reaction time
For 1~12h.
7. preparation method according to claim 1, it is characterised in that the compound shown in the lithium hexafluoro phosphate and formula (I)
The mol ratio of middle silica group is 1：(2~4).
8. preparation method according to claim 1, it is characterised in that the solvent of the reaction be carbonates, carboxylic acid esters,
Alcohols or ethers；The concentration of the lithium hexafluoro phosphate in a solvent is 1~10mol/L.
9. preparation method according to claim 1, it is characterised in that the reaction is carried out in the environment of inert gas, institute
State the one kind of inert gas in nitrogen, helium, argon gas, neon and xenon.
10. preparation method according to claim 8, it is characterised in that also include after the reaction filtering, with eluent solvent,
Drying obtains product；The drying temperature is 80~150 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108793118A (en) * | 2018-08-13 | 2018-11-13 | 合肥天徽新材料有限公司 | A kind of process units and production method of difluorophosphate |
| CN109422257A (en) * | 2017-08-31 | 2019-03-05 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphate |
| CN110380150A (en) * | 2019-08-02 | 2019-10-25 | 中国科学院宁波材料技术与工程研究所 | A kind of innoxious recovery method of waste and old power battery electrolyte |
| CN114634170A (en) * | 2020-12-15 | 2022-06-17 | 江苏国泰超威新材料有限公司 | Preparation method of lithium difluorophosphate |
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| CN109422257A (en) * | 2017-08-31 | 2019-03-05 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorophosphate |
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