CN103098284A - Producing solvent mixtures having a low water content - Google Patents
Producing solvent mixtures having a low water content Download PDFInfo
- Publication number
- CN103098284A CN103098284A CN2011800432813A CN201180043281A CN103098284A CN 103098284 A CN103098284 A CN 103098284A CN 2011800432813 A CN2011800432813 A CN 2011800432813A CN 201180043281 A CN201180043281 A CN 201180043281A CN 103098284 A CN103098284 A CN 103098284A
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- China
- Prior art keywords
- compound
- solvent mixture
- formula
- exchanger
- ion
- Prior art date
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Links
- 239000011877 solvent mixture Substances 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 claims abstract description 42
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 31
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 150000008053 sultones Chemical class 0.000 claims abstract description 13
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 32
- 229910001416 lithium ion Inorganic materials 0.000 claims description 32
- -1 halo organic carbonate Chemical class 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 7
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 5
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 5
- 229910013131 LiN Inorganic materials 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 4
- 150000005677 organic carbonates Chemical class 0.000 abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 230000004087 circulation Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 150000001793 charged compounds Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000003109 Karl Fischer titration Methods 0.000 description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Chemical group 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical group OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical group FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910003251 Na K Inorganic materials 0.000 description 1
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- MJIULRNAOLSIHL-UHFFFAOYSA-N carbonic acid;fluoroethene Chemical class FC=C.OC(O)=O MJIULRNAOLSIHL-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical group O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 229910052698 phosphorus Chemical group 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Chemical group 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical group ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/14—Base exchange silicates, e.g. zeolites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
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Abstract
A process for producing a solvent mixture comprising (A) at least one compound of formula (I), (B) at least one compound of formula (II a) or (II b), (C) optionally at least one additive selected from aromatic compounds, sultones and exo- methylene ethylene carbonates, melamine, urea, organic phosphates and halogenated organic carbonates, (D) optionally at least one lithium salt, and from 3 to 30 weight ppm of water, which process comprises (a) components (A), (B) and, if used, (C) being mixed with one another, (b) dried over at least one ion exchanger or molecular sieve, (c) separated from ion exchanger or, respectively, molecular sieve, and (d) at least one lithium salt, if used, being added, where the variables are defined as follows: R1, R2 are each the same or different and selected from C1-C4-alkyl, and R3 is selected from hydrogen and C1-C4-alkyl.
Description
The present invention relates to produce the method for the solvent mixture that comprises following component:
(A) at least one formula (I) compound:
(B) at least one formula (IIa) or (IIb) compound:
(C) optionally at least one is selected from the additive of aromatic compounds, sultone and outer-methylene carbonic acid ethyl, organophosphorus ester and halo organic carbonate,
(D) optional at least one lithium salts,
With the water of 3-30ppm weight,
Described method comprises
(a) by component (A), (B) and if use, (C) be mixed with each other,
It is (b) dry at least one ion-exchanger or molecular sieve,
(c) with ion-exchanger or molecular sieve, separate, and
(d) if use, add at least one lithium salts,
Wherein each variable-definition is as follows:
R
1, R
2identical or different and be selected from C separately
1-C
4alkyl,
R
3be selected from hydrogen and C
1-C
4alkyl.
In alternative, the present invention relates to a kind of method of producing solvent mixture, wherein by each component (A), (B) and if use, (C) carry out drying or by these components each self-desiccation before it mixes.Therefore, the present invention also relates to produce the method for the solvent mixture that comprises following component:
(A) at least one formula (I) compound:
(B) at least one formula (IIa) or (IIb) compound:
(C) optionally at least one is selected from the additive of aromatic compounds, sultone and outer-methylene carbonic acid ethyl, organophosphorus ester, melamine, urea and halo organic carbonate,
(D) optional at least one lithium salts,
With the water of 3-30 ppm by weight,
Described method comprises
I. by component (A), (B) and if use, independent dry at least one each comfortable at least one ion-exchanger or molecular sieve in (C),
Ii. ion-exchanger or molecular sieve are separated with component dry in step (i), and
Iii. by component (A), (B) and if use, if (C) and use, at least one lithium salts is mixed with each other, wherein each variable-definition is as follows:
R
1, R
2identical or different and be selected from C separately
1-C
4alkyl,
R
3be selected from hydrogen and C
1-C
4alkyl.
The invention further relates to solvent mixture and the purposes of solvent mixture of the present invention in lithium ion battery, this solvent mixture comprises:
(A) at least one formula (I) compound,
(B) at least one formula (IIa) or (IIb) compound,
(C) optionally at least one is selected from the additive of aromatic compounds, sultone and outer-methylene carbonic acid ethyl, organophosphorus ester and halo organic carbonate, and
(D) optional at least one lithium salts,
Water with the 3-30 ppm by weight.
The method of finding effective storage of electrical energy is lasting for years.Effective storage of electric energy allows electric energy to produce when favourable and uses when needed.
Known storage battery is as lead accumulator and nickel-cadmium accumulator for many years.Known lead accumulator has relative low energy density and the shortcoming of memory effect with nickel-cadmium accumulator, and it has reduced filling property again so reduction of service life of lead accumulator and nickel-cadmium accumulator.
Use lithium-ions battery, usually also referred to as lithium ion battery thing as an alternative.They provide than the high energy density of storage battery of the heavy metal based on plumbous or relatively expensive.
Because many lithium ion batteries are used lithium metal, lithium metal is water-sensitive.Therefore, water can not be as the solvent of lithium salts used in lithium ion battery.And the solvent using organic carbonate, ether and ester as enough polarity.Therefore, recommend anhydrous solvent is used for to the document of electrolyte for example referring to WO2007/049888.
Yet anhydrous solvent inconvenience is produced and processing.Many intrinsic solvents for lithium ion battery comprise about 100ppm or more water.Yet, to most of lithium ion batteries a high proportion of water like this, be unacceptable.Because the most prior art lithium ion battery is not to comprise single solvent but the fact of the very large solvent mixture of some of activity and drier difference, make to provide the problem complexity that fully is applicable to the solvent of lithium ion battery.
For this reason, the invention provides the solvent mixture that is suitable as the electrolyte in lithium ion battery.For this reason, the present invention further provides a kind of method of producing the solvent mixture that is applicable to lithium ion battery.For this reason, the present invention finally provides the lithium ion battery with works fine characteristic.
While having found this purpose by beginning, the method for definition realizes.
For the present invention, lithium-ions battery is called to lithium ion battery.
The inventive method provides the solvent mixture that comprises following component:
(A) at least one formula (I) compound:
(B) at least one formula (IIa) or (IIb) compound:
With the 3-30 ppm by weight, the water of preferred 5-25 ppm by weight.
Each variable-definition in formula is as follows:
R
1, R
2identical or different and be selected from C separately
1-C
4alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, preferable methyl or ethyl,
R
3be selected from C
1-C
4alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, preferable methyl, and
Hydrogen more especially.
It is 1:10-10:1 that one embodiment of the invention comprise weight ratio, preferably formula (I) compound of 3:1-1:1 and formula (IIa) and (IIb) compound.
Preferred formula (I) compound is dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate and composition thereof, the mixture of at least two kinds in compound dimethyl carbonate, diethyl carbonate and the methyl ethyl carbonate of enumerating.
In one embodiment of the invention, the mixed solvent obtained according to the present invention comprises two or more formulas (I) compound, for example diethyl carbonate and methyl ethyl carbonate.
In one embodiment, the solvent mixture obtained according to the present invention comprises at least one formula (IIa) compound, but not containing formula (IIb) compound.In other embodiment of the present invention, the solvent mixture obtained according to the present invention comprises at least one formula (IIb) compound, but not containing formula (IIa) compound.In other embodiment of the present invention, the solvent mixture obtained according to the present invention comprises at least one formula (IIa) compound and at least one (IIb) compound.
The ratio of water can be determined via multiple known method own.For example, particularly suitable is the Ka Er Karl Fischer titration, for example, according to DIN51777 or ISO760:1978.
The solvent mixture obtained according to the present invention can comprise other components, for example:
(C) at least one is selected from the additive of aromatic compounds, sultone and outer-methylene carbonic acid ethyl, halo organic carbonate, organophosphorus ester, and/or
(D) at least one lithium salts.
Therefore, for the purpose of the present invention, " solvent mixture " is not only applicable to salt-free solvent mixture and is applicable to the solution of lithium salts in solvent mixture yet.
The example that is suitable as the aromatic compounds of additive is biphenyl, cyclohexyl benzene and Isosorbide-5-Nitrae-dimethoxy benzene.
Sultone can be replacement or unsubstituted.The propylene sultone that the example of suitable sultone is butane sultone and formula (III):
And particularly per molecule has the sultone of the two keys of at least one C-C.The example that replaces sultone is 1-phenyl-1, the 3-butane sultone.
The example of outward-methylene carbonic acid ethyl is in particular formula (IV) compound:
R in each case wherein
4and R
5can be selected from identical or different and separately C
1-C
10alkyl and hydrogen.In a preferred embodiment, R
4and R
5be methyl.
The halo organic carbonate, more especially the fluoro organic carbonate comprises that per molecule has at least one halogen atom, preferably per molecule has the ring-type of one or two halogen atom or the organic carbonate of acyclic.Halogen atom is preferably chlorine and fluorine more preferably.Example is fluoroethylene carbonate and two fluoro ethylene carbonates:
Organophosphorus ester comprises phosphoric acid and one or more Organic Alcohols, three fat of preferred a kind of Organic Alcohol.Available Organic Alcohol comprises and for example replacing or unsubstituted alkanol and replacement or unsubstituted phenol.The preferred embodiment of organophosphorus ester is tris（chloroethyl）phosphate, tricresyl phosphate (3-chloropropyl) ester, tricresyl phosphate (2-isopropyl) ester, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (ω, ω '-bis-chloro isopropyl) ester, tri-2-ethylhexyl phosphate, Resorcino diphosphonic acid diphenyl, mono phosphoric acid ester-, two-and three (isopropyl phenyl) ester (isopropylated triphenyl phosphates) and bisphenol-A diphenyl phosphoester.Organophosphorus ester can be used as fire retardant.
The example of other suitable flame retardant is melamine and urea.
One embodiment of the invention comprise that the total solvent mixture added based on obtaining according to the present invention is total up to the 0-30 % by weight, preferably 1-10 % by weight additive (C).
In a scheme, the method for production solvent mixture provided by the invention at least comprises following three steps:
(a) for example by stirring said components (A), (B) and if use, (C) be mixed with each other.Can use predrying or commercial components (A), (B) and if use, (C).
(b) dry this mixture at least one ion-exchanger or preferred molecular sieve.
(c) dry solvent mixture is separated with ion-exchanger or molecular sieve.
(d) the 4th, the optional step of adding at least one lithium salts or component (C).
In other scheme, the method for production solvent mixture provided by the invention at least comprises following three steps:
I. by component (A), (B) and if use, independent dry at least one each comfortable at least one ion-exchanger or molecular sieve in (C),
Ii. ion-exchanger or molecular sieve are separated with component dry in step (i), and
Iii. by component (A), (B) and if use, if (C) and use, at least one lithium salts is mixed with each other.
In this scheme in drying steps without whole components (A), (B) are provided and if use, (C).If a kind of in must dry these compounds, be greater than a kind of or all make mix after these components and use the water that the solvent mixture of at least one lithium salts (D) comprises ratio of the present invention.
According to the drying of each component of step (i), in the mode of the drying corresponding to according to step (b) solvent mixture, carry out.Equally, according to step (ii), each component of drying is separated in the mode corresponding to according to step (c), dry solvent mixture being separated with ion-exchanger or molecular sieve and carried out with ion-exchanger or molecular sieve.Finally, according to step (iii), each component is mixed and carried out in the mode of the mixing corresponding to according to step (a).
Step (a), (b) and (c) are now more specifically described.
Can arbitrarily temperature required lower by component (A), (B) and if use (C) mixing.
Step (a):
One embodiment of the invention are included at the temperature of 10-100 ° of C mixes.
One embodiment of the invention are included in peak melting point component (A) or mix at the temperature of at least 1 ° of C more than fusing point (B).
The volatility of the ceiling temperature of married operation volatile components in solvent mixture is determined.Preferably in mixture, at temperature below the volatile components boiling point, mix.
Mixing can be carried out under any required pressure, and preferred atmosphere is pressed.The duration of mixing may be selected to be for example 5 minutes to 24 hours.
Step (b):
Ion-exchanger and molecular sieve itself is known.
Hereinafter molecular sieve is preferably selected from natural and synthetic zeolite, and it can be ball (bead), powder or bar form.Preferably use 4
molecular sieve and more preferably 3
molecular sieve.
Ion-exchanger can be used as sheet-like article and uses, and for example, with bead or bar form, or uses with powder or post.Preferred sheet-like article is bead especially for example.
One embodiment of the invention comprise the use cation-exchanger.
In one embodiment of the invention, ion-exchanger or molecular screening are from the ion-exchanger of at least part of lithiumation or the molecular sieve of at least part of lithiumation.The ion-exchanger of lithiumation comprises following cation-exchanger, wherein Li at least partly
+can replace very fully H
+and/or Na
+or K
+.In other embodiment of the present invention, use ion-exchanger or the molecular sieve of lithiumation not (even not part lithiumation).
One embodiment of the invention comprise mixes the solvent mixture from step (a) and allows molecular sieve or ion-exchanger to act on solvent mixture with molecular sieve or preferred ion exchanger, for example, by stirring continuously or at certain intervals molecular sieve or the ion-exchanger suspension in solvent mixture.Also can use jolting or pumping circulation to replace stirring.
Other embodiments comprise by solvent mixture is applied to and comprise that ion-exchanger/molecular sieve is as fixedly post or the filter area of phase make ion-exchanger/molecular sieve act on solvent mixture, then allow solvent mixture to pass through this post or filter, for example, under gravity or the power by the pump increase.
Preferably make ion-exchanger or molecular sieve act on solvent mixture not existing under chemical drier.For the purpose of the present invention, chemical drier is highly acid, alkalescence or strong reducing property drier, is selected from more especially low molecular weight compound, salt and simple substance.Known acid drier comprises that for example alkyl aluminum, as trimethyl aluminium, also has phosphorus pentoxide and the concentrated sulfuric acid.Known alkaline drier comprises for example potash and CaH
2.Known reproducibility drier comprises for example SODIUM METAL, simple substance potassium and Na-K alloy.
One embodiment of the invention are included in 4-100 ° of C, and preferably 15-40 ° of C, more preferably carry out step (c) at the temperature of 20-30 ° of C.
In one embodiment of the invention, the time that allows ion-exchanger or molecular sieve to act on solvent mixture be a few minutes as at least 5 minutes to several days, preferred no more than 24 hours, 1-6 hour more preferably.
In one embodiment of the invention, ion-exchanger or molecular sieve rear use the in the post of packing into.Such embodiment is preferably 0.1-50m/h at linear flow rate (flow velocity/void column column section), preferably under 0.5-15m/h, operates.
For making the dry process can be via Ka Er Karl Fischer titration record, when step (c) is carried out, a small amount of solvent mixture can be removed one or more times.
Preferably will stir or jolting maintenance minimum.Undue vigorous stirring/jolting can cause molecular sieve or the disintegration of ion-exchanger part, and this can produce the problem by removing by filter.
Acting as of ion-exchanger/molecular sieve significantly removed any acid traces of water and existence from solvent mixture.Yet some water still residue in solvent.
Step (c)
After molecular sieve or ion-exchanger act on solvent mixture, must isolate molecular sieve or ion-exchanger.Separation in step (c) can be passed through solvent mixture distillation or decantation are realized, or preferably realize by filtration.
Step (c) is preferably carried out under inert gas, as carried out under drying nitrogen or dry argon gas.Yet, replacing dry inert gas, step (c) also can be carried out under dry air.
Select wherein solvent mixture to be applied to and comprise that ion-exchanger/molecular sieve is as the fixedly post of phase or the scheme of filter surfaces, then allow solvent mixture to be equivalent to carry out step (b) and (c) by post/filter, this equally within the scope of the present invention simultaneously.
When for example with bead or bar form, using molecular sieve/ion-exchanger, the aperture of filter material preferably adapts with the average grain diameter of molecular sieve/ion-exchanger.
A scheme is included in rear one or more components of all or part of interpolation (C) of step (c).
Step (d)
If need, can add in step (d) and at least one lithium salts of preferred dissolution (D).Suitable lithium salts (D) must sufficiently soluble in the solvent mixture obtained according to the present invention, 1g/L at least under room temperature for example.The example of suitable lithium salts (D) is LiPF
6, LiBF
4, LiClO
4, LiAsF
6, LiCF
3sO
3, LiC (C
nf
2n+1sO
2)
3, dioxalic acid lithium borate, difluoro dioxalic acid lithium borate (lithium difluorbisoxalatoborat), imino group lithium be as LiN (C
nf
2n+1sO
2)
2, the integer that wherein n is 1-20, LiN (SO
2f)
2, Li
2siF
6, LiSbF
6, LiAlCl
4and general formula (C
nf
2n+1sO
2)
mthe salt of XLi, wherein m is defined as follows:
When X is selected from oxygen and sulphur, m=1,
When X is selected from nitrogen and phosphorus, m=2, and
When X is selected from carbon and silicon, m=3.
Preferably conducting salt is selected from LiC (CF
3sO
2)
3, LiN (CF
3sO
2)
2, LiPF
6, LiBF
4and LiClO
4, be particularly preferably LiPF
6and LiN (CF
3sO
2)
2.
Except adding lithium salts (D), can or be promoted other measures that lithium salts (D) dissolves by the solvent mixture heating, as jolting, stirring or pumping circulation in step (d).
An embodiment comprises that the total solvent mixture added based on obtaining according to the present invention is the 1-30 % by weight, preferably the lithium salts (D) of 10-20 % by weight.
In a scheme of the present invention, one or more additives (C) can add after carrying out step (a)-(c).Yet this is only wise when related additive does not make the water content of the solvent mixture that obtains according to the inventive method be increased to altogether to surpass 30 ppm by weight.
In a scheme of the present invention, can add component (B) other components of in addition at least one (B) of mixing with component (A) at first.
The solvent mixture obtained by the inventive method is very suitable for or for the production of lithium ion battery.
The present invention further provides the solvent mixture that comprises following component:
(A) at least one formula (I) compound:
(B) at least one formula (IIa) or (IIb) compound:
(C) optionally at least one is selected from aromatic compounds, sultone and outer-methylene carbonic acid ethyl, organophosphorus ester, melamine, urea and halo organic carbonate, is in particular the additive of one or more fluoro organic carbonates,
(D) optional at least one lithium salts,
With the water of 3-30 ppm by weight, the water of preferred 5-25 ppm by weight,
Wherein each variable-definition is as follows:
R
1, R
2identical or different and be selected from C separately
1-C
4alkyl,
R
3be selected from hydrogen and C
1-C
4alkyl.
Solvent mixture of the present invention can advantageously obtain by said method.
Component (A), (B) and water and optional component (C) and (D) as described above.
In one embodiment of the invention, but solvent mixture of the present invention does not comprise the protic organic compound of detection ratio as alcohol or primary amine or secondary amine.
In one embodiment of the invention, solvent mixture of the present invention comprises and is no more than 50 ppm by weight, preferably is no more than 20 ppm by weight, more preferably no more than the protic organic compound of 10 ppm by weight.
In one embodiment of the invention, solvent mixture of the present invention comprises:
Be total up to the 9-90 % by weight, formula (I) compound of preferred 20-80 % by weight,
Be total up to the 9-90 % by weight, the preferably formula (IIa) of 20-80 % by weight or (IIb) compound,
The 3-30 ppm by weight, the water of preferred 5-25 ppm by weight,
0 % by weight is to being total up to 30 % by weight, the preferred additive (C) of 1-10 % by weight,
0 % by weight is to being total up to 30 % by weight, preferably the lithium salts (D) of 10-20 % by weight.
In one embodiment of the invention, formula (I) compound is selected from dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate and composition thereof, the mixture of at least two kinds in the compound dimethyl carbonate of enumerating, diethyl carbonate, methyl ethyl carbonate.
In one embodiment of the invention, solvent mixture of the present invention comprises at least one (IIa) compound and at least one formula (IIb) compound.
In one embodiment of the invention, solvent mixture of the present invention comprises at least one and is selected from LiPF
6, LiBF
4, LiN (CF
3sO
2)
2, LiClO
4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, LiAsF
6, LiN (FSO
2)
2, LiC (CF
3sO
2)
3, LiN (C
2f
5sO
2)
2, preferred LiPF
6, LiBF
4, LiN (CF
3sO
2)
2lithium salts (D) with dioxalic acid lithium borate (LiBOB).
Lithium salts (D) can be with 0.1-3M, and preferably the concentration of 0.5-1.5M adds solvent mixture.
In one embodiment of the invention, solvent mixture of the present invention comprises the formula (I) that altogether is less than 50 ppm by weight, (IIa) and/or (IIb) catabolite of compound, for example aliphatic C
1-C
4alkanol, ethylene glycol or following general formula compound:
Each R wherein
3as described above.Catabolite is as aliphatic C
1-C
4alkanol, ethylene glycol or above formula compound can detect by for example gas chromatography.
In preferred embodiments, but solvent mixture of the present invention does not comprise the formula (I), (IIa) of detection ratio and/or (IIb) catabolite of compound.
Solvent mixture of the present invention is highly suitable for and for the production of lithium ion battery.Therefore, the present invention further provides solvent mixture of the present invention or for the production of the purposes in lithium ion battery.The present invention further provides the lithium ion battery that comprises solvent mixture of the present invention.Lithium ion battery of the present invention shows good circulation characteristic and excellent stability.The solvent mixture that this lithium ion battery utilizes the present invention to comprise at least one lithium salts (D).
Lithium ion battery of the present invention can comprise for example one or more negative electrodes based on the transition metal mixed oxide, for example, based on LiMnO
2, LiCoO
2, LiNiO
2, Li
1+w(Ni
aco
bmn
1-a-b)
1-wo
2negative electrode, wherein w can be 0-0.2, is preferably up to the number that 0.1, a and b are selected from the 0-1 of the a+b that satisfies condition≤1.
Negative electrode based on the transition metal mixed oxide can further comprise the carbon of the form of for example conducting electricity, for example carbon black, cigarette ash, graphite, Graphene or carbon nano-tube.
Negative electrode in battery of the present invention for example can further comprise for example polymer adhesive of adhesive.Copolymer and the polyacrylonitrile of copolymer, tetrafluoroethene and vinylidene fluoride that specially suitable polymer adhesive is Kynoar (PVdF), polytetrafluoroethylene, tetrafluoroethene and hexafluoropropylene.
Lithium ion battery of the present invention can further comprise the anode consisted of self known materials, is preferably graphite substantially.Lithium ion battery of the present invention can further comprise common assembly, for example one or more dividing plates, one or more current-collector and cover.
In the other embodiment of the present invention, lithium ion battery of the present invention can be selected from so-called lithium-air battery, i.e. the reversible reaction based on lithium and aerial oxygen and form oxide or peroxide forms Li
2o or Li
2o
2the battery of principle.In the other embodiment of the present invention, lithium ion battery of the present invention can be selected from lithium-sulfur cell, based on sulphur via the polysulfide ion to S
2-the battery of reaction, it reoxidizes when battery charges.
The present invention illustrates by production example.
In the value of ppm all based on ppm by weight.Mensuration detects and carries out with coulomb according to DIN51777 or ISO760:1978 by the Ka Er Karl Fischer titration.
I. production lithium ion battery of the present invention
I.1 production solvent mixture LGM.1 of the present invention
On the HS1000 filter, by 37kg3
molecular sieve (zeolite based on alumino-silicate, bead form, average diameter 16mm, with
mS564C is commercial) on the filter of the filtering surface of suction filter under 10 bar by being heated to 150 ° of C and keeping activating in 114 hours.
Following component is mixed in the stirred vessel be connected with suction filter with pumping circulation under 25 ° of C and dry argon gas:
78.2kg ethylene carbonate (II.a.1), water content: 20ppm
97.6kg methyl ethyl carbonate (I.1), water content: 53ppm.
The mixture of the organic carbonate that can so obtain is via the molecular sieve circulation pumping in suction filter.Obtained after 7.5 hours and measure the solvent mixture of the present invention that its water content is 15ppm.Utilize this solvent mixture to dissolve 31.0kg LiPF
6the solvent mixture LGM.1 of the present invention that comprises lithium salts with acquisition with the 4.4kg vinylene carbonate.
I.2 the electrode of production lithium ion battery of the present invention
I.2.1 produce negative electrode
Mix following component in mortar under argon gas:
89g?Li
1.01Ni
0.5Co
0.2Mn
0.3O
2.01，
5gPVdF (from Aldrich),
The 3g carbon black (
from Timcal),
3g carbon black (KS6, from Timcal),
And add 100g NMP until form sweet shape suspension.By described sweet shape suspension blade coating on aluminium foil and in dry 16 hours of 120 ° of C.The bed thickness of the dried cathode material that can so obtain is 40 μ m.This lamination is prolonged to compress 25% to 30 μ m.Then, cutting be measured as 50mm * 50mm electrode, weigh, with Al current-collector welding vacuumize under 120 ° of C again.
Recording cathode active material is 225mg.
I.2.2 production lithium ion battery of the present invention
To be transferred to from dried electrode I.2.1 the glove box that is filled with argon gas, and carry out therein following operation: the anode coated side is placed in heat sealable PET/Al/PE composite membrane (NEFAB) upward above and utilizes approximately 500 μ L LGM.1 to soak.The polyolefin separator (Celgard) that is measured as 55mm * 55mm is not folded and placed to the center of the wetting anode of electrolyte and wetting with LGM.1 equally.Then, negative electrode is placed in the center of dividing plate equally down by the wetting also coated side of LGM.1.Finally, removing excessive LGM.1 and accumulation body (PET/Al/PE composite membrane, anode, dividing plate, negative electrode) is covered by heat sealable PET/Al/PE composite membrane and uses heat seal equipment to seal on four limits.
Obtain lithium ion battery LIB.1 of the present invention.
II. the chemical property of lithium ion battery LIB.1 of the present invention:
LIB.1 is taken out from glove box and utilizes battery test system (MACCOR) under 25 ° of C, to utilize following setting to carry out charging and discharging (simultaneously measuring battery capacity):
Charging: from 3.2V to 4.2V, then keep 1 hour under 4.2V under the C speed of record.
The electric discharge: under described C speed from 4.2V to 3.2V.
Electric current: circulate 1 and 2 under 0.1C (formation), circulation 3-300 is under 0.5C.Specific capacity C is made as specified 139mAh/g.
Result:
Fig. 1 has described LIB.1 and has periodically relied on capacitance and charge/discharge efficiency.Obviously the 135mAh/g capacitance (based on cathode material) recorded in the 3rd circulation does not almost descend in the charging and discharging process.After 300 circulations, capacitance is still 128mAh/g.This is corresponding to only 5% decline.Have afterwards efficient (> 99.95% in several circulations only) charging and discharging.
Claims (15)
1. the method for the solvent mixture that a production comprises following component:
(A) at least one formula (I) compound:
(B) at least one formula (IIa) or (IIb) compound:
(C) optionally at least one is selected from the additive of aromatic compounds, sultone and outer-methylene carbonic acid ethyl, organophosphorus ester, melamine, urea and halo organic carbonate,
(D) optional at least one lithium salts,
With the water of 3-30 ppm by weight,
Described method comprises:
(a) by component (A), (B) and if use, (C) be mixed with each other,
It is (b) dry at least one ion-exchanger or molecular sieve,
(c) with ion-exchanger or molecular sieve, separate, and
(d) if use, add at least one lithium salts,
Wherein each variable-definition is as follows:
R
1, R
2identical or different and be selected from C separately
1-C
4alkyl,
R
3be selected from hydrogen and C
1-C
4alkyl.
2. the method for the solvent mixture that a production comprises following component:
(A) at least one formula (I) compound:
(B) at least one formula (IIa) or (IIb) compound:
(C) optionally at least one is selected from the additive of aromatic compounds, sultone and outer-methylene carbonic acid ethyl, organophosphorus ester, melamine, urea and halo organic carbonate,
(D) optional at least one lithium salts,
With the water of 3-30 ppm by weight,
Described method comprises:
I. by component (A), (B) and if use, independent dry at least one each comfortable at least one ion-exchanger or molecular sieve in (C),
Ii. ion-exchanger or molecular sieve are separated with component dry in step (i), and
Iii. by component (A), (B) and if use, if (C) and use, at least one lithium salts is mixed with each other, wherein each variable-definition is as follows:
R
1, R
2identical or different and be selected from C separately
1-C
4alkyl,
R
3be selected from hydrogen and C
1-C
4alkyl.
3. according to the method for claim 1 or 2, the water that wherein said solvent mixture comprises the 5-25 ppm by weight.
4. according to the method for any one in claim 1-3, wherein ion-exchanger or molecular sieve pass through isolated by filtration in step (c).
5. according to the method for any one in claim 1-4, wherein ion-exchanger or molecular screening are from the ion-exchanger of at least part of lithiumation or the molecular sieve of at least part of lithiumation.
6. according to the method for any one in claim 1-4, wherein ion-exchanger or molecular screening are from the ion-exchanger of lithiumation not or the molecular sieve of lithiumation not.
7. according to the method for any one in claim 1-6, its Chinese style (I) compound is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and composition thereof.
8. according to the method for any one in claim 1-7, wherein select at least one formula (IIa) compound and at least one formula (IIb) compound.
9. a solvent mixture comprises:
A. at least one formula (I) compound:
B. at least one formula (IIa) or (IIb) compound:
C. optionally at least one is selected from the additive of aromatic compounds, sultone and outer-methylene carbonic acid ethyl, organophosphorus ester and halo organic carbonate,
D. optional at least one lithium salts,
With the water of 3-30 ppm by weight,
Wherein each variable-definition is as follows:
R
1, R
2identical or different and be selected from C separately
1-C
4alkyl,
R
3be selected from hydrogen and C
1-C
4alkyl.
10. according to the solvent mixture of claim 9, the water that it comprises the 5-25 ppm by weight.
11., according to the solvent mixture of claim 9 or 10, its Chinese style (I) compound is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and composition thereof.
12., according to the solvent mixture of any one in claim 9-11, it comprises at least one formula (IIa) compound and at least one formula (IIb) compound.
13., according to the solvent mixture of any one in claim 9-12, wherein lithium salts (D) is selected from LiPF
6, LiBF
4, LiN (CF
3sO
2)
2or dioxalic acid lithium borate.
14. the purposes of solvent mixture in lithium ion battery is manufactured according to any one in claim 9-13.
15. the lithium ion battery comprised according to the solvent mixture of any one in claim 9-13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10176200 | 2010-09-10 | ||
| EP10176200.3 | 2010-09-10 | ||
| PCT/IB2011/053899 WO2012032471A1 (en) | 2010-09-10 | 2011-09-06 | Producing solvent mixtures having a low water content |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103098284A true CN103098284A (en) | 2013-05-08 |
Family
ID=43500323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800432813A Pending CN103098284A (en) | 2010-09-10 | 2011-09-06 | Producing solvent mixtures having a low water content |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2614550A4 (en) |
| JP (1) | JP2013541140A (en) |
| KR (1) | KR20130115249A (en) |
| CN (1) | CN103098284A (en) |
| WO (1) | WO2012032471A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414908A (en) * | 2022-07-29 | 2022-12-02 | 化学与精细化工广东省实验室 | Lithium ion battery electrolyte solvent water remover and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6925176B2 (en) * | 2017-06-14 | 2021-08-25 | 三菱ケミカル株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
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| CN1204162A (en) * | 1997-06-27 | 1999-01-06 | 三井化学株式会社 | Non-aqueous electrolytic solution and secondary battery containing non-aqueous electrolytitic solution |
| CN1943071A (en) * | 2004-04-20 | 2007-04-04 | 三菱化学株式会社 | Nonaqueous electrolyte solution and lithium secondary battery using same |
| CN101297433A (en) * | 2005-10-24 | 2008-10-29 | 株式会社Lg化学 | Inhibitor of redox interaction additive life cycle reduction and nonaqueous electrolyte and secondary battery containing the same |
| CN101645521A (en) * | 2009-01-20 | 2010-02-10 | 万向电动汽车有限公司 | Low temperature functional electrolyte of lithium-ion secondary battery and preparation method thereof |
| CN101685880A (en) * | 2008-09-25 | 2010-03-31 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of electrolyte of low-temperature lithium ion battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW375844B (en) * | 1997-06-27 | 1999-12-01 | Mitsui Chemicals Inc | Non-aqueous electrolytic solution and secondary battery containing non-aqueous electrolytic solution |
| DE19915056A1 (en) * | 1999-04-01 | 2000-10-05 | Riedel De Haen Gmbh | Organic lithium salt solutions, especially battery electrolytes, are dehydrated by contact with alkali or alkaline earth metal ion exchanged zeolite granules |
| EP2259375B1 (en) * | 2003-02-27 | 2012-05-16 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and lithium secondary battery |
| EP1744394A4 (en) * | 2004-04-20 | 2014-07-23 | Mitsubishi Chem Corp | Nonaqueous electrolyte solution and lithium secondary battery using same |
-
2011
- 2011-09-06 EP EP11823143.0A patent/EP2614550A4/en not_active Withdrawn
- 2011-09-06 JP JP2013527721A patent/JP2013541140A/en not_active Withdrawn
- 2011-09-06 CN CN2011800432813A patent/CN103098284A/en active Pending
- 2011-09-06 KR KR1020137009024A patent/KR20130115249A/en not_active Withdrawn
- 2011-09-06 WO PCT/IB2011/053899 patent/WO2012032471A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204162A (en) * | 1997-06-27 | 1999-01-06 | 三井化学株式会社 | Non-aqueous electrolytic solution and secondary battery containing non-aqueous electrolytitic solution |
| CN1943071A (en) * | 2004-04-20 | 2007-04-04 | 三菱化学株式会社 | Nonaqueous electrolyte solution and lithium secondary battery using same |
| CN101297433A (en) * | 2005-10-24 | 2008-10-29 | 株式会社Lg化学 | Inhibitor of redox interaction additive life cycle reduction and nonaqueous electrolyte and secondary battery containing the same |
| CN101685880A (en) * | 2008-09-25 | 2010-03-31 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of electrolyte of low-temperature lithium ion battery |
| CN101645521A (en) * | 2009-01-20 | 2010-02-10 | 万向电动汽车有限公司 | Low temperature functional electrolyte of lithium-ion secondary battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414908A (en) * | 2022-07-29 | 2022-12-02 | 化学与精细化工广东省实验室 | Lithium ion battery electrolyte solvent water remover and preparation method and application thereof |
| CN115414908B (en) * | 2022-07-29 | 2024-03-15 | 化学与精细化工广东省实验室 | Lithium ion battery electrolyte solvent water removing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2614550A1 (en) | 2013-07-17 |
| WO2012032471A1 (en) | 2012-03-15 |
| KR20130115249A (en) | 2013-10-21 |
| JP2013541140A (en) | 2013-11-07 |
| EP2614550A4 (en) | 2014-03-19 |
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