CN1934657B - 复合高分子电解质组合物 - Google Patents
复合高分子电解质组合物 Download PDFInfo
- Publication number
- CN1934657B CN1934657B CN2004800020565A CN200480002056A CN1934657B CN 1934657 B CN1934657 B CN 1934657B CN 2004800020565 A CN2004800020565 A CN 2004800020565A CN 200480002056 A CN200480002056 A CN 200480002056A CN 1934657 B CN1934657 B CN 1934657B
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- China
- Prior art keywords
- cation
- monomer
- polymer electrolyte
- electrolyte composition
- alkyl
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 58
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
- 229920002959 polymer blend Polymers 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 44
- -1 1-vinyl imidazole cation Chemical class 0.000 claims description 41
- 150000003839 salts Chemical class 0.000 claims description 37
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 28
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 22
- 230000002787 reinforcement Effects 0.000 claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 230000005518 electrochemistry Effects 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229940006487 lithium cation Drugs 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 23
- 239000003990 capacitor Substances 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000012779 reinforcing material Substances 0.000 abstract 4
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 229960003328 benzoyl peroxide Drugs 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229920000867 polyelectrolyte Polymers 0.000 description 5
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CVZYZFFCMHSVCM-UHFFFAOYSA-N 1-[(4-ethenylphenyl)methyl]-3-methyl-2h-imidazole Chemical class C1=CN(C)CN1CC1=CC=C(C=C)C=C1 CVZYZFFCMHSVCM-UHFFFAOYSA-N 0.000 description 3
- ZETBDNNBXMTTLZ-UHFFFAOYSA-N 2-methylpropanamide Chemical compound CC(C)C(N)=O.CC(C)C(N)=O ZETBDNNBXMTTLZ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920000131 polyvinylidene Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- RSGSRVZMECOJNA-UHFFFAOYSA-M (4-ethenylphenyl)methyl-triethylazanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=C(C=C)C=C1 RSGSRVZMECOJNA-UHFFFAOYSA-M 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- DOVIZUBCLACUJT-UHFFFAOYSA-M 1-[(4-ethenylphenyl)methyl]-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].C1=[N+](C)C=CN1CC1=CC=C(C=C)C=C1 DOVIZUBCLACUJT-UHFFFAOYSA-M 0.000 description 1
- PREZSYXZLYLHNH-UHFFFAOYSA-M 1-ethenyl-3-ethylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C=C)=C1 PREZSYXZLYLHNH-UHFFFAOYSA-M 0.000 description 1
- LAKYLJMGQGMRCY-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1.C=CN1C=CN=C1 LAKYLJMGQGMRCY-UHFFFAOYSA-N 0.000 description 1
- WWVMHGUBIOZASN-UHFFFAOYSA-N 1-methyl-3-prop-2-enylimidazol-1-ium Chemical compound CN1C=C[N+](CC=C)=C1 WWVMHGUBIOZASN-UHFFFAOYSA-N 0.000 description 1
- KLFDZFIZKMEUGI-UHFFFAOYSA-M 1-methyl-3-prop-2-enylimidazol-1-ium;bromide Chemical compound [Br-].C[N+]=1C=CN(CC=C)C=1 KLFDZFIZKMEUGI-UHFFFAOYSA-M 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- ICFXCSLDPCMWJI-UHFFFAOYSA-N 2,3-dimethylbut-2-enoic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CC(C)=C(C)C(O)=O.CCC(CO)(CO)CO ICFXCSLDPCMWJI-UHFFFAOYSA-N 0.000 description 1
- HQGFCGSTNFPVQT-UHFFFAOYSA-N 2-methylprop-2-enoic acid 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound CC(=C)C(O)=O.SCC(=O)OCCOC(=O)CS HQGFCGSTNFPVQT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- QNEIVIRHAAOUAE-UHFFFAOYSA-N C1(=CC=CC=C1)CCC.C(C1CO1)[O] Chemical class C1(=CC=CC=C1)CCC.C(C1CO1)[O] QNEIVIRHAAOUAE-UHFFFAOYSA-N 0.000 description 1
- YMMLEYWDSKRSNG-UHFFFAOYSA-N CC(C#N)CC(C)C.CC(CCC#N)C Chemical compound CC(C#N)CC(C)C.CC(CCC#N)C YMMLEYWDSKRSNG-UHFFFAOYSA-N 0.000 description 1
- OMMURBPFLUOYFV-UHFFFAOYSA-N CN1C=NC=C1.CN1C=NC=C1.CN1C=NC=C1.Br Chemical compound CN1C=NC=C1.CN1C=NC=C1.CN1C=NC=C1.Br OMMURBPFLUOYFV-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
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- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
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- 229910015645 LiMn Inorganic materials 0.000 description 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- HXJJZRHJRMMKNN-UHFFFAOYSA-N O1C(COC2(C(C=CC=C2)CCC)OCC2CO2)C1 Chemical compound O1C(COC2(C(C=CC=C2)CCC)OCC2CO2)C1 HXJJZRHJRMMKNN-UHFFFAOYSA-N 0.000 description 1
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical compound NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
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- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 125000005131 dialkylammonium group Chemical group 0.000 description 1
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- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- YRHAJIIKYFCUTG-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;bromide Chemical compound [Br-].C=CC[N+](C)(C)CC=C YRHAJIIKYFCUTG-UHFFFAOYSA-M 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种具有高离子电导率和优良力学性质的全固体高分子电解质组合物。此电解质组合物是在高分子补强材料的存在下,使含有导入了聚合性官能团的季铵盐熔融盐和电荷移动离子源的单体组合物进行聚合而制成的。就高分子补强材料而言,在合适的有机溶剂中溶解单体组合物与补强材料后,可通过聚合该溶液以共混聚合物的形式进行复合化。也可以在多孔质片材或是薄膜中含浸单体组合物,并通过聚合进行复合化。作为电荷移动离子源可以选择锂盐,由此可以得到锂离子电池用的电解质,选择质子供给体可以得到燃料电池用的电解质,选择氧化还原离子对可以得到色素增感太阳电池用的电解质。不含有电荷移动离子源的本发明的高分子电解质组合物,也可以用作电容器的电解质。
Description
技术领域
本发明涉及一种复合高分子电解质组合物,具体涉及例如配置在锂离子电池、燃料电池、色素增感太阳电池、电解电容器等电化学性装置的电极间的复合高分子电解质组合物。
背景技术
在锂二次电池中,一般使用含有锂盐的非水电解液。此溶液是在碳酸乙烯酯(ethylene carbonate)、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯等碳酸酯类、γ—丁内酯等内酯类、以及四氢呋喃等醚类之类的非质子性极性溶剂中溶解锂盐而成。但是,这些有机溶剂容易挥发、具易燃性,在过量充电、过量放电、以及短路时存在安全性等问题。另外,液体电解液在对电池进行液体密封时,在处理上较麻烦。即使使用凝胶化的非水电解液,有机溶剂的挥发及易燃性问题仍然不能得到解决,仍然存在由凝胶相分离的电解液的泄漏问题。
最近提出了使用非水电解质的锂二次电池的方案,其中所述非水电解质是在含有季铵阳离子(ammonium cation)的常温熔融盐中溶解锂盐而成的。例如可以参照日本专利特开平10-92467、特开平10-265674、特开平11-92467、特开2002-11230。常温熔融盐在常温为液状,而且既不挥发也不易燃,因此较为安全,但是即使用基础聚合物(matrix polymer)作成凝胶,由于含有液体,其力学性质不充分,而且有时存在液体的相分离,因此处理上的问题以及电池设计上的问题仍然存在。
另外,也有人提出了在形成离子传导性熔融盐的咪唑鎓盐(imidazolium salt)中导入乙烯基,并通过聚合此单体来制造全固体高分子电解质的方案。可以参照日本专利特开平10-83821及特开平2000—11753。但是此高分子电解质也不具有充分的力学强度。
因而,对具有高离子电导率和能满足要求的力学性质且安全的高分子电解质的需求仍然存在。
发明内容
本发明的目的在于提供一种复合高分子电解质组合物,以满足上述的要求,该复合高分子电解质组合物是在电化学惰性的高分子补强材料的存在下,使单体组合物进行聚合而制造的,所述单体组合物含有熔融盐单体和电荷移动离子源,所述熔融盐单体具有由季铵阳离子和含氟阴离子所构成的季铵盐结构和聚合性官能团。
当本发明的高分子电解质组合物被用于锂离子电池时,上述电荷移动离子源是锂阳离子与含氟阴离子的盐,使用于燃料电池时是质子化的含氟阴离子。使用于色素增感太阳电池时是以I-/I3 -对(pair)为代表的氧化还原系统(redox system)。
本发明的原理,也可以应用在电解电容器的电解质。此时,可通过在所述高分子补强材料的存在下,聚合不含电荷移动离子源的所述单体组合物而获得。
使聚偏氟乙烯(polyvinylidene fluoride)为代表的电化学惰性高分子补强材料与熔融盐单体的聚合物复合化的方法有数种。第1种方法是将含有离子源的熔融盐单体和高分子补强材料溶解在适当的溶剂中,将此溶液以薄膜状流延后进行聚合的方法。第2种方法基本上与第1种方法相同,不同的是使用预先导入如碳一碳双键之类的能形成交联点的官能团的高分子补强材料。第3种方法是使用高分子补强材料的多孔质片材或是薄膜。使用熔融盐单体溶液含浸此片材,使片材中所含有的单体进行聚合而复合化。任何一种情况下都可以利用热、光(紫外线)或是电子射线照射来进行。
可以使含有聚合前的熔融盐单体的溶液在玻璃、聚酯等非接着基材上以薄膜状流延,聚合后经剥离作为独立膜来使用,也可以涂布在电极的活泼物质面上,之后在此状态下进行聚合来形成与电极一体化的薄膜。
由此形成的本发明高分子电解质薄膜,因为高分子补强材料的存在,与不含高分子补强材料的薄膜相比,以拉伸强度为代表的力学性质明显得到了改善。根据需要,可使熔融盐单体和小比率的多官能单体共聚合,以进一步改善力学性质。补强之后可使用本发明的复合高分子电解质组合物,组装体积小且能源密度高的高性能电池等。
具体实施方式
作为含有由季铵阳离子与含氟原子的阴离子所构成的季铵盐结构及聚合性官能团的单体的盐结构,是由脂肪族、脂环族、芳香族或是杂环的季铵阳离子与含有氟原子的阴离子所构成的盐结构。这里所称的“季铵阳离子”是指“氮的阳鎓离子(onium cation)”,含有如咪唑鎓(imidazolium)、吡啶鎓(pyridium)之类的杂环鎓离子。可以举出从下述铵阳离子群选出的至少一种铵阳离子与从下述阴离子群所选出至少一种阴离子所构成的盐结构。
(铵阳离子群)吡咯鎓阳离子(pyrrolium cation)、吡啶鎓阳离子(pyridinium cation)、咪唑鎓阳离子(imidazolium cation)、吡唑鎓阳离子(pyrazolium cation)、苯并咪唑鎓阳离子(benzimidazolium cation)、吲哚鎓阳离子(indolium cation)、咔唑鎓阳离子(carbazolium cation)、喹啉鎓阳离子(quinolium cation)、吡咯烷鎓阳离子(pyrrolidium cation)、哌啶鎓阳离子(piperidium cation)、哌嗪鎓阳离子(piperalium catiOn)、烷基铵阳离子(allkyl ammonium cation)(其中,含有被碳数1-30的烃基、羟基烷基(hydroxyalkyl group)、烷氧基烷基(alkoxyalkyl group)取代的离子)
上述任何一种都包括在N及/或环上结合有碳数1-10的烃基、羟基烷基、烷氧基烷基的离子。
(阴离子群)BF4、PF6、CnF2n+1CO2(其中n是1-4的整数)、CnF2n+1SO3(其中n是1-4的整数)、(FSO2)2N、(CF3SO2)2N、(C2F5SO2)2N、(CF3SO2)3C、CF3SO2-N-COCF3、R-SO2-N-SO2CF3(R是脂肪族基)、ArSO2-N-SO2CF3(Ar是芳香族基)
上述铵阳离子及阴离子种的耐热性、耐还原性或是耐氧化性优良,可取较宽的电化学窗(electrochemical window),可适用于电池、电容器。
作为单体中的聚合性官能团,可以例示的有乙烯基、丙烯基、甲基丙烯基(methacrylic group)、烯丙基等碳一碳不饱和基、环氧基、氧杂环丁烷基(oxetane group)等环状烷氧化物基(alkoxide group)和异氰酸酯基(isocyanate group)、羟基、羧基等。
作为特佳的铵阳离子种,可以例示的有1—乙烯基—3—烷基咪唑鎓阳离子、4—乙烯基—1—烷基吡啶鎓阳离子、1—烷基—3—烯丙基咪唑鎓阳离子、1-(4—乙烯基苄基)—3—烷基咪唑鎓阳离子、1-(乙烯基氧乙基)—3—烷基一咪唑鎓阳离子、1—乙烯基咪唑鎓阳离子、1—烯丙基咪唑鎓阳离子、N—烯丙基苯并咪唑鎓阳离子、二烯丙基一二烷基铵阳离子等,其中烷基是碳数为1-10的烷基。
作为特佳的阴离子种,可以例示的有双{(三氟甲基)磺酰}胺阴离子、2,2,2—三氟—N-(三氟甲基磺酰)乙酰胺阴离子、双{(五氟乙基)磺酰}胺阴离子、双{(氟)磺酰}胺阴离子、四氟硼酸酯阴离子、三氟甲烷磺酸盐阴离子等。
作为特佳的单体,可以例示的有1—乙烯基—3—烷基咪唑鎓双{(三氟甲基)磺酰}胺(烷基为C1-C10烷基)、1—乙烯基—3—烷基咪唑鎓四氟硼酸盐(烷基为C1-C10烷基)、4—乙烯基—1—烷基吡啶鎓双{(三氟甲基)磺酰}胺(烷基为C1-C10烷基)、4—乙烯基—1—烷基吡啶鎓四氟硼酸盐(烷基为C1-C10烷基)、1-(4—乙烯基苄基)—3—烷基咪唑鎓双{(三氟甲基)磺酰}胺(烷基为C1-C10烷基)、1-(4—乙烯基苄基)—3—烷基咪唑鎓四氟硼酸盐(烷基为C1-C10烷基)、1—缩水甘油基—3—烷基一咪唑鎓双{(三氟甲基)磺酰}胺(烷基为C1-C10烷基)、1—缩水甘油基—3—烷基一咪唑鎓四氟硼酸盐(烷基为C1-C10烷基)、N—乙烯基咔唑鎓四氟硼酸盐等。
锂离子电池的电荷移动离子源是锂盐,本发明中优选使用下述的由锂离子与含有氟原子的阴离子所构成的锂盐。
LiBF4、LiPF6、CnF2n+1CO2Li(n是1-4的整数)、
CnF2n+1SO3Li(其中n是1-4的的整数)、(FSO2)2NLi、
(CF3SO2)2NLi、(C2F5SO2)2NLi、(CF3SO2)3CLi、Li(CF3SO2-N-COCF3)、Li(R-SO2-N-SO2CF3)(R是脂肪族基)、Li(ArSO2-N-SO2CF3)(Ar是芳香族基)。
另外,燃料电池的电荷移动离子源(质子源),是相当于上述熔融盐单体的季铵盐结构的阴离子种的质子供给体。
作为典型的色素增感太阳电池的电荷移动离子,有I-/I3 -氧化还原对(pair),其他的有Br-/Br3 -对、醌/氢醌对等。
高分子补强材料,是具有优良耐氧化性、耐还原性、耐溶剂性、低吸水性、阻燃性等电化学/化学安定性、耐热性、耐寒性等温度特性,且力学特性(高延伸度、柔软性)和加工性优良的聚合物。可以举出的有聚四氟乙烯、聚偏氟乙烯等含氟聚合物、聚乙烯、聚丙烯等聚烯烃、聚丙烯腈、聚苯乙烯等乙烯基系聚合物、聚砜、聚醚砜等聚砜系聚合物、聚醚酮、聚醚醚酮等聚醚酮系聚合物、聚醚酰亚胺、聚酰胺酰亚胺、聚酰亚胺等聚酰亚胺系聚合物(任何一种都包括共聚物)。
高分子补强材料以氟系聚合物为佳,以聚偏氟乙烯及其共聚物、其改性聚合物为特佳,其分子量以数均分子量计优选为2000-2000000,3000-100000为佳,以5000-50000为特佳。
下面以使用于锂二次电池的电解质组合物为例说明其调制方法。通过将锂盐变更为其他电荷移动离子源,本方法也可以应用在燃料电池或是色素增感太阳电池用的电解质组合物,这对于本领域技术人员来讲是公知的常识。
高分子补强材料的复合化方法包括,使含有锂盐的熔融盐单体含浸于该材料的多孔质片材或是薄膜中,并在此种状态下进行聚合反应的方法;将高分子补强材料纤维分散在含有锂盐的熔融盐单体中,进行聚合反应的方法。
此时,高分子补强材料,具体为织物、无纺布、多孔质薄膜、片材类等,厚度为5-100μm,以10-50μm为佳。无纺布的透气度(依照JIS-1096)为5-40cc/m2.sec,多孔质薄膜孔径为0.05μm-1μm,以0.05μm-0.5μm为佳,气孔率为20%-80%,以35%-60%为佳,这些补强材料可以使用既有的制法、设备来制造,也可以使用市售品。
进而,将熔融盐单体、锂盐及高分子补强材料溶解在如二甲基乙酰胺之类的适当溶剂中,并将此溶液流延或涂布在如玻璃、聚酯薄膜之类的基材上,聚合后加以剥离,就可以得到复合化的高分子电解质组合物的薄膜。根据补强材料的高分子种类,也可以不使用溶剂而经由熔融与单体复合化。
由熔融盐单体的聚合物和补强材料形成共混聚合物的电解质组合物的情况下,高分子补强材料的比率可被设定为能使力学性质及离子电导率度得到最佳平衡的值。
相对熔融盐单体的补强材料的重量比一般为0.1-0.8,以0.35-0.65之间为特佳。关于特定熔融盐单体和特定高分子补强材料的组合,可以根据力学性质与离子电导率的最适当平衡通过实验决定。
使用熔融盐单体含浸补强材料的多孔质片材或是薄膜时,含有锂盐的高分子电解质会形成连续相,因此没有必要使力学性质与离子电导率达到最佳平衡。
同样地,掺合型电解质组合物的情况下,锂盐与力学性质的最适当平衡依赖于锂盐对熔融盐单体的比率。此比以重量而言,一般是0.05-0.8,以0.1-0.7为佳,以0.15-0.5的范围为特佳。特定熔融盐单体与特定锂盐的最适当组合比可以容易地通过实验来决定。使用多孔质片材或是薄膜时,因上述理由,锂盐对熔融盐单体的比只要是足以使离子电导率达到最大的量即可。
熔融盐单体可以单独聚合,或者也可以与能够与此共聚的单体进行共聚。
优先的方式之一,是使用具有能与熔融盐单体反应的官能团的高分子补强材料来形成接枝交联聚合物。作为共聚合单体也可以使用2种以上的熔融盐单体,也可以是不含盐结构的单体以及具有多个聚合性官能团的多官能单体。
本聚合反应中,添加单体热聚合引发剂或固化剂,通常是在40℃一200℃进行加热。聚合性官能团为碳一碳不饱和基时,作为热聚合引发剂可以举出的有过氧化苯甲酰(benzoylperoxide)、过氧化二异丙苯(dicumylperoxide)、二叔丁基过氧化物(di-ter-butylperoxide)、1,1—双(叔丁基过氧化)环己烷(1,1-bis(ter-butylperoxy)cyclohexane)、异丙苯化氢过氧化物(cuminehydroperoxide)等的过氧化物类、2,2’—偶氮二异丁腈(2,2’—azobisobutyronitrile)、2,2’—偶氮二(2,4—二甲基戊腈(2,4-dimethylvaleronitrile)等偶氮二化合物、过硫酸铵等无机引发剂。
聚合引发剂的使用量,相对聚合性单体总重量通常为0.1-10%,以1-5%为佳。
聚合性官能团为环氧基时,固化剂可以使用胺类、酸酐、羧酸等,反应催化剂可以使用烷基咪唑(alkylimidazole)衍生物。
为了使其聚合,也可以照射紫外线(使用光聚合引发剂)、电子射线等放射线。通过电子射线聚合也有望完成高分子补强材料自身的交联反应或单体补强材料的接枝反应,是较佳状态。照射量为0.1-50Mrad,以1-20Mrad为佳。
含有2个以上能够与熔融盐共聚合的聚合性官能团的多官能单体,例如有二乙烯苯、邻苯二甲酸二烯丙基酯(diallylphathalate)、乙二醇二(甲基)丙烯酸酯(ethyleneglycol-di(meta)acrylate)、二甘醇二(甲基)丙烯酸酯(diethyleneglycol-di(meta)acrylate)、三甘醇二(甲基)丙烯酸酯(triethyleneglycol-di(meta)acrylate)、三羟甲基丙烷三(甲基)丙烯酸酯(trimethylolpropane tri(meta)acrylate)、季戊四醇四(甲基)丙烯酸酯(pentaerythritol tetra(meta)acrylate)、三烯丙基三聚异氰酸酯(triallylisocyanurate)、三烯丙基三聚氰酸酯(triallylcyanurate)、二烯丙基一二甲基铵双一{(三氟甲基)磺酰}胺(diallyl-dimethylammoniumbis—{(trifluoromethyl)salfonyl}amide)、二烯丙基一二甲基铵四氟硼酸盐(diallyl-dimethylammoniumterafluoroborate)、2,2—双(环氧丙基氧)苯基丙烷(2,2-bis(glycidyloxy)phenylpropane)等。这些多官能单体可以使用的量为熔融盐单体的0.5-10mol%。
本发明的复合高分子电解质组合物在共混聚合物的情况下,可以认为是含有电荷移动离子源的熔融盐单体和补强材料聚合物间产生微细相分离,发挥赋予各自离子电导性力学性质的功能。含有补强材料的多孔质片材或是薄膜时,含有电荷移动离子源的单体连续相承担离子电导性。
本发明的复合高分子电解质组合物,例如被夹在锂离子电池、燃料电池、色素增感太阳电池、电解电容器等电化学装置的相向电极之间。各装置所使用的电极为这些技术领域中所熟知的电极。
例如,锂离子电池的典型例子中使用的是,具备由能吸藏放出锂离子的石墨碳材料所构成的活性物质层的负极,和具有由含有锂的复合金属氧化物所构成的活性物质层的正极,所述复合金属氧化物以LiCoO2、LiFeO、LiNinCo1-n、LiMn2O4等为代表,能吸藏放出锂离子。当作为负极活性物质使用金属锂或是其合金时,正极活性物质可以使用如二氧化锰、TiS2、MoS2、NbS2、MoO3以及V2O5等不含Li的金属氧化物或硫化物。
燃料电池中,一般使用赋加了以Pt为代表的催化剂的多孔质电极。作为色素增感太阳电池的作用极,可以使用在具有导电性表面的基板上形成的TiO2、ZnO等氧化物半导体膜上吸附色素而成的半导体电极。对极是以铂蒸镀玻璃基板为代表的导电性电极。电容器的电极对可以使用与以往的液型电解电容器中所使用的电极对相同的电极。
实施例
以下举出实施例来证明本发明,但本发明并不限于此。这些实施例中以锂离子电池的电解质为目标,但是如上所述,本领域技术人员通过变更电荷移动离子源,可以容易地修饰这些实施例,从而将共应用于其他电化学装置。
实施例中所有的份及%,若没有特别记载都以重量为基准,实施例中的测定是依照下述的方法进行。
离子电导率:在电极面积为0.95cm2的铂电极间夹住试料,在室温、65%RH下,使用交流阻抗法(0.1V,频率1Hz-10MHz)测定膜电阻,算出离子电导率。
拉伸强度:使用A&D社制的拉伸试验机TENSIRONRT1350,以23℃、5cm/min进行测定。
另外,在实施例中所合成的化合物是使用IR光谱、NMR光谱来加以监定。
实施例1
1—甲基—3-(4—乙烯基苄基)咪唑鎓双{(三氟甲基)磺酰}胺(1-methy1-3-(4-vinylbenzyl)imidazolium bis{trifluoromethyl}sulfonyl)amide)[简称为MVBI.TFSI]的合成
在200ml的1,1,1—三氟乙烷中溶解1—甲基咪唑(1—methylimidazole)37.0克(0.45mol),在室温搅拌的同时,用1小时滴入在100ml的1,1,1—三氟乙烷中溶解了对一氯甲基苯乙烯(p-chlorometylstyrene)68.7g(0.45mol)所成的溶液,进而在65℃连续搅拌l 0小时使其进行反应。分离生成物,每次以100ml的1,1,1—三氯乙烷(1,1,1-trichloroethane)清洗生成物二次後,在65℃、0.1mm下乾燥2小时,得到淡黄色的固体1—甲基—3-(4—乙烯基苄基)咪唑鎓氯化物(1-methy1-3-(4-Vinylbenzyl)imidazolinmchloride)[简称MVBI.Cl]52.8g(50%)。
接着,在100ml的水中在70℃下溶解钾双{(三氟甲基)磺酰}}胺(Kaliumbis{(trifluoromethyl)sufonyl}amide)(简称KTFSI)31.9g(0.1mol),在50℃下搅拌的同时,用15分钟的时间滴入并混合在50ml水中溶解了由上述得到的MVBI.C123.4g(0.1mol)所得到的溶液。在50℃下激烈搅拌的同时,进一步进行复分解反应2小时,之后,分离生成的油层。分别以50ml的水清洗生成物二次后,在60℃、0.1mmHg下干燥2小时,得到1—甲基—3-(4—乙烯基苄基)咪唑鎓双{(三氟甲基)磺酰}胺(1-methy1-3-(4-vinylbenzyl)imidazoliumbis{(trifluoromethyl)sufonyl}amide)(简称为MVBI.TFSI)40.8g(收率85%)。
实施例2
含有碳一碳双键的聚偏氟乙烯(polyVinylidene)改性聚合物[简称为DBF]的合成
在附有搅拌器的300ml三口烧瓶中加入日本阿多非纳(株)制聚偏氟乙烯(Kynar461)15g与N—甲基吡咯烷酮—2(N-methyl pyrrolidone-2)[NMP]85g,在90℃下溶解。以同温度搅拌的同时,以约10分钟时间,滴入三乙胺(triethylamine)2.37g。进而在同温度下搅拌30分钟使其反应。冷却后,在搅拌下加入到300ml的水中,使其再沈淀。分别以500ml的水,二次含浸、清洗所沈淀得到的聚合物,过滤,在60℃下真空干燥10小时。
使用NMR光谱分析回收的聚合物,得知约导入了8mol%的双键。
实施例3
调制在二甲基乙酰胺(dimethyl acetoamide)80g中溶解实施例1中得到的1—甲基—3-(4—乙烯基苄基)咪唑鎓双{(三氟甲基)磺酰}胺[简称为MVBI.TFSI]8.4g及实施例2中得到的聚偏氟乙烯(Polyvinylidene)改性聚合物[简称为DBF]10.0g、过氧化苯甲酰0.17g而成的溶液。在此溶液中溶解锂双{(三氟甲基)磺酰}胺(lithiumbis {(trinuoromethyl)sulfonyl}amide)[简称LiTFSI]4.0g,调制电解质前体液(precursor liquid)。在100μm的聚酯薄膜(日本TORAY制T型)上涂布该溶液,以热风干燥机在130℃加热30分钟,干燥的同时进行聚合反应。将涂布膜由聚酯薄膜剥离,得到膜厚为25μm的透明薄膜。此薄膜的离子电导率在20℃下为2.1×10-3S/cm,拉伸强度为11MPa。
实施例4
采用与实施例1相同的方法,由三乙基胺(triethyl amine)和对一氯甲基苯乙烯(p-chlorometylstyrene)合成三乙基—(4—乙烯基苄基)铵氯化物(triethyl-(4-vinylbenzyl)ammonium chloride),进而将此与KTFSI反应,合成三乙基—(4—乙烯基苄基)铵·双{(三氟甲基)磺酰}胺(triethyl-(4-Vinylbenzyl)ammoniumbis{(trifluoromethyl)sulfonyl}amide)[简称TEVBA·TFSI]。
接着,在二甲基乙酰胺(dimethyl acetoamide)80g中溶解上述中得到的TEVBA·TFSI 7.0g、日本阿多非纳(株)制聚偏氟乙烯(Kynar461)13g、过氧化苯甲酰0.14g、LiTFSI 7.0g来调制电解质前体液。在3mm的玻璃板上涂布该溶液,与玻璃板一同以热风干燥机在130℃加热30分钟,进行干燥和聚合反应。将涂布膜由玻璃板剥离,得到膜厚30μm的薄膜。该薄膜的离子电导率为3.0×10-4S/cm,拉伸强度为6MPa。
实施例5
多孔质聚偏氟乙烯(polyvinylidene)薄膜。
制造在二甲基乙酰胺(dimethyl acetoamide)450g中溶解聚偏氟乙烯树脂(日本吴羽化学杜制、#1700)50g及聚乙二醇(分子量1000)50g而成的溶液,在3mm厚的玻璃板上涂布该溶液。与玻璃板一同放入热风干燥机中,在150℃加热10分钟,干燥后冷却至室温,接着在室温、大量的水中浸渍30分钟,经萃取去除了聚乙二醇。换成新鲜的水之后再浸渍30分钟进行水洗,然后在100℃干燥30分钟,得到聚偏氟乙烯的穿孔薄膜,该薄膜的厚度为25μm、空穴率为59%,平均孔径为5μm(用扫描型电子显微镜照片评价)。
实施例6
采用与实施例1相同的方法,由1—乙烯基咪唑(1-vinylimidazole)与乙基溴(ethyl bromide)合成1—乙烯基—3—乙基咪唑鎓溴化物(1—vinyl-3-ethylimidazoliumbromide)[简称EVI·Br]。由EVI·Br与钾双{(三氟甲基)磺酰}胺(Kaliumbis{(trifluoromethyl)sufonyl}amide)(简称KTFSI)合成1—乙烯基—3—乙基咪唑鎓双{(三氟甲基)磺酰}胺(1-vinyl-3-ethylimidazoliumbis{(trifluoromethyl)sufonyl}amide)[简称EVI·TFSI]。
接着,在该EVI·TFSI 42g中溶解LiTFSI 15g、过氧化苯甲酰0.8g成为溶液,用此溶液真空含浸由上述所制成的穿孔薄膜。含浸率为57%。含浸率由含浸率%={(含浸后的重量一含浸前的穿孔薄膜的重量)/含浸后的重量}×100求得。另外,由气孔率和含浸液的比重计算得到的理论含浸率为55%。
在130℃加热该含浸薄膜30分钟进行聚合,制造复合薄膜。
该复合薄膜的离子电导率为6.5×10-4S/cm,拉伸强度为12MPa。
实施例7
锂离子电池
高分子复合电解质前体液的调制:采用与实施例1相同的方法,由烯丙基溴(allyl bromide)与1—甲基咪唑(1-methylimidazole)合成1—烯丙基—3—甲基咪唑鎓溴化物(1-allyl-3—methylimidazoliumbromide),将其与钾双{(三氟甲基)磺酰}胺(Kaliumbis{(trifluoromethyl)sufonyl}amide)(简称KTFSI)反应,合成1—烯丙基—3—甲基咪唑鎓双{(三氟甲基)磺酰}胺(1-allyl-3—methylimidazolium bis{(trifluoromethyl)sufonyl}amide)[简称AMI·TFSI]。同样地,由二烯丙基一二甲基铵溴化物(diallyl-dimethylammoniumbromide)和KTFSI合成二烯丙基一二甲基铵双{(三氟甲基)磺酰}胺(diallyl-dimethylammonium bis{(trifluoromethyl)sufollyl}amide)[简称DAA·TFSI]。
在N—甲基吡咯烷酮—2(N-methylpyrrolidone-2)95g中溶解上述AMI·TFSI 2.4g、DAA·TFSI 2.4g、LiTFSI 2.0g、过氧化苯甲酰0.24g、日本阿多非纳(株)制聚偏氟乙烯(Kynar#461)5.0g。
正极的制作:
向上述高分子复合电解质前体溶液中混合正极活性物质LiCoO2和导电剂乙炔黑制成正极合剂液,将其涂布在集电体铝箔上,在130℃加热10分钟干燥,之后施加压力,使正极合剂厚度达到90μm。
负极的制作:
向上述高分子复合电解质前体溶液中混合负极活性物质天然石墨和导电剂ケツチ工ン碳黑,制成负极合剂液,将其涂布在作为集电体的铜箔上,在130℃加热l0分钟进行干燥,之后施加压力,使负极合剂厚度达到90μm。
电极间电解质膜:
在100μm的聚酯薄膜(日本TORAY制T型)上,涂布上述高分子复合电解质前体液,在130℃加热30分钟使其干燥并同时聚合,在聚酯薄膜上形成膜厚为30μm的高分子复合电解质膜。
在上述的正极涂布面上,重叠上述复合电解质膜面,在130℃的辊之间进行层叠后,将聚酯薄膜剥离,制成正极/电解质膜层叠片材。在此层叠片材的电解质膜面上,重叠上述负极的涂布面,同样地,在130℃的辊之间进行层叠,制成正极/电解质膜/负极层叠体。在150℃×10kg/cm2的条件下对此层叠体进行30分钟的加热压接,同时使其聚合。
以15mm的直径打穿该层叠体,放入铝制容器中,重叠同材料的弹簧和盖子,加压后制成钱币型电池。
接着使用该钱币型电池,在20℃下进行充放电循环试验。
充放电循环试验条件:充电是在电流1mA、终止电压为4.0V的条件下进行恒电流充电。放电是在电流1mA、终止电压为2.5V的条件下进行恒电流放电。
将与电池设计容量的比值设为放电容量(%),充放电初期的放电容量为95%,在第20循环也可以保持85%的放电容量。
Claims (10)
1.一种锂离子电池用复合高分子电解质组合物,其特征在于,在电化学惰性的高分子补强材料的存在下,使含有熔融盐单体和锂盐的单体组合物进行聚合而制得,所述熔融盐单体具有由季铵阳离子和含氟阴离子构成的季铵盐结构和聚合性官能团,所述锂盐由锂阳离子和含氟阴离子构成,所述电化学惰性的高分子补强材料为聚偏氟乙烯及其共聚物、其改性聚合物。
2.如权利要求1所述的复合高分子电解质组合物,其中所述单体组合物中含有能与所述熔融盐单体共聚的多官能单体。
3.如权利要求1所述的复合高分子电解质组合物,其中所述熔融盐单体是,从1-乙烯基-3-烷基咪唑鎓阳离子、4-乙烯基-1-烷基吡啶鎓阳离子、1-烷基-3-烯丙基咪唑鎓阳离子、1-(4-乙烯基苄基)-3-烷基-咪唑鎓阳离子、1-(乙烯基氧乙基)-3-烷基-咪唑鎓阳离子、1-乙烯基咪唑鎓阳离子、1-烯丙基咪唑鎓阳离子、N-烯丙基苯并咪唑鎓阳离子、以及二烯丙基二烷基季铵阳离子中选出的季铵阳离子;和从双{(三氟甲基)磺酰}胺阴离子、2,2,2-三氟-N-(三氟甲基磺酰)乙酰胺阴离子、双{(五氟乙基)磺酰}胺阴离子、双{(氟)磺酰}胺阴离子、四氟硼酸盐阴离子、以及三氟甲烷磺酸盐阴离子中选出的阴离子的盐。
4.如权利要求1所述的复合高分子电解质组合物,其中所述高分子补强材料与所述熔融盐单体的聚合物形成共混聚合物。
5.如权利要求1所述的复合高分子电解质组合物,其中所述高分子补强材料,是含有连续细孔的多孔质薄膜或片材,所述熔融盐单体的聚合物在该多孔质薄膜或片材中形成连续相。
6.如权利要求1所述的复合高分子电解质组合物,其中所述单体组合物可以在热的作用下进行聚合。
7.如权利要求1所述的复合高分子电解质组合物,其中所述单体组合物可以在紫外线照射下进行聚合。
8.如权利要求1所述的复合高分子电解质组合物,其中所述单体组合物可以在电子射线的照射下进行聚合。
9.如权利要求1所述的复合高分子电解质组合物,其中所述锂盐是从LiBF4、LiPF6;CnF2n+1CO2Li,其中n是1-4的整数;CnF2n+1SO3Li,其中n是1-4的整数;(FSO2)2NLi;(CF3SO2)2NLi;(C2F5SO2)2NLi;(CF3SO2)3CLi;(CF3SO2-N-COCF3)Li;以及(R-SO2-N-SO2CF3)Li,R是烷基或芳基;中选出的锂盐。
10.一种锂离子电池,其中具有在相向的负极与正极间配置的权利要求9的复合高分子电解质组合物。
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US6878475B2 (en) * | 2002-11-22 | 2005-04-12 | T/J Technologies, Inc. | Membrane for fuel cell, and fuel cell incorporating that membrane |
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2004
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Also Published As
Publication number | Publication date |
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CN1934657A (zh) | 2007-03-21 |
JP4674660B2 (ja) | 2011-04-20 |
TW200503304A (en) | 2005-01-16 |
CA2507438C (en) | 2013-08-06 |
EP1612809A4 (en) | 2009-03-25 |
WO2004088671A1 (ja) | 2004-10-14 |
JPWO2004088671A1 (ja) | 2006-07-06 |
EP1612809A1 (en) | 2006-01-04 |
TWI343138B (en) | 2011-06-01 |
CA2507438A1 (en) | 2004-10-14 |
EP1612809B1 (en) | 2015-08-19 |
US20060057465A1 (en) | 2006-03-16 |
US7732099B2 (en) | 2010-06-08 |
KR101211455B1 (ko) | 2012-12-12 |
KR20050114607A (ko) | 2005-12-06 |
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