WO1993026057A1 - Materiau a conduction ionique, comportant comme solvant un copolymere bloc - Google Patents
Materiau a conduction ionique, comportant comme solvant un copolymere bloc Download PDFInfo
- Publication number
- WO1993026057A1 WO1993026057A1 PCT/FR1992/000542 FR9200542W WO9326057A1 WO 1993026057 A1 WO1993026057 A1 WO 1993026057A1 FR 9200542 W FR9200542 W FR 9200542W WO 9326057 A1 WO9326057 A1 WO 9326057A1
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- WO
- WIPO (PCT)
- Prior art keywords
- segment
- material according
- radical
- block copolymer
- group
- Prior art date
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 title claims abstract description 14
- 239000004020 conductor Substances 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 38
- -1 oxymethylene, oxetane Chemical class 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 19
- 150000003254 radicals Chemical class 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 125000003010 ionic group Chemical group 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- CALBZAJAQLUBHG-UHFFFAOYSA-N ethenylsulfamic acid Chemical class OS(=O)(=O)NC=C CALBZAJAQLUBHG-UHFFFAOYSA-N 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- 150000004291 polyenes Chemical group 0.000 claims description 3
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- RUGWIVARLJMKDM-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)furan Chemical compound C1OC1COCC1=CC=CO1 RUGWIVARLJMKDM-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002892 organic cations Chemical class 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920006301 statistical copolymer Polymers 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- OHNNZOOGWXZCPZ-UHFFFAOYSA-N exo-norbornene oxide Chemical compound C1CC2C3OC3C1C2 OHNNZOOGWXZCPZ-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 2
- MUUOUUYKIVSIAR-UHFFFAOYSA-N 2-but-3-enyloxirane Chemical compound C=CCCC1CO1 MUUOUUYKIVSIAR-UHFFFAOYSA-N 0.000 description 2
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BVHMITOWPMCRLY-HZJYTTRNSA-N (6z,9z)-18-chlorooctadeca-6,9-diene Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCCl BVHMITOWPMCRLY-HZJYTTRNSA-N 0.000 description 1
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- UKTHULMXFLCNAV-UHFFFAOYSA-N 2-hex-5-enyloxirane Chemical compound C=CCCCCC1CO1 UKTHULMXFLCNAV-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000909 amidinium group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229920005605 branched copolymer Polymers 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 150000005217 methyl ethers Chemical class 0.000 description 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
-
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- Ionically conductive material comprising as solvent a block copolymer.
- the present invention relates to ionically conductive materials and their uses.
- the polymer electrolytes obtained by dissolving a salt in a solvating polymer comprising heteroatoms are known.
- Such electrolytes, the solvent of which is a polyethylene oxide or a copolymer of ethylene oxide are described for example in EP 13199 (M. Armand, M. Duclot).
- These polymer electrolytes have numerous applications, in particular in the field of electrochemical generators, light modulation systems (M. Armand et al, EP-87401555), sensors, for example for selective or reference membranes.
- ⁇ rence A. Hammou et al, FR-86.09602.
- Polyethylene oxide is a semi-crystalline polymer which forms with salts stoechio etric complexes.
- the conductive amorphous phases of these complexes only exist above a eutectic temperature generally between 40 "C and 65 ° C depending on the nature of the complexed salts.
- Good conductivities at ordinary temperature are only obtained with macromolecular systems with little or no crystallinity. Numerous studies have been carried out to improve the conduction properties of these materials. They have resulted, for example, in the formation of copolymers based on ethylene oxide (M. Armand et al, FR-83.09886).
- REPLACEMENT SHEET amorphous with good conductivity, but poor mechanical strength [CV Nicholas, DJ ilson, C. Booth & RJM Gilles, Brit. Polym. J. ⁇ > 289 (1988)].
- these materials do not have reactive functions and therefore cannot be crosslinked.
- they are easily degraded in an acid medium.
- the present invention aims to provide ionically conductive materials comprising a solid electrolyte and having both good conductivity and good mechanical strength.
- the subject of the invention is an ionically conductive material comprising a salt in solution in a solid polymer electrolyte.
- the invention also relates to various uses of said material.
- the ionically conductive material according to the present inven ⁇ tion comprises at least one salt dissolved in a polymer solvent. It is characterized in that the polymer solvent consists essentially of a block copolymer comprising at least one solvating segment A and at least one segment B having good intrinsic mechanical properties or after crosslinking between several segments B.
- the block copolymer constituting the solvent for a material according to the present invention can have different shapes.
- the segment A of the block copolymer is a solvating segment which gives the material its conductivity properties.
- the mass of the polymer segment is preferably between 150 and 20,000, more particularly between 150 and 10,000.
- the segment A consists of units deriving from monomers of the ether, ester or amine type.
- the segment A is derived from a homopolymer of ethylene oxide or from a statistical or trendy copolymer consisting essentially of ethylene oxide units.
- the copolymers those which contain at least 70% of ethylene oxide units, relative to the total number of monomer units, are particularly preferred.
- the comonomers are chosen from the monomers which retain the solvating nature of the segment A. By way of example, mention may be made of propylene oxide, oxymethylene, oxetane, tetrahydrofuran, dioxolane and glycidyl alkyl ethers.
- Segment B is intended to give the material the mechanical properties required for the use of said material as a solid electrolyte in the form of thin films. These properties are obtained either by the rigidity of the chain constituting the segment B, or by the functional groups present on B and allowing the crosslinking or crystallization of the segments B with one another.
- a segment B can consist of a mainly hydrocarbon radical.
- a polyene an alkyl group CpH 2 p + ⁇ , an acyl group Cp_ _H 2 p- ⁇ CO, an alkylaryl group CpH 2 p- ⁇ - ⁇ , an alkylaroyl group CpH2p + ⁇ , a alkenyl group CpH 2 p--, an alkenoyl group Cp __. 1H2p-.3CO, p being an integer less than 31, q being an odd integer less than p.
- Segment B can also be derived from a polymer of at least one monomer chosen from styrene, ⁇ -methylstyrene and their derivatives, styrene oxide, exo-2,3 epoxynorbornane, phenylglycidyl ether, 1-epoxy-3-phenoxypropane, ethylene sulfide, 1 allyl-glycidyl ether, acrylate or glycidyl methacrylate, epoxyalkenes, furfuryl-glycidyl ether, 1 acrylonitrile, methacrylonitrile, acrylates and ionic methacrylates or precursors of ionic groups corresponding respectively to the formulas below in which X represents an alkyl radical, an alkenyl radical, a metal or a radical -SiR ⁇ ,
- R represents an alkyl radical having a number of carbon atoms less than 6.
- R ' represents a methyl radical.
- Particularly preferred epoxyalkenes are butadiene monoxide, 1,2 epoxy-5-hexene, 1,2 epoxy-7-octene.
- Exo-2,3 epoxynorbornane the formula of which is given below, styrene oxide and phenylglycidyl ether are particularly preferred monomers for the preparation of segment B.
- R represents an organic radical having from 1 to 10 atoms of carbon.
- the radical R is advantageously a trimethylene methane radical, a trimethylene ethane radical, a trimethylene propane radical or a pentaerythrityl radical whose formulas are given below in order, or a glyceryl radical.
- the materials of the present invention are particularly advantageous when the solvent is a branched polymer.
- This particular structure of the copolymer makes it possible to simultaneously increase the local concentration in solvating segments at several points in space, and the probability of good crosslinking between several segments B when these are either derived from crosslinkable monomers, either represent a mainly unsaturated hydrocarbon radical.
- the structure of these branched polymers promotes crystallization between them of the B segments when these represent mainly saturated hydrocarbon radicals.
- These branched copolymers more easily retain the amorphous nature of the segment A favorable to conductivity.
- a process for the preparation of a type AB or type BAB copolymer consists in first of all preparing a precursor polymer of segment A from the appropriate monomer (s). This preparation can be carried out by anionic or cationic polymerization or by polycondensation, depending on the nature of the reactive functions carried by the monomers. It is also possible to use commercial polymers such as, for example, polyethylene glycols with a mass of 400, 600, 1000, 1500, 2000 or 20000 supplied by Aldrich. Polymers having a mass of about 2000 are particularly preferred.
- the precursor polymer of segment A carries reactive terminal functions for the grafting of segment B.
- segment B is fixed on segment A by the reaction appropriate to the reactive functions, according to methods known to those skilled in the art. .
- segment B is an essentially hydro ⁇ carbon radical such as a polyene, an alkyl group CpH 2 p + ⁇ , an acyl group Cp_ 1 H 2 p- ⁇ CO, an alkylaryl group Cp ⁇ p + i ⁇ , an alkylaroyl group CpH2p + ⁇ , an alkenyl group CpH2p-q, an alkenoyl group Cp_ ⁇ H 2 p-3 c0 il " is fixed on A by a condensation reaction via appropriate reactive functions present at the ends of A.
- an alkyl group CpH 2 p + ⁇ an acyl group Cp_ 1 H 2 p- ⁇ CO
- an alkylaryl group Cp ⁇ p + i ⁇ an alkylaroyl group CpH2p + ⁇
- an alkenyl group CpH2p-q an alkenoyl group Cp_ ⁇ H 2 p-3 c0 il
- segment B is a radical derived from a polymer of at least one monomer
- two methods are possible: either segment B is first prepared by polymerization of the chosen onomer (s), then the segment B is grafted onto A by means of appropriate reactive functions present at the ends of A; either segment A is brought into contact with the monomer (s) constituting B, and polymerization is initiated either by the anionic route or by the radical route, depending on the reactive functions present on A. This latter route can also be used when segment B is a polyene radical.
- the reactive ends of the precursor polymer of segment A can be hydroxyl radicals -OH, amino groups - NHR, carboxylic groups -COOH. These reactive ends, after treatment with a deprotonating base such as NaH, KH, KOC (CH3) 3, KOH , Na + [naphthalene], serve to initiate an anionic polymerization of the reactants constituting B.
- a deprotonating base such as NaH, KH, KOC (CH3) 3, KOH , Na + [naphthalene
- groups generating free radicals are grafted to the reactive ends of the precursor polymer of segment A by means of molecules containing for example azo groups, peroxide, disulfide.
- molecules containing for example azo groups, peroxide, disulfide mention may be made of azobis (cyanovaleric) acid, peroxybenzoic acid, dithiodipropionic acid.
- azobis (cyanovaleric) acid peroxybenzoic acid, dithiodipropionic acid.
- These molecules are easily transformed into their corresponding esters or amides by reaction on the OH or RNH functions of the ends of the solvating segment A precursors in the presence of molecular dehydrating agents such as, for example, dicyclohexyl carbodiimide, carbonyl diimidazole, carbonate succinimidyle.
- the segment A precursor thus functionalized is brought into contact with the monomers intended to constitute segment B at the temperature of dissociation into free radicals, preferably at a temperature between 50 °
- the triblock copolymers BAB 'in which B is different from B' can be obtained according to different methods. For example, one of the reactive ends of the precursor polymer of segment A is protected; then segment B is grafted by the routes described above, then after deprotection of the second reactive end, segment B 'is grafted. Another method consists in using a preformed segment AB ′ preformed, then in grafting a segment B on the reactive end of A. It is also possible to use a polymer precursor of segment A having two different reactive ends.
- the monomers which can be used to form segment B by the radical route are advantageously chosen from styrene, 1 '-methylstyrene and their derivatives, acrylonitrile, methacrylonitrile, ionic acrylates and methacrylates or precursors of ionic groups, vinylsulfonates or vinylsulfamates ionic or precursors of ionic groups.
- a process for the preparation of BA or ABA copolymers consists in first of all preparing a precursor polymer of segment B by polymerization of the monomer (s) constituting it, or else a precursor of a mainly hydro ⁇ carbon radical is used. Then the segment (s) A is added.
- segment A is first prepared by polymerization of the chosen monomer (s), or else a commercial polymer such as a polyethylene glycol or an ethylene oxide copolymer is used as segment A, then the segment A is grafted onto B by means of appropriate reactive functions present at the ends ⁇ mites of B; either the precursor of segment B, which has reactive ends, is brought into contact with the monomer (s) constituting A, and polymerization is initiated either by an anionic route, or by cationic route, or by polycondensation, according to the reactive functions present on the precursor of segment B and on the monomers intended to constitute A.
- Block copolymers of the type A'BA when A is different from A ' can be prepared by routes analogous to those which allow the preparation of the copolymers BAB '.
- a process for the preparation of copolymers of type (AB) n R, or (BA) n R consists in reacting the precursor compound of group R with multiple functionality with the monomer (s) intended to constitute A for prepare a branched polymer A n R or with the monomer (s) intended (s) to constitute B to prepare a branched polymer B n R. Then graft respectively ve the segments B or A by one of the two routes mentioned above: preliminary preparation of the segment to be grafted then grafting; or bringing the entity A n R or the entity B n R into contact respectively with the monomer (s) intended to constitute the segment B or the monomer (s) intended ( s) to constitute segment A.
- the block copolymers obtained present residual reactive groups. It is preferable to deactivate them by transformation into ether, ester or amide groups in order to avoid the formation of parasitic reactions when using the material of the invention.
- the materials of the present invention also contain a salt dissolved in the block copolymer.
- the salt can be chosen from the salts usually used for solid materials with ionic conduction.
- X representing an anion with delocalized electronic charge, for example Br ⁇ , ClO ⁇ -, R F S0 3 ⁇ or (R F S0 2 ) 2 N;
- R F representing a perfluoroalkyl or perfluoroaryl group.
- Mixtures of salts can be used.
- additives can be added to the material of the present invention to modify the properties of the final material.
- a plasticizing agent such as ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, dimethylformamide, N-methylpyrrolidone, tetraalkylsulfamide ⁇ , methyl ethers of polyethylene glycols of mass between 200 and 2000 and, in general, derivatives of polar molecules of low volatility.
- the proportion of these additives can range from 1 to 90% of the total mass.
- the ion-conducting materials of the present invention are particularly useful as an electrolyte in various electrochemical systems.
- electrolyte in various electrochemical systems.
- EXAMPLE 1 To 40 g of commercial poly (ethylene glycol) of mass 1000 (sold by Aldrich under the reference 20,242-8) 5 ml of 2,2-dimethoxypropane are added. Next, the mixture is dried in a rotary evaporator at 60 ° C. to remove the residual water from the polymer. Operating in a glove box under an inert atmosphere, 5 g of the poly (ethylene glycol) thus dehydrated are introduced into solution in 25 ml of anhydrous THF in a container which can be hermetically sealed, and 0.3 g of sodium hydride is added thereto. The end of the evolution of hydrogen indicates that all of the terminal OH groups are metallized. styrene oxide and the mixture is stirred at 55 ° C. for 6 hours in the closed container The block polymer obtained is separated by precipitation in a 50/50 ether / hexane mixture.
- EXAMPLE 2 A solution of 20 g of commercial polyethylene glycol of mass 2000 (marketed by Aldrich under the reference 29.590-6) in 150 ml of toluene is prepared. The solution obtained is dried by azeotropic dehydration. Then added 5.5 g of palmitoyl chloride and 10 ml of pyridine. The mixture obtained is stirred at ordinary temperature for 3 hours, then the precipitate of pyridinium hydrochloride formed is removed by filtration. The block polymer obtained, which corresponds to the formula C 16 H 33 C0 2 (C 2 H 0) n C0C 16 H 33 > n being of the order of 44, is separated by precipitation in ether.
- This polymer is in the form of a fusible wax at 45 "C. 5 g of the block copolymer obtained and 1.7 g of lithium salt of bis (trifluoromethanesulfonimide) are dissolved in 10 ml of methyl formate. After evaporation of the solvent , we obtain a material with an ionic conductivity of 2.10 -5 ( ⁇ cm) -1 at 25 ° C.
- EXAMPLE 3 A block copolymer is prepared according to the procedure of Example 2, but replacing palmitoyl chloride with 6 g of linoleyl chloride.
- the polymer obtained, after complexation with the lithium salt used in Example 2 is mixed with 0.3% by weight of benzoyl peroxide. After shaping by spreading in a film 30 ⁇ m thick, the material is heated at 80 ° C for 8 hours.
- the crosslinked product obtained is a material having both good mechanical properties and good ionic conductivity [1.4.10 -5 ( ⁇ cm) -1 at 25 ° C].
- EXAMPLE 4 60 g of commercial polyethylene glycol of mass 1500 (sold by Aldrich under the reference 20,243-6) are dried with 10 ml of 2,2-dimethoxypropane; the excess dehydrating agent, the methanol and the acetone formed are eliminated under reduced pressure. In a glove box under an inert atmosphere, the polymer is dissolved in 300 ml of anhydrous THF and then 3.9 g of sodium hydride is added with stirring. The metallation reaction is complete in 4 hours, which is indicated by the end of the evolution of hydrogen. The mixture is cooled to 0 ° C. and 40 g of ethylene sulfide are then gradually added while stirring is maintained.
- the container is hermetically sealed and the polymerization is complete after 2 hours at ordinary temperature.
- the polymer obtained is precipitated in ether and purified by washing in isopropanol, dissolution in dichloromethane, centrifugation and reprecipitation in hexane.
- EXAMPLE 5 A random copolymer of ethylene oxide and propylene oxide is obtained by cationic initiation with boron trifluoride. 4 g of this copolymer, having a mass of 1600 and containing 15% of propylene oxide units are metallized under the conditions of Example 1 with 0.6 g of potassium tert-butoxide, instead of sodium hydride. To the reaction mixture, 3.3 g of exo-2, 3-epoxynorbornane are added, and the temperature is maintained at 60 ° C. for 3 hours. The block copolymer obtained is precipitated with ether and washed by trituration in isopropanol containing 1% of acetic acid, then dried under vacuum at 60 ° C.
- Lithium trifluorosulfonate is dissolved in the block poly ⁇ mother obtained at a concentration corresponding to a ratio of oxygen atoms in the solvating segment / Li atoms of 16/1.
- the ionic conductivity of the material obtained is 1.1.10 " ⁇ ( ⁇ cm) - 1 at 44 ° C.
- Example 7 70 g of polyethylene glycol with a mass of 2000 (sold by Aldrich under the reference 29.590-6) are dehydrated according to the procedure of Example 1. To the solution in THF of the dehydrated polyethylene glycol, 3 g of hydride is added. potassium, then 25 ml of allyl glycidyl ether. The mixture is maintained at 50 ° C. for 2 hours, then the polymer is precipitated in ether and purified by dissolution in acetone and precipitation in ether three times.
- a crosslinked membrane is prepared by dissolving the polymer and 1% by weight of benzoyl peroxide in acetone and spreading using a template. After evaporation of the acetone, the polymer is heated at 80 ° C for 2 hours under an argon atmosphere. An elastic membrane of crosslinked poly ⁇ is obtained. The material becomes ionic conductor after immersion of the membrane in a 1 M solution of the lithium salt of bis (trifluoromethanesulfonimide) in acetone, the volume of the solution being calculated to correspond to an O / Li ratio of 15/1. The membrane obtained has an ionic conductivity of 1.1.10 -4 ( ⁇ cm) -1 at 50 ° C.
- EXAMPLE 7 10 g of ⁇ , C-diaminopoly (oxypropyleneoxyethylene) of mass 4000 (Jeffamine® ED 4000, Texaco Corporation) are dissolved in 75 ml of 1 acetonitrile and 15 ml of pyridine. 1.2 g of dicyclohexylcarbodii ide and 0.75 g of azobis (cyanovaleric) acid are added. The mixture is stirred for 9 hours at ordinary temperature. The precipitate of dicyclohexylurea formed is removed by centrifugation and a polyamide is obtained by precipitation in ether.
- EXAMPLE 8 80 g of polybutadiene diol of mass 1000 containing 20% of vinyl groups, 20% of cis double bonds and 60% of trans 1,4 double bonds (marketed by Aldrich under the reference 19.079-9) are dissolved in 500 ml of Anhydrous THF in a sealed reactor and 7 g of potassium hydride are added. After the end of the metallation reaction of the OH ends, 180 g of ethylene oxide are gradually added so as to maintain the temperature below 80 "C. When the polymerization reaction is complete, the polymer is added to the co ⁇ obtained 8% by weight of lithium trifluoromethane sulfonate and 0.5% of benzoyl peroxide After spreading this mixture and heating under argon at 110 ° C. for 2 hours, a crosslinked membrane is obtained which has elasticity. is greater than 10 -4 ( ⁇ cm) -1 at 55 ° C.
- EXAMPLE 9 11 g of polyoxyethylene 20 monocetyl ether (BRU® 58 from the company ICI) are dried under vacuum at 60 ° C. and then dissolved in a 50/50 toluene / THF mixture. A solution of naphthalene-sodium is added dropwise until the green color characteristic of the anion radical C ⁇ Q H Q ⁇ persists, then 4 g of 1,2-epoxy-5-hexene are added. The polymerization by opening the epoxy cycle is carried out in 1 hour at ordinary temperature. The cetyl-polyethylene oxide-1,2-epoxy-5-hexene block polymer is separated by precipitation in ethyl ether at -10 ° C.
- BRU® 58 from the company ICI
- This membrane can be used for the manufacture of electrochromic glazings based on Prussian blue K x Fe (CN) 6 , used to modulate the light fluxes by application of an electrical voltage.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CA002138372A CA2138372C (fr) | 1992-06-16 | 1992-06-16 | Materiau a conduction ionique, comportant comme solvant un copolymere bloc |
US08/351,312 US5523180A (en) | 1992-06-16 | 1992-06-16 | Ionically conductive material having a block copolymer as the solvent |
PCT/FR1992/000542 WO1993026057A1 (fr) | 1992-06-16 | 1992-06-16 | Materiau a conduction ionique, comportant comme solvant un copolymere bloc |
Applications Claiming Priority (1)
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PCT/FR1992/000542 WO1993026057A1 (fr) | 1992-06-16 | 1992-06-16 | Materiau a conduction ionique, comportant comme solvant un copolymere bloc |
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Cited By (6)
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EP0769212A1 (fr) * | 1994-07-22 | 1997-04-23 | Motorola, Inc. | Electrolytes a base de polyurethane destines a des cellules electrochimiques et cellules electrochimiques employant ces electrolytes |
US5916475A (en) * | 1994-03-21 | 1999-06-29 | Centre National De La Recherche Scientifique | Ionic conducting material having good anticorrosive properties |
FR2781932A1 (fr) * | 1998-07-10 | 2000-02-04 | Giat Ind Sa | Electrolyte solide polymere et ses procedes de preparation |
EP1011165A1 (fr) * | 1997-08-22 | 2000-06-21 | Daikin Industries, Ltd. | Batterie secondaire au lithium, electrolyte a base de gel polymere et liant pour batteries secondaires au lithium |
WO2003098205A1 (fr) * | 2002-05-21 | 2003-11-27 | Rhocraft Research And Development Ltd. | Membranes echangeuses d'ions et detecteurs de gaz dissous |
DE19527362B4 (de) * | 1994-07-28 | 2008-01-10 | Centre National De La Recherche Scientifique (C.N.R.S.) | Ionenleitendes makromolekulares Material und dessen Verwendung als Elektrolyt in einer aufladbaren Batterie oder als Bindemittel in einer Verbundelektrode |
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JP2002511179A (ja) * | 1996-10-11 | 2002-04-09 | マサチューセッツ・インスティテュート・オブ・テクノロジー | 電池のための固体電解質、インターカレーション化合物及び電極 |
US6165641A (en) * | 1997-05-09 | 2000-12-26 | The United States Of America As Represented By The United States Department Of Energy | Nanodisperse transition metal electrodes (NTME) for electrochemical cells |
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JP2813834B2 (ja) * | 1990-05-31 | 1998-10-22 | 第一工業製薬株式会社 | イオン導伝性ポリマー電解質 |
DD297281A5 (de) * | 1990-08-14 | 1992-01-02 | Ernst-Moritz-Arndt-Universitaet Greifswald,De | Verfahren zur herstellung polymerer festelektrolyte |
FR2673769B1 (fr) * | 1991-03-07 | 1993-06-18 | Centre Nat Rech Scient | Materiaux polymeriques a conduction ionique. |
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- 1992-06-16 WO PCT/FR1992/000542 patent/WO1993026057A1/fr active Application Filing
- 1992-06-16 CA CA002138372A patent/CA2138372C/fr not_active Expired - Lifetime
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WO1988003154A1 (fr) * | 1986-10-27 | 1988-05-05 | The Secretary Of State For Defence In Her Britanni | Conducteurs ioniques polymeres |
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Cited By (10)
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US5916475A (en) * | 1994-03-21 | 1999-06-29 | Centre National De La Recherche Scientifique | Ionic conducting material having good anticorrosive properties |
US6254797B1 (en) * | 1994-03-21 | 2001-07-03 | Centre National De La Recherche Scientifique | Ionic conducting material having good anticorrosive properties |
EP0769212A1 (fr) * | 1994-07-22 | 1997-04-23 | Motorola, Inc. | Electrolytes a base de polyurethane destines a des cellules electrochimiques et cellules electrochimiques employant ces electrolytes |
EP0769212A4 (fr) * | 1994-07-22 | 1997-10-08 | Motorola Inc | Electrolytes a base de polyurethane destines a des cellules electrochimiques et cellules electrochimiques employant ces electrolytes |
DE19527362B4 (de) * | 1994-07-28 | 2008-01-10 | Centre National De La Recherche Scientifique (C.N.R.S.) | Ionenleitendes makromolekulares Material und dessen Verwendung als Elektrolyt in einer aufladbaren Batterie oder als Bindemittel in einer Verbundelektrode |
EP1011165A1 (fr) * | 1997-08-22 | 2000-06-21 | Daikin Industries, Ltd. | Batterie secondaire au lithium, electrolyte a base de gel polymere et liant pour batteries secondaires au lithium |
EP1011165A4 (fr) * | 1997-08-22 | 2001-01-24 | Daikin Ind Ltd | Batterie secondaire au lithium, electrolyte a base de gel polymere et liant pour batteries secondaires au lithium |
US6387570B1 (en) | 1997-08-22 | 2002-05-14 | Daikin Industries, Ltd. | Lithium secondary battery, polymer gel electrolyte and binder for use in lithium secondary batteries |
FR2781932A1 (fr) * | 1998-07-10 | 2000-02-04 | Giat Ind Sa | Electrolyte solide polymere et ses procedes de preparation |
WO2003098205A1 (fr) * | 2002-05-21 | 2003-11-27 | Rhocraft Research And Development Ltd. | Membranes echangeuses d'ions et detecteurs de gaz dissous |
Also Published As
Publication number | Publication date |
---|---|
CA2138372A1 (fr) | 1993-12-23 |
US5523180A (en) | 1996-06-04 |
CA2138372C (fr) | 2003-08-19 |
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