CA2285007A1 - Method for producing shaped bodies for lithium ion batteries - Google Patents
Method for producing shaped bodies for lithium ion batteries Download PDFInfo
- Publication number
- CA2285007A1 CA2285007A1 CA002285007A CA2285007A CA2285007A1 CA 2285007 A1 CA2285007 A1 CA 2285007A1 CA 002285007 A CA002285007 A CA 002285007A CA 2285007 A CA2285007 A CA 2285007A CA 2285007 A1 CA2285007 A1 CA 2285007A1
- Authority
- CA
- Canada
- Prior art keywords
- mixture
- solid
- compound
- group
- blend
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 128
- 150000001875 compounds Chemical class 0.000 claims abstract description 87
- 239000007787 solid Substances 0.000 claims abstract description 57
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001125 extrusion Methods 0.000 claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 21
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 238000013329 compounding Methods 0.000 claims abstract description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims abstract description 10
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- MJHNUUNSCNRGJE-UHFFFAOYSA-N trimethyl benzene-1,2,4-tricarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(C(=O)OC)=C1 MJHNUUNSCNRGJE-UHFFFAOYSA-N 0.000 claims abstract description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011164 primary particle Substances 0.000 claims abstract description 7
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960001826 dimethylphthalate Drugs 0.000 claims abstract description 5
- -1 polyethylene Polymers 0.000 claims description 97
- 238000000034 method Methods 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 30
- 239000011888 foil Substances 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 20
- 239000007784 solid electrolyte Substances 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 239000004014 plasticizer Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 235000021317 phosphate Nutrition 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- CZDSWLXAULJYPZ-UHFFFAOYSA-J molybdenum(4+);dicarbonate Chemical compound [Mo+4].[O-]C([O-])=O.[O-]C([O-])=O CZDSWLXAULJYPZ-UHFFFAOYSA-J 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 239000007962 solid dispersion Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- FOZHTJJTSSSURD-UHFFFAOYSA-J titanium(4+);dicarbonate Chemical compound [Ti+4].[O-]C([O-])=O.[O-]C([O-])=O FOZHTJJTSSSURD-UHFFFAOYSA-J 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 4
- 229910011623 LiCrTiO4 Inorganic materials 0.000 claims 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims 1
- 229910011687 LiCu Inorganic materials 0.000 claims 1
- 229910010584 LiFeO2 Inorganic materials 0.000 claims 1
- 229910003005 LiNiO2 Inorganic materials 0.000 claims 1
- 229910020042 NbS2 Inorganic materials 0.000 claims 1
- 229910020039 NbSe2 Inorganic materials 0.000 claims 1
- 229910009965 Ti2O4 Inorganic materials 0.000 claims 1
- 229910003092 TiS2 Inorganic materials 0.000 claims 1
- 229910006247 ZrS2 Inorganic materials 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229910052960 marcasite Inorganic materials 0.000 claims 1
- 229910052961 molybdenite Inorganic materials 0.000 claims 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims 1
- 229910052683 pyrite Inorganic materials 0.000 claims 1
- 239000004902 Softening Agent Substances 0.000 abstract 2
- 239000002491 polymer binding agent Substances 0.000 abstract 2
- TUUWVHDHPUNCTO-UHFFFAOYSA-N 2,2,2-tributoxyethyl dihydrogen phosphate Chemical compound CCCCOC(COP(O)(O)=O)(OCCCC)OCCCC TUUWVHDHPUNCTO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 21
- 150000002148 esters Chemical class 0.000 description 20
- 150000001298 alcohols Chemical class 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 150000005846 sugar alcohols Polymers 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 229910002012 Aerosil® Inorganic materials 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229920006370 Kynar Polymers 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 150000001735 carboxylic acids Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 238000003490 calendering Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- FIWILGQIZHDAQG-UHFFFAOYSA-N NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F Chemical compound NC1=C(C(=O)NCC2=CC=C(C=C2)OCC(F)(F)F)C=C(C(=N1)N)N1N=C(N=C1)C1(CC1)C(F)(F)F FIWILGQIZHDAQG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 3
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
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- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- QLNUSZCPEUTHBS-UHFFFAOYSA-N tris(2-methoxyethyl) phosphate Chemical compound COCCOP(=O)(OCCOC)OCCOC QLNUSZCPEUTHBS-UHFFFAOYSA-N 0.000 description 1
- VOSUIKFOFHZNED-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,3,5-tricarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=CC(C(=O)OCC=C)=C1 VOSUIKFOFHZNED-UHFFFAOYSA-N 0.000 description 1
- MWIGYZRZXFMGFN-UHFFFAOYSA-N tris[2-(2-methoxyethoxy)ethyl] phosphate Chemical compound COCCOCCOP(=O)(OCCOCCOC)OCCOCCOC MWIGYZRZXFMGFN-UHFFFAOYSA-N 0.000 description 1
- NPXKBAHNVUNXSI-UHFFFAOYSA-N tris[2-(diethylamino)ethyl] phosphate Chemical compound CCN(CC)CCOP(=O)(OCCN(CC)CC)OCCN(CC)CC NPXKBAHNVUNXSI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
-
- 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
- H01G9/02—Diaphragms; Separators
-
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- Microelectronics & Electronic Packaging (AREA)
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- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for producing shaped bodies, preferably for a film-like shaped body, comprising the following steps: I) compounding and melt extrusion of a mixture (I) comprising a mixture (II) containing a) 1 to 95 wt. % of at least a pigment (III) with a primary particle size ranging from 5 nm to 20mm, selected from the group consisting of one electrochemically inert solid (IIIa), of a compound (IIIb) capable of giving off lithium ions when charged, and a compound (IIIc), capable of receiving lithium ions when charged, and a mixture of solid (IIIa) with compounds (IIIb) or compound (IIIc), b) 5 to 99 wt. % of at least one polymer binding agent (IV), and c) 0 to 200 wt. % of at least one softening agent (V) in relation to the overall amount of constituents a) and b), wherein the weight percentage of mixture (II) in mixture (I) ranges from 1 to 100 wt. %, and excluding mixtures (I) comprising mixtures (II) containing a copolymer consisting of vinylidene fluoride (Vdf) and hexafluoropropylene (HFP) with a HFP content ranging from 8 to 25 wt. % as a polymer binding agent (IV) and a compound as a softening agent (V) which is selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, tris(butoxy)ethyl phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof.
Description
METHOD FOR PRODUCING SHAPED BODIES
FOR LITHIUM ION BATTERIES
The present invention relates to a method for the production of molded articles suitable, inter alia, as solid electrolytes, separators and electrodes for electro-chemical cells, and preferably of sheet-type molded articles for electrochemical cells by melt extrusion; solid electrolytes, separators, electrodes, sensors, electrochromic ~'~dows, displays, capacitors and ion-conducting foils per se which, in each case, comprise such a molded article; and electrochemical cells comprising such solid electrolytes, separators andlor electrodes.
Electrochemical cells, in particular rechargeable ones, are generally known, for example from "Ullmann's Encyclopedia of Industrial Chemistry", 5th edition, Vol.
A3, VCH Verlagsgesellschaft mbH, Weinheim, 1985, pp. 343-397.
Among these cells, a special position is occupied by lithium batteries and lithium ion batteries, in particular as secondary cells, owing to their high specific energy storage 2 0 density.
As described inter alia in the above quotation from "Ullmann", such cells include, in the cathode, mixed oxides containing lithium ions and ions of manganese, of cobalt, of vanadium or of nickel, such mixed oxides being suitably described, in the stoichiometrically simplest case, as LiMn204, LiCoOZ, LiV205 or LiNi02.
These mixed oxides react reversibly with compounds which are able to intercalate lithium ions into their lattice, for example graphite, the lithium ions being removed from the crystal lattice and the metal ions such as manganese ions, cobalt ions or 3 0 nickel ions in this lattice being oxidized in the process. This reaction can be utilized O.Z. 0050/47880 in an electrochemical cell for storing electrical energy by the compound which takes up the lithium ions, in other words the anode material, and the lithium-containing mixed oxide, in other words the cathode material, being separated by an electrolyte for which the lithium ions migrate from the mixed oxide into the anode material (charging operation).
In so doing, the compounds suitable for storing lithium ions reversibly are usually fixed on collector electrodes by means of a binder.
1o When the cell is charged, electrons flow through an external voltage source and lithium cations through the electrolyte towards the anode material. When the cell is utilized, the lithium cations flow through the electrolyte, whereas the electrons flow through a load from the anode material to the mixed oxide (cathode material).
So as to avoid a short circuit within the electrochemical cell, inbetween the two electrodes there is an electrically insulating, but lithium cation-permeable layer, a solid electrode or separator.
As is known, solid electrolytes and separators consist of a support material into 2o which a dissociable compound containing lithium cations is incorporated to enhance the lithium ion conductivity, as are, normally, further additives such as solvents.
In this context a solid electrolyte is understood to be a material which can either be used without a solvent in the electrochemical cells or which, in the case of a solvent being used, largely contains the latter in physically bound form.
To prepare the solid electrolytes or separators, the general approach is to apply a solution from the support material, the compound containing lithium canons and, if required, further additives to a support, and the solvent is then evaporated.
One support material, proposed e.g. by US S 540 741 and US S 478 668, is a .. CA 02285007 1999-09-22 copolymer from vinylidene difluoride and hexafluoropropene.
O.Z. 0050/47880 Production of these battery foils in accordance with the above publications involves dispersing the solid, plasticizer and binder (see Table).
Anode Cathode Separator Solid Graphite LiMnzOa Aerosil PlasticizerDibutyl phthalateDibutyl phthalateDibutyl phthalate Binder COPO COPO COPO
(PVDF/HFP) (PVDF/H~P) (PVDF/HFP) Solvent Acetone Acetone Acetone ExtractantDiethyl ether Diethyl ether Diethyl ether ~
The dispersion is then cast, and the filin is dried. Then the plasticizer is extracted with diethyl ether. The binder is a random copolymer of vinylidene fluoride and hexafluoropropene (8-25%).
The method described there has the following drawbacks:
1. Use of organic solvents 2. Film has to be dried 3. Extraction of the plasticizer is required 4. The extractant is explosive 5. Extraction of plasticizer from the sheet is not 100% effective.
Also known are solid electrolytes on the basis of poly-(alkylene oxides);
these solid electrolytes are described e.g. in EP-A 559 317, EP-A 576 686, EP-A 537 930, EP-A 585 072 and US 5' 279 910. The polyethers described there are modified at the end " CA 02285007 1999-09-22 groups or func-tional groups, e.g. by (meth)acryloyl groups, and are cross-linked, prior to being used as a solid electrolyte, by means of energy input (heat, light).
Additionally they generally contain a conducting salt, e.g. LiPF6, to improve their conductivity. The methods for producing the systems described there include conventional casting, laminating and compression-molding processes.
US 5 348 824 relates to a method for coating a positive electrode of an Li battery by melt extrusion of a solid polymer electrolyte which comprises a polymer as defined therein and an Li salt. EP-B 145 498 likewise describes a method for producing molded articles suitable for electrochemical cells, which involves melt-blending of a mixture of a conducting salt, an organic polymer and a plasticizer and producing a sheet from the melt, e.g. by extrusion. The electrochemical load-carrying capacity of the sheets thus obtained is inadequate, as a rule.
All these methods have in common that they are very complicated and/or result in molded articles which are unsatisfactory in terms of resistance to pressure and/or thermal stability.
It is therefore an object of the present invention to provide an improved method for producing such molded articles and to provide these molded articles per se which, owing to the production process, have a special microstructure and improved mechanical characteristics.
Owing to, in particular, the presence of a pigment III and the special process parameters used here, as defined hereinafter, molded articles are obtained which, when used as a solid electrolyte, separator or electrode, exhibit improved short-circuit withstand capability, enhanced resistance to pressure, in particular at elevated temperatures of above 120°C, and a greater porosity, all compared with the systems known hitherto, and in addition are capable of lasting suppression of Li dendrite formation. Furthermore, the presence of the pigment accounts for improved cycle AMENDED SHEET
O.Z. 0050/47880 stability and a higher current rating of an electrochemical cell. Another point is that if the preferentially used basic solids IIIa are employed, the acid formed during preparation of an electrochemical cell is scavenged or neutralized.
The invention therefore relates to a method for producing a molded article, prefer-ably a sheet-type molded article, which method comprises the following stage:
I) Compounding and melt extrusion of a mixture I which comprises a blend II
which contains:
a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from S nm to 20 mm which is selected from the group consisting of an electrochemically inert solid IZIa, a compomd IIIb which during charging is able to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IIIa with the compound ITIb or the compound ITIc, b) from 5 to 99 wt% of at least one polymeric binder N, and 2o c) from 0 to 200 wt%, based on the total amount of the components a) and b), of at Least one plasticizes V, wherein the proportion by weight of the blend II in the mixture I is from 1 to wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder N, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (I~'P) having an HFP content of from 8 to 25 wt% and, as the plasticizes V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, 3o tris(butoxyethyl)phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
FOR LITHIUM ION BATTERIES
The present invention relates to a method for the production of molded articles suitable, inter alia, as solid electrolytes, separators and electrodes for electro-chemical cells, and preferably of sheet-type molded articles for electrochemical cells by melt extrusion; solid electrolytes, separators, electrodes, sensors, electrochromic ~'~dows, displays, capacitors and ion-conducting foils per se which, in each case, comprise such a molded article; and electrochemical cells comprising such solid electrolytes, separators andlor electrodes.
Electrochemical cells, in particular rechargeable ones, are generally known, for example from "Ullmann's Encyclopedia of Industrial Chemistry", 5th edition, Vol.
A3, VCH Verlagsgesellschaft mbH, Weinheim, 1985, pp. 343-397.
Among these cells, a special position is occupied by lithium batteries and lithium ion batteries, in particular as secondary cells, owing to their high specific energy storage 2 0 density.
As described inter alia in the above quotation from "Ullmann", such cells include, in the cathode, mixed oxides containing lithium ions and ions of manganese, of cobalt, of vanadium or of nickel, such mixed oxides being suitably described, in the stoichiometrically simplest case, as LiMn204, LiCoOZ, LiV205 or LiNi02.
These mixed oxides react reversibly with compounds which are able to intercalate lithium ions into their lattice, for example graphite, the lithium ions being removed from the crystal lattice and the metal ions such as manganese ions, cobalt ions or 3 0 nickel ions in this lattice being oxidized in the process. This reaction can be utilized O.Z. 0050/47880 in an electrochemical cell for storing electrical energy by the compound which takes up the lithium ions, in other words the anode material, and the lithium-containing mixed oxide, in other words the cathode material, being separated by an electrolyte for which the lithium ions migrate from the mixed oxide into the anode material (charging operation).
In so doing, the compounds suitable for storing lithium ions reversibly are usually fixed on collector electrodes by means of a binder.
1o When the cell is charged, electrons flow through an external voltage source and lithium cations through the electrolyte towards the anode material. When the cell is utilized, the lithium cations flow through the electrolyte, whereas the electrons flow through a load from the anode material to the mixed oxide (cathode material).
So as to avoid a short circuit within the electrochemical cell, inbetween the two electrodes there is an electrically insulating, but lithium cation-permeable layer, a solid electrode or separator.
As is known, solid electrolytes and separators consist of a support material into 2o which a dissociable compound containing lithium cations is incorporated to enhance the lithium ion conductivity, as are, normally, further additives such as solvents.
In this context a solid electrolyte is understood to be a material which can either be used without a solvent in the electrochemical cells or which, in the case of a solvent being used, largely contains the latter in physically bound form.
To prepare the solid electrolytes or separators, the general approach is to apply a solution from the support material, the compound containing lithium canons and, if required, further additives to a support, and the solvent is then evaporated.
One support material, proposed e.g. by US S 540 741 and US S 478 668, is a .. CA 02285007 1999-09-22 copolymer from vinylidene difluoride and hexafluoropropene.
O.Z. 0050/47880 Production of these battery foils in accordance with the above publications involves dispersing the solid, plasticizer and binder (see Table).
Anode Cathode Separator Solid Graphite LiMnzOa Aerosil PlasticizerDibutyl phthalateDibutyl phthalateDibutyl phthalate Binder COPO COPO COPO
(PVDF/HFP) (PVDF/H~P) (PVDF/HFP) Solvent Acetone Acetone Acetone ExtractantDiethyl ether Diethyl ether Diethyl ether ~
The dispersion is then cast, and the filin is dried. Then the plasticizer is extracted with diethyl ether. The binder is a random copolymer of vinylidene fluoride and hexafluoropropene (8-25%).
The method described there has the following drawbacks:
1. Use of organic solvents 2. Film has to be dried 3. Extraction of the plasticizer is required 4. The extractant is explosive 5. Extraction of plasticizer from the sheet is not 100% effective.
Also known are solid electrolytes on the basis of poly-(alkylene oxides);
these solid electrolytes are described e.g. in EP-A 559 317, EP-A 576 686, EP-A 537 930, EP-A 585 072 and US 5' 279 910. The polyethers described there are modified at the end " CA 02285007 1999-09-22 groups or func-tional groups, e.g. by (meth)acryloyl groups, and are cross-linked, prior to being used as a solid electrolyte, by means of energy input (heat, light).
Additionally they generally contain a conducting salt, e.g. LiPF6, to improve their conductivity. The methods for producing the systems described there include conventional casting, laminating and compression-molding processes.
US 5 348 824 relates to a method for coating a positive electrode of an Li battery by melt extrusion of a solid polymer electrolyte which comprises a polymer as defined therein and an Li salt. EP-B 145 498 likewise describes a method for producing molded articles suitable for electrochemical cells, which involves melt-blending of a mixture of a conducting salt, an organic polymer and a plasticizer and producing a sheet from the melt, e.g. by extrusion. The electrochemical load-carrying capacity of the sheets thus obtained is inadequate, as a rule.
All these methods have in common that they are very complicated and/or result in molded articles which are unsatisfactory in terms of resistance to pressure and/or thermal stability.
It is therefore an object of the present invention to provide an improved method for producing such molded articles and to provide these molded articles per se which, owing to the production process, have a special microstructure and improved mechanical characteristics.
Owing to, in particular, the presence of a pigment III and the special process parameters used here, as defined hereinafter, molded articles are obtained which, when used as a solid electrolyte, separator or electrode, exhibit improved short-circuit withstand capability, enhanced resistance to pressure, in particular at elevated temperatures of above 120°C, and a greater porosity, all compared with the systems known hitherto, and in addition are capable of lasting suppression of Li dendrite formation. Furthermore, the presence of the pigment accounts for improved cycle AMENDED SHEET
O.Z. 0050/47880 stability and a higher current rating of an electrochemical cell. Another point is that if the preferentially used basic solids IIIa are employed, the acid formed during preparation of an electrochemical cell is scavenged or neutralized.
The invention therefore relates to a method for producing a molded article, prefer-ably a sheet-type molded article, which method comprises the following stage:
I) Compounding and melt extrusion of a mixture I which comprises a blend II
which contains:
a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from S nm to 20 mm which is selected from the group consisting of an electrochemically inert solid IZIa, a compomd IIIb which during charging is able to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IIIa with the compound ITIb or the compound ITIc, b) from 5 to 99 wt% of at least one polymeric binder N, and 2o c) from 0 to 200 wt%, based on the total amount of the components a) and b), of at Least one plasticizes V, wherein the proportion by weight of the blend II in the mixture I is from 1 to wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder N, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (I~'P) having an HFP content of from 8 to 25 wt% and, as the plasticizes V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, 3o tris(butoxyethyl)phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
O.Z. 0050/47880 It further relates to a method as defined hereinabove, wherein the pigment III
is an electrochemically inert solid IITa which is selected from the group consisting of an inorganic solid, preferably an inorganic basic solid, selected from the group consisting of oxides, mixed oxides, carbonates, silicates, sulfates, phosphates, amides, imides, nitrides and carbides of the elements of the Ist, ILnd, IIIrd or Nth main group or the IVth subgroup of the Periodic Table of the Elements; a polymer selected from the group consisting of polyethylene, polypropylene, polystyrene, poly(tetrafluoroethylene), poly(vinylidene fluoride), polyamides, polyimides;
a solid to dispersion containing a polymer of this type; glass powder, nano glass particles, such as MonosperC~ (company Merck), micro glass particles, such as Spheriglass~
(company Potters-Ballotini), nano whiskers and a mixture of two or more thereof, a molded article being obtained in the process which can be used as a solid electrolyte and/or a separator.
Examples to be mentioned are, in particular: oxides such as e.g. silicon dioxide, aluminum oxide, magnesium oxide or titanium dioxide, mixed oxides, for example of the elements silicon, calcium, aluminum, magnesium, titanium; silicates such as e.g. ladder-type silicates, inosilicates, phyllosilicates and tectosilicates;
such as 2o talcum, pyrophyllite, muscovite, phlogopite, amphiboles, nesosilicates, pyroxenes, sorosilicates, zeolithes, feldspar, glimpse, phyllosilicates; sulfates such as e.g. alkali metal sulfates and alkaline earth metal sulfates; carbonates, for example alkali metal carbonates and alkaline earth metal carbonates such as e.g. calcium carbonate, magnesium carbonate or barium carbonate or lithium carbonate, potassium carbonate or sodium carbonate; phosphates, for example apatites; amides;
imides;
nitrides; carbides; polymers such as e.g. polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, poly(vinylidene fluoride), polyamides, polyimides or other thermoplastics, thermosets or microgels, cross-linked polymer particles such as Agfaperl~ solid dispersions, in particular those containing the abovementioned 3o polymers, and mixtures of two or more of the abovementioned solids.
_7_ O.Z. 0050/47880 Furthermore, as the inert solid IIZa, inorganic solids, which conduct Li-ions, preferably an inorganic basic solid, which conducts Li-ions, may be used according to the invention.
The following may be mentioned:
Lithium borates such as LiaB60a * xHzO, Li3(BOz)3, LizBa07 * xHzO, wherein x may be a number of from 0 to 20; lithium aluminates, such as LizO * AlzO3 *
HzO, LizAlzOa, LiAIOz; lithium aluminosilicates, such as lithium containing zeolithes, to feldspar, compounds of feldspar-type, phyllosilicates and inosilicates, and particularly LiAlSiz06 (spodumen), LiAlSiaOio (petullite), LiAlSiOa (eucryptite), glimmers, such as K[Li,AI]3[AISi]aO~o(F-OH)z, K[Li,AI,Fe]3 [AISi]a0io(F-OH)z;
li-thium zeolithes, particularly those in fiber-, sheet-, oder cube-form, particularly those having the general formula LiziZO * A1z03 * xSiOz * yHzO wherein z ~ 5 corresponds to the valancy, x=1.8 to about 12 and y=0 to about 8; lithium carbides, such as LizCz, Li.~C; Li3N; lithium oxides and mixed oxides, such as LiAIOz, LizMn03, LizO, LizOz, LizMnOa, LizTi03; LizNH; LiNHz; lithium phosphates, such as Li3P04, LiP03, LiAIFPOa, LiAI(OH)POa, LiFePOa, LiMnPOa; LizC03; lithium silicates of the ladder type, sheet type and tecto silicates, such as e.g.
LizSi03, 2o LizSiOa ~d Li6Siz; lithium sulfate, such as LizS04, LiHSOa, LiKSOa; as well as the lithium compounds as mentioned under solid nlb, under the proviso that when used as solid lea the presence of conductive black is excluded; and mixtures of two or more of the Li ion conducting solids as mentioned above.
25 Particularly suitable in this context are basic solids, where basic solids are to be understood as those whose mixture with a liquid diluent which contains water and itself has a pH of at most 7, has a higher pH than said diluent.
Advantageously, the solids should be very largely insoluble in the liquid used as an 3o electrolyte and be electrochemically inert in the battery medium.
' CA 02285007 1999-09-22 _g_ O.Z. 0050/47880 The invention further relates to a method, wherein the pigment III is a compound )ZIb which, during charging, is able to give off lithium ions and which is selected from the group consisting of LiCoOz, LiNiOz, LiNiXCoyOz, LiNiXCoyAIZOz(O<x,y,z<1), LixMnOz _ -(0<x<1), LiXMnzOa (0<x<2), LixMoOz (0<x<2), Li;~Mn03 (0<x<1), LiXMnOz (0<x<2), LixMnzOa (0<x<2), LiXV20a (0<x<2.5), LiXVz03 (0<x<3.5), LixVOz (0<x<1), LiXWOz (0<x<1), LiXW03 (0<x<1), Li;~TiOz (0<x<1), LiXTizOa (0<x<2), Li,~RuOz (0<x<1), LiXFez03 (0<x<2), LiXFe30a _ _ _(0<x<2), LiYCrz03 (0<x<3), LiXCr30a (0<x<3.8), LirV3S;
(0<x<1.8), LiXTa2Sz _ _ _ _(0<x<1), LixFeS (0<x<1), LiXFeS2 (0<x<1), LiXNbSz (0<x<2.4), LiXMoSz to (0<x<3), LixTiSz _ _ _(0<x<2), LixZrSz (0<x<2), LiXNbSez (0<x<3), LixVSez (0<x<_1), LirNiPSz _(0<x_<1.5), LiXFePSz (0<x<1.5), LiNixBi-XOz (0 < x < 1), LiNiXAh-XOz (0 <
x < 1), LiNirMg~-,~Oz (0 < x < 1), LiNiXCot-XVOa (1 >_ x >_ 0), LiNirCoyMnZOz (x+y+z = 1), LiFeOz, LiCrTiOa, LiaMbL,~Oa (1,15 >_ a > 0; 1,3 >_ b+c >- 0,8;
2,5 >_ d >1,7; M - Ni, Co, Mn; L = Ti, Mn, Cu, Zn, alkaline earth metals, LiCuxuCuY~Mn~z-~:~+y~~0a (2 > x+y > 0), LiCrTiOa, LiGaXMnz-XOa (0,1 >_ x >_ 0), polycarbonsulfides of the general structure: -[C(SX)]n-, VzOs, a mixture of two or more thereof, and a mixture of the compound ILTIb with the solid IIZa; and the mixture I additionally contains from 0.1 to 20 wt%, based on the blend lI, of conductive black, a molded article being obtained which can be used, in particular, 2o as a cathode.
moreover, the invention relates to a method, wherein the pigment III is a compound >IIc which, during charging, is able to take up lithium ions and which is selected from the group consisting of lithium, a lithium-containing metal alloy, rnicronized carbon black, natural and synthetic graphite, synthetically graphitized carbon dust, a carbon fiber, titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, titanium carbonate, molybdenum carbonate, zinc carbonate, LirMySiOz (1 > x >_ 0, 1 > y >_ 0, z > 0), SnzBPOa, conjungated polymers such as polypyrroles, polyanilines, polyacetylenes, polyphenylenes, lithium metal compounds LixM, such 3o as those, wherein M = Sn, Bi, Sb, Zn, Cd, Pb and 5 >_ x >_ 0; Li-Sn-Cd, CdO, PbO, a .. CA 02285007 1999-09-22 a O.Z. 0050147880 mixture of two or more thereof, and a mixture of the compound ITIc with the solid Illa; and the mixture I additionally contains up to 20 wt%, based on the blend II, of conductive black, a molded article being obtained which can be used, in particular, as an anode.
Particularly suitable are pigments III having a primary particle size of from 5 nm to 20 mm, preferably from 0.01 to 10 mm and in particular from 0.1 to 5 mm, the specified particle sizes being determined by electron microscopy. The melting point of the pigments is preferably above the normal operating temperature for the electro-l0 chemical cell, melting points of above 120°C, in particular of above 150°C having proved particularly beneficial.
In this context the pigments, in terms of their external shape, can be symmetrical, i.e.
have a size ratio height:width:length (aspect ratio) of approximately 1 and be present in the form of spheres, granules, approximately round structures, but also in the form of any type of polyhedron such as e.g. cuboids, tetrahedra, hexahedra, octahedra or as a bipyramid or be distorted or asymmetrical, i.e. have a size ratio height:width:length (aspect ratio) different from 1 and be present e.g. as needles, asymmetric tetrahedra, asymmetric bipyramids, asymmetric hexahedra or octahedra, laminae, disks or fibrous structures. Insofar as the solids are present as asymmetric particles, the above-specified upper limit for the primary particle size in each case refers to the shortest axis.
In the course of the production of the molded articles which can be used as a cathode or anode, the conductive black, if present, is preferably added to the blend II in the form of a masterbatch. The masterbatch is a composition which contains from 20 to 50 wt% of conductive black, from 5 to 30 wt% of polymeric binder IV and from to 75 wt% of plasticizer IV, the amount and composition chosen of the masterbatch being such that, based on the blend II, the amount of conducting salt added in total does not exceed 20 wt%. The masterbatch is preferably prepared by compounding .. CA 02285007 1999-09-22 and melt extrusion of the abovementioned components.
O.Z. 0050/47880 The blends II should comprise, according to the invention, from 1 to 95 wt%, preferably from 25 to 90 wt% and in particular from 30 to 70 wt% of a pigment III
and from 5 to 99 wt%, preferably from 10 to 75 wt% and in particular from 30 to 70 wt% of a polymeric binder N, where the polymeric binder should advantageously have a mean molec-ular weight (number average) of from 5000 to 100,000,000, preferably from 50,000 to 8,000,000.
to The following additional feedstocks are used in producing the molded article or in the mixture I used or the blend II:
Used as the polymeric binders N are thermoplastic and ion-conductive polymers, examples to be mentioned in particular being:
1) Homopolymers, block polymers or copolymers Na (polymers Na) which can be obtained by polymerization of bl) from 5 to 100 wt%, based on the polymer IVa, of a condensation 2o product VI of a) at least one compound VII which is able to react with a carboxylic acid or a sulfonic acid or a derivative or a mixture of two or more of these, and at least 1 mol per mole of the compound VII of a carboxylic acid z5 or sulfonic acid VIII which has at least one free-radical poly-merizable functional group or of a derivative thereof or of a mixture of two or more of these and b2) from 0 to 95 wt%, based on the polymer IVa, of a further compound IX
O.Z. 0050147880 having a mean molecular weight (number average) of at least 5000 comprising polyether segments in the main chain or a side chain.
The polymer Na is preferably obtainable via bl) from 5 to 100 wt%, based on the polymer IVa, of a condensation product VI of a) a polyhydric alcohol VII which contains carbon atoms and l0 oxygen atoms in the main chain, and (~) at least 1 mol per mole of the polyhydric alcohol VII of an a, ~ -unsaturated carboxylic acid VILLI, and b2) from 0 to 95 wt%, based on the polymer Na, of a further 2o compound IX having a mean molecular weight (number average) of at least 5000 comprising polyether segments in the main chain or a side chain.
Suitable, in principle, as the compound VII which is capable of reacting with a carboxylic acid or a sulfonic acid VIII or a derivative or a mixture of two or more thereof are all compounds which satisfy this criterion.
The compound VII is preferentially selected from the group consisting of a mono- or polyhydric alcohol which in its main chain solely comprises carbon 3o atoms; a mono- or polyhydric alcohol which in its main chain, in addition to at least two carbon atoms, has at least one atom which is selected from the group .. CA 02285007 1999-09-22 O.Z. 0050147880 consisting of oxygen, phosphorus and nitrogen; a silicon-containing compound;
an amine having at least one primary amino group; an amine having at least one secondary amino group; an amino alcohol; a mono- or polyhydric thiol; a compound having at least one thiol and at least one hydroxyl group; and a mixture of two or more of these.
Among these, in turn, compounds VII are preferred which have two or more functional groups which are able to react with the carboxylic acid or sulfonic acid.
If compounds VII are used which as the functional group contain amino groups, preference is given to the use of those having secondary amino groups, so that after the condensation/cross-linking either no free NH groups or only small amounts of these are present in the mixture Ia.
To be mentioned individually as preferred compounds are:
mono- or polyhydric alcohols whose main chain consists exclusively of carbon atoms and which have from 1 to 20, preferably from 2 to 20 and in particular from 2 to 10 alcoholic OH groups, in particular dihydric, trihydric and 2o tetrahydric alcohols, preferably having from 2 to 20 carbon atoms, such as e.g.
ethylene glycol, propane-1,2- or -1,3-diol, butane-1,2- or -1,3-diol, butene-1,4-or butyne-1,4-diol, hexane-1,6-diol, neopentyl glycol, dodecane-1,2-diol, glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, hydroquinone, novolak, bisphenol A, an alternative option, however, as follows from the above definition, being the use of monohydric alcohols such as e.g. methanol, ethanol, propanol, n-, sec- or t-butanol etc.; furthermore it is also possible to employ polyhydroxyolefins, preferably those having two terminal hydroxyl groups, such as e.g. a,~-dihydroxybutadiene;
polyester polyols such as those known e.g. from Ullinann's Encyklopddie der technischen Chemie, 4'h edition, vol. 19, pp. 62-65 and obtainable, for example, by the reaction of dihydric alcohols with polybasic, preferably dibasic ~~
O.Z. 0050/47880 polycarboxylic acids;
mono- or polyhydric alcohols which in their main chain, in addition to at least two carbon atoms, contain at least one oxygen atom, preferably polyether alcohols such as e.g. polymerization products of alkylene epoxides, for example isobutylene oxide, propylene oxide, ethylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, tetrahydrofuran, styrene oxide, an additional option being the use of polyether alcohols modified at their terminal groups, such as e.g. polyether alcohols modified by means of NH2 terminal groups; these alcohols preferably have a molecular weight {number average) of 1o from 100 to 5000, more preferably from 200 to 1000 and in particular from to 800; compounds of this type are known per se and are commercially available, for example, under the brands Pluriol~ or Pluronic~ (BASF Aktien-gesellschaft);
alcohols as defined above, in which some or all of the carbon atoms have been replaced by silicon, a particular option in this context being the use of polysiloxanes or alkylene oxide/siloxane copolymers or mixtures of polyether alcohols and polysiloxanes, as described, for example, in EP-B 581 296 and EP-A 525 728, what was said above likewise applying to the molecular weight of these alcohols;
2o alcohols as defined above, in particular polyether alcohols in which some or all the oxygen atoms have been replaced by sulfur atoms, what was said above likewise applying to the molecular weight of these alcohols;
mono- or polyhydric alcohols which, in their main chain, in addition to at least two carbon atoms contain at least one phosphorus atom or at least one nitrogen atom such as e.g. diethanolamine, triethanolamine;
lactones which are derived from compounds of the general formula HO-(CHz)Z-COOH, where z is a number from 1 to 20, such as e.g. ~-caprolactone, (~-propiolactone, Y-butyrolactone or methyl- E -caprolactone;
a silicon-containing compound such as e.g. di- or trichlorosilane, 3o phenyltrichlorosilane, diphenyldichlorosilane, dimethylvinylchlorosilane;
silanols such as e.g. trimethylsilanol;
~
. CA 02285007 1999-09-22 O.Z. 0050/47880 an amine having at least one primary and/or secondary amino group, such as e.g. butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, aniline, phenylenediamine;
polyetherdiamines such as e.g. 4,7-dioxadecane-1,10-diamine, 4,11-dioxatetradecane-1,14-diamine;
a mono- or polyhydric thiol such as e.g. aliphatic thiols such as e.g.
methanethiol, ethanethiol, cyclohexanethiol, dodecanethiol; aromatic thiols such as e.g. thiophenol, 4-chlorothiophenol, 2-mercaptoaniline;
to a compound having at least one thiol and at least one hydroxyl group, such as e.g. 4-hydroxythiophenol and monothio derivatives of the above-defined polyhydric alcohols;
amino alcohols such as e.g. ethanolamine, N-methyl-ethanolamine, N-ethylethanolamine, N-butylethanolamine, 2-amino-1-propanol, 2-amino-1-phenylethanol;
mono- or polyaminopolyols having more than two aliphatically bound hydroxyl groups, such as e.g. tris(hydroxymethyl)methylamine, glucamine, N,N'-bis-(2-hydroxyethyl)ethylenediamine, and mixtures of these.
It is also possible to use mixtures of two or more of the above-described compounds VII.
The abovementioned compounds VII are condensed, according to the invention, with a carboxylic acid or sulfonic acid VIII which has at least one free-radical polymerizable functional group or with a derivative thereof or a mixture of two or more of these, at least one, preferably all of the free groups capable of condensation within the compounds VII being condensed with the compound VIII.
3o Suitable in principle as the carboxylic acid or sulfonic acid VIII within the scope of the present invention are all those carboxylic and sulfonic acids which O.Z. 0050/47880 have at least one free-radical polymerizable functional group, as are their derivatives. In this context, the term "derivatives" as used herein comprises both compounds derived from a carboxylic or sulfonic acid which has been modified at the acid function (such as e.g. esters, acid halides or acid anhydrides) and compounds derived from a carboxylic or sulfonic acid which has been modified on the carbon skeleton of the carboxylic or sulfonic acid, such as e.g. halocarboxylic or halosulfonic acids.
Particular examples to be mentioned of compound VIII are:
to a,~-unsaturated carboxylic acids or a,'Y-unsaturated carboxylic acids or derivatives thereof.
Particularly suitable a,~-unsaturated carboxylic acids in this context are those of the formula R3 ~C=C~
COOH
where Rl, RZ and R3 are hydrogen or Ci-Ca-alkyl, among which in turn acrylic acid and methaclylic acid are preferred; also expediently usable are cinnamic acid, malefic acid, fiunaric acid, itaconic acid or p-vinylbenzoic acid and - derivatives of these, such as e.g. anhydrides such as e.g, malefic or itaconic anhydride;
halides, in particular chlorides, such as e.g. acryloyl or methacryloyl chloride;
esters such as e.g. (cyclo)alkyl (meth)acrylates having up to 20 C atoms in the alkyl radical, such as e.g. methyl (meth)acrylate, ethyl (meth)acrylate, propyl -(meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, trifluoromethyl (meth)acrylate, hexa-fluoropropyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, polypropylene-O.Z. 0050147880 glycol mono(meth)acrylates, polyethylene mono(meth)acrylates, poly(meth)acrylates of polyhydric alcohols, such as e.g. glycerol di(meth)-acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di- or tri(meth)acrylate, diethylene glycol bis(mono-(2-acryloxy)ethyl)carbonate, poly(meth)acrylates of alcohols which themselves in turn have a free-radical polymerizable group, such as e.g. esters from (meth)acrylic acid and vinyl andlor allyl alcohol;
vinyl esters of other aliphatic or aromatic carboxylic acids, such as e.g.
vinyl acetate, vinyl propionate, vinyl butanoate, vinyl hexanoate, vinyl octanoate, 1o vinyl decanoate, vinyl stearate, vinyl palmitate, vinyl crotonate, divinyl adipate, divinyl sebacate, vinyl 2-ethylhexanoate, vinyl trifluoroacetate;
allyl esters of other aliphatic or aromatic carboxylic acids, such as e.g.
allyl acetate, allyl propionate, allyl butanoate, allyl hexanoate, allyl octanoate, allyl decanoate, allyl stearate, allyl palmitate, allyl crotonate, allyl salicylate, allyl lactate, diallyl oxalate, allyl stearate, allyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, allyl cinnamate, diallyl maleate, diallyl phthalate, diallyl isophthalate, triallyl benzene-1,3,5-tricarboxylate, allyl fluoroacetate, allyl perfluorobutyrate, allyl perfluorooctanoate;
~~Y-unsaturated carboxylic acids and derivatives thereof, such as e.g.
2o vinylacetic acid, 2-methylvinylacetic acid, isobutyl 3-butenoate, allyl 3-butenoate, allyl 2-hydroxy-3-butenoate, diketene;
sulfonic acids such as, e.g. vinylsulfonic acid, allyl- and methallylsulfonic acid, and their esters and halides, vinyl benzenesulfonate, 4-vinylbenzene-sulfonamide.
It is also possible for mixtures of two or more of the above-described carboxylic and/or sulfonic acids to be used.
The polymer Na can be obtained by the reaction of from 5 to 100 wt%, preferably from 30 to 70 wt%, based on the polymer IVa, of a condensation O.Z. 0050/47880 product VI and from 0 to 95 wt%, in particular from 30 to 70 wt%, based on the polymer IVa, of a compound IX.
2) Homopolymers, block polymers or copolymers Nb (polymers IVb), obtainable by polymerization of bl) frorn 5 to 75 wt%, based on the polymer IVb, of an unsaturated compound X which is capable of free-radical polymerization and differs from the above carboxylic acid or the sulfonic acid or a derivative 1o thereof, or of a mixture of two or more of these and b2) from 25 to 95 wt%, based on the polymer IVb, of a further compound IX, having a mean molecular weight (number average) of at least 5000 and comprising polyether segments in the main chain or a side chain as a polymeric binder.
Examples to be mentioned in particular of the compound X which can be used 2o for the preparation of the polymer IVb and is capable of free-radical polymer ization include the following:
olefmic hydrocarbons such as e.g. ethylene, propylene, butylene, isobutene, hexene or higher homologs and vinyl cyclohexane;
(meth)acrylonitrile;
halogen-containing olefinic compounds such as e.g. vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, tri-fluoropropene, 1,2-dichloroethylene, 1,2-difluoroethylene and tetrafluoro-ethylene;
vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole, vinylformamide;
phosphonitrile chlorides such as e.g. phosphonitrile dichloride, ~
O.Z. 0050/47880 hexachloro(triphosphazene), and their derivatives partially or completely substituted by alkoxy, phenoxy, amino and fluoroalkoxy groups, i.e.
compounds which can be polymerized to give polyphosphazenes;
aromatic, olefinic compounds such as e.g. styrene, a-methylstyrene;
vinyl ethers such as e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, tetrafluoropropyl vinyl ether.
Of course it is also possible to employ mixtures of the abovementioned l0 compounds X, in which case copolymers are then formed which, depending on the preparation route, contain the monomers in random distribution or result in block copolymers.
These compounds X, like the condensation products VI, are polymerized in a conventional manner well known to those skilled in the art, preferably by free-radical polymerization, the molecular weights obtained being subject to the same points as made below regarding the compound IX.
Potentially suitable, in the first instance, for compound IX are compounds having a mean molecular weight (number average) of at least 5000, preferably from 5000 to 20,000,000, in particular from 100,000 to 6,000,000, which are able to solvate lithium cations and to act as a binder. Examples of suitable compounds IX include polyethers and copolymers which comprise at least 30 wt% of the following structural unit, based on the total weight of the compound IX:
T, 2 ~C-C~~' O-n ~
O.Z. 0050/47880 where R~, R2, R3 and R4 are aryl, alkyl, preferably methyl, or hydrogen, may be identical or different and may include hetero atoms such as oxygen, nitrogen, sulfur or silicon.
Such compounds are described, for example, in: M. B. Armand et al., Fast Ion Transport in Solids, Elsevier, New York, 1979, pp. 131-136, or in FR-A
7832976.
The compound IX may alternatively consist of mixtures of such compounds.
l0 The polymer IVb can be obtained by the reaction of from 5 to 75 wt%, preferably from 30 to 70 wt%, based on the polymer IVb, of a compound X and from 25 to 95 wt%, in particular from 30 to 70 wt%, based on the polymer IVb, of a compound IX;
3) Polycarbonates such as e.g. polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate, polyvinylidene carbonate.
4) Homopolymers, block polymers and copolymers prepared from 2o a) olefinic hydrocarbons such as e.g. ethylene, propylene, butylene, isobutene, propene, hexene or higher homologs, butadiene, cyclopentene, cyclohexene, norbornene, vinylcyclohexane, 1,3-pentadiene, 1,3-, 1,4-, 1,5-hexadiene, isoprene, vinyl norbornene;
b) aromatic hydrocarbons such as e.g. styrene and methylstyrene;
c) acrylic acid or methacrylic acid ester such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, tetrafluoropropyl acrylate or methacrylate;
d) acrylonitrile, methacrylonitrile, N-methylpyrrolidone, N-3o vinylimidazole, vinyl acetate;
e) vinyl ethers such as e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, O.Z. 0050/47880 hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoro-methyl, hexafluoropropyl, tetrafluoropropyl vinyl ether;
f) halogen-containing olefinic compounds such as vinyl chloride, vinyl fluoride, vinylidene fluoride, vinylidene chloride, hexafluoropropene, trifluoropropene, 1,2-dichloroethene, 1,2-difluoroethene, tetrafluoroethene.
g) 2-vinylpyridine, 4-vinylpyridine, vinylene carbonate.
Within the preparation of the above mentioned polymers, controlling compounds, such as e.g. mercaptane may be used if desired or regarded as being necessary.
5) Polyurethanes, for example obtainable by the reaction of a) organic diisocyanates having from 6 to 30 C atoms, such as e.g.
aliphatic acyclic diisocyanates such as e.g. 1,5-hexamethylene diisocya-nate and 1,6-hexamethylene diisocyanate, aliphatic cyclic diisocyanates such as e.g. 1,4-cyclohexylene diisocyanate, dicyclohexylinethane diisocyanate and isophorone diisocyanate or aromatic diisocyanates such as e.g. 2,4-diisocyanotoluene, 2,6-diisocyanotoluene, m-tetra-2o methylxylene diisocyanate, p-tetramethylxylene diisocyanate, 1,5-diisocyanatotetrahydronaphthalene and 4,4'-diisocyanatodiphenylenemethane or mixtures of such compounds with b) polyhydric alcohols such as e.g. polyesterols, polyetherols and diols.
The polyesterols are expediently predominantly linear polymers having terminal OH groups, preferably those having two or three, in particular two OH
terminal groups. The acid value of the polyesterols is less than 10 and prefer-ably less than 3. The polyesterols can be prepared in a simple manner by 3o esterification of aliphatic or aromatic dicarboxylic acids having from 4 to atoms, preferably from 4 to 6 C atoms, with glycols, preferably glycols having ~
O.Z. 0050/47880 from 2 to 25 C atoms, or by polymerization of lactones having from 3 to 20 C
atoms. Examples of dicarboxylic acids which can be used include glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanoic acid and preferably adipic acid and succinic acid. Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, phthalic acid or mixtures of these dicarboxylic acids with other dicarboxylic acids, e.g. diphenic acid, sebacic acid, succinic acid and adipic acid. The dicarboxylic acids can be used individually or as mixtures.
For the purpose of preparing the polyesterols it may be advantageous for the dicarboxylic acids to be replaced by the corresponding acid derivatives such as to carboxylic acid anhydrides or carboxylic acid chlorides. Examples of suitable glycols are diethylene glycol, 1,5-pentanediol, 1,10-decanediol and 2,2,4-trimethylpentanediol-1,5. Preferentially used are 1,2-ethanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylpropanediol-1,3, 1,4-dimethylolcyclohexane, 1,4-diethanolcyclohexane and ethoxylated or propoxylated products of 2,2-bis-(4-hydroxyphenylene)propane (bisphenol A). Depending on the desired properties of the polyurethanes, the polyols may be used on their own or as a mixture in various quantitative proportions. Suitable as lactones for the preparation of the polyesterols are, e.g. a,a-dimethyl-~-propiolactone, 'Y-butyrolactone and preferably E-caprolactone.
The polyetherols are essentially linear substances which have terminal hydroxyl groups and contain ether bonds. Suitable polyetherols can readily be prepared by polymerization of cyclic ethers such as tetrahydrofuran or by one or more alkylene oxides having from 2 to 4 C atoms in the alkylene radical being reacted with a starter molecule which contains two active hydrogen atoms bound in the alkylene radical. Examples to be mentioned of alkylene oxides include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide, 2,3-butylene oxide. The alkylene oxides can be used singly, alternately in succession or as a mixture. Examples of potentially suitable starter molecules include water, glycols such as ethylene glycol, propylene glycol, 1,4-O.Z. 0050/47880 butanediol and 1,6-hexanediol, amines such as ethylenediamine, hexa-methylenediamine and 4,4'-diaminodiphenylinethane and amino alcohols such as ethanolamine. Suitable polyesterols and polyetherols and their preparation are described, for example, in EP-B 416 386, suitable polycarbonate diols, preferably those based on 1,6-hexanediol, and their preparation are described, for example, in US-A 4 131 731.
Potentially advantageous, in amounts of up to 30 wt%, based on the total mass of the alcohols, are aliphatic diols having from 2 to 20, preferably from 2 to 1o C atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane-diol, 1,5-pentanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, 1,4-dimethylolcyclohexane, neopentyl glycol hydroxypivalate, diethylene glycol, triethylene glycol and methyl diethanolamine or aromatic-aliphatic or aromatic-cycloaliphatic diols having from 8 to 30 C atoms, potentially suitable aromatic structures being heterocyclic ring systems or preferably isocyclic ring systems such as naphthalene and in particular benzene derivatives such as bisphenol A, doubly symmetrically ethoxylated bisphenol A, doubly symmetrically propoxylated bisphenol A, bisphenol A derivatives or bisphenol F derivatives ethoxylated or propoxylated to a higher degree, and mixtures of such compounds.
Potentially advantageous in amounts of up to 5 wt%, based on the total mass of the alcohols, are aliphatic triols having from 3 to 15, preferably from 3 to atoms, such as trimethylolpropane or glycerol, the reaction product of such compounds with ethylene oxide and/or propylene oxide and mixtures of such compounds.
The polyhydric alcohols may carry functional groups, for example neutral 3o groups such as siloxane groups, basic groups such as, in particular, tertiary amino groups or acidic groups or their salts, or groups which are readily O.Z. 0050147880 converted into acidic groups, these functional groups being introduced via a polyhydric alcohol. Preferentially, diol components carrying such groups can be used, such as N-methyldiethanolamine, diethyl N,N-bis(hydroxyethyl)-aminomethylphosphonate or 3-sulfopropyl N,N-bis(hydroxyethyl)-2-aminoacetate or dicarboxylic acids which carry such groups and can be used for the preparation of polyesterols, such as 5-sulfoisophthalic acid.
Acidic groups include, in particular, the phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acid, carboxyl or ammonium group.
Examples of groups which are readily converted into acidic groups include the ester group or salts, preferably of the alkali metals such as lithium, sodium or potassium.
6) The above-described polyesterols per se, in which case care should be taken to ensure that molecular weights in the range of from 10,000 to 2,000,000, preferably from 50,000 to 1,000,000 are obtained.
is an electrochemically inert solid IITa which is selected from the group consisting of an inorganic solid, preferably an inorganic basic solid, selected from the group consisting of oxides, mixed oxides, carbonates, silicates, sulfates, phosphates, amides, imides, nitrides and carbides of the elements of the Ist, ILnd, IIIrd or Nth main group or the IVth subgroup of the Periodic Table of the Elements; a polymer selected from the group consisting of polyethylene, polypropylene, polystyrene, poly(tetrafluoroethylene), poly(vinylidene fluoride), polyamides, polyimides;
a solid to dispersion containing a polymer of this type; glass powder, nano glass particles, such as MonosperC~ (company Merck), micro glass particles, such as Spheriglass~
(company Potters-Ballotini), nano whiskers and a mixture of two or more thereof, a molded article being obtained in the process which can be used as a solid electrolyte and/or a separator.
Examples to be mentioned are, in particular: oxides such as e.g. silicon dioxide, aluminum oxide, magnesium oxide or titanium dioxide, mixed oxides, for example of the elements silicon, calcium, aluminum, magnesium, titanium; silicates such as e.g. ladder-type silicates, inosilicates, phyllosilicates and tectosilicates;
such as 2o talcum, pyrophyllite, muscovite, phlogopite, amphiboles, nesosilicates, pyroxenes, sorosilicates, zeolithes, feldspar, glimpse, phyllosilicates; sulfates such as e.g. alkali metal sulfates and alkaline earth metal sulfates; carbonates, for example alkali metal carbonates and alkaline earth metal carbonates such as e.g. calcium carbonate, magnesium carbonate or barium carbonate or lithium carbonate, potassium carbonate or sodium carbonate; phosphates, for example apatites; amides;
imides;
nitrides; carbides; polymers such as e.g. polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, poly(vinylidene fluoride), polyamides, polyimides or other thermoplastics, thermosets or microgels, cross-linked polymer particles such as Agfaperl~ solid dispersions, in particular those containing the abovementioned 3o polymers, and mixtures of two or more of the abovementioned solids.
_7_ O.Z. 0050/47880 Furthermore, as the inert solid IIZa, inorganic solids, which conduct Li-ions, preferably an inorganic basic solid, which conducts Li-ions, may be used according to the invention.
The following may be mentioned:
Lithium borates such as LiaB60a * xHzO, Li3(BOz)3, LizBa07 * xHzO, wherein x may be a number of from 0 to 20; lithium aluminates, such as LizO * AlzO3 *
HzO, LizAlzOa, LiAIOz; lithium aluminosilicates, such as lithium containing zeolithes, to feldspar, compounds of feldspar-type, phyllosilicates and inosilicates, and particularly LiAlSiz06 (spodumen), LiAlSiaOio (petullite), LiAlSiOa (eucryptite), glimmers, such as K[Li,AI]3[AISi]aO~o(F-OH)z, K[Li,AI,Fe]3 [AISi]a0io(F-OH)z;
li-thium zeolithes, particularly those in fiber-, sheet-, oder cube-form, particularly those having the general formula LiziZO * A1z03 * xSiOz * yHzO wherein z ~ 5 corresponds to the valancy, x=1.8 to about 12 and y=0 to about 8; lithium carbides, such as LizCz, Li.~C; Li3N; lithium oxides and mixed oxides, such as LiAIOz, LizMn03, LizO, LizOz, LizMnOa, LizTi03; LizNH; LiNHz; lithium phosphates, such as Li3P04, LiP03, LiAIFPOa, LiAI(OH)POa, LiFePOa, LiMnPOa; LizC03; lithium silicates of the ladder type, sheet type and tecto silicates, such as e.g.
LizSi03, 2o LizSiOa ~d Li6Siz; lithium sulfate, such as LizS04, LiHSOa, LiKSOa; as well as the lithium compounds as mentioned under solid nlb, under the proviso that when used as solid lea the presence of conductive black is excluded; and mixtures of two or more of the Li ion conducting solids as mentioned above.
25 Particularly suitable in this context are basic solids, where basic solids are to be understood as those whose mixture with a liquid diluent which contains water and itself has a pH of at most 7, has a higher pH than said diluent.
Advantageously, the solids should be very largely insoluble in the liquid used as an 3o electrolyte and be electrochemically inert in the battery medium.
' CA 02285007 1999-09-22 _g_ O.Z. 0050/47880 The invention further relates to a method, wherein the pigment III is a compound )ZIb which, during charging, is able to give off lithium ions and which is selected from the group consisting of LiCoOz, LiNiOz, LiNiXCoyOz, LiNiXCoyAIZOz(O<x,y,z<1), LixMnOz _ -(0<x<1), LiXMnzOa (0<x<2), LixMoOz (0<x<2), Li;~Mn03 (0<x<1), LiXMnOz (0<x<2), LixMnzOa (0<x<2), LiXV20a (0<x<2.5), LiXVz03 (0<x<3.5), LixVOz (0<x<1), LiXWOz (0<x<1), LiXW03 (0<x<1), Li;~TiOz (0<x<1), LiXTizOa (0<x<2), Li,~RuOz (0<x<1), LiXFez03 (0<x<2), LiXFe30a _ _ _(0<x<2), LiYCrz03 (0<x<3), LiXCr30a (0<x<3.8), LirV3S;
(0<x<1.8), LiXTa2Sz _ _ _ _(0<x<1), LixFeS (0<x<1), LiXFeS2 (0<x<1), LiXNbSz (0<x<2.4), LiXMoSz to (0<x<3), LixTiSz _ _ _(0<x<2), LixZrSz (0<x<2), LiXNbSez (0<x<3), LixVSez (0<x<_1), LirNiPSz _(0<x_<1.5), LiXFePSz (0<x<1.5), LiNixBi-XOz (0 < x < 1), LiNiXAh-XOz (0 <
x < 1), LiNirMg~-,~Oz (0 < x < 1), LiNiXCot-XVOa (1 >_ x >_ 0), LiNirCoyMnZOz (x+y+z = 1), LiFeOz, LiCrTiOa, LiaMbL,~Oa (1,15 >_ a > 0; 1,3 >_ b+c >- 0,8;
2,5 >_ d >1,7; M - Ni, Co, Mn; L = Ti, Mn, Cu, Zn, alkaline earth metals, LiCuxuCuY~Mn~z-~:~+y~~0a (2 > x+y > 0), LiCrTiOa, LiGaXMnz-XOa (0,1 >_ x >_ 0), polycarbonsulfides of the general structure: -[C(SX)]n-, VzOs, a mixture of two or more thereof, and a mixture of the compound ILTIb with the solid IIZa; and the mixture I additionally contains from 0.1 to 20 wt%, based on the blend lI, of conductive black, a molded article being obtained which can be used, in particular, 2o as a cathode.
moreover, the invention relates to a method, wherein the pigment III is a compound >IIc which, during charging, is able to take up lithium ions and which is selected from the group consisting of lithium, a lithium-containing metal alloy, rnicronized carbon black, natural and synthetic graphite, synthetically graphitized carbon dust, a carbon fiber, titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, titanium carbonate, molybdenum carbonate, zinc carbonate, LirMySiOz (1 > x >_ 0, 1 > y >_ 0, z > 0), SnzBPOa, conjungated polymers such as polypyrroles, polyanilines, polyacetylenes, polyphenylenes, lithium metal compounds LixM, such 3o as those, wherein M = Sn, Bi, Sb, Zn, Cd, Pb and 5 >_ x >_ 0; Li-Sn-Cd, CdO, PbO, a .. CA 02285007 1999-09-22 a O.Z. 0050147880 mixture of two or more thereof, and a mixture of the compound ITIc with the solid Illa; and the mixture I additionally contains up to 20 wt%, based on the blend II, of conductive black, a molded article being obtained which can be used, in particular, as an anode.
Particularly suitable are pigments III having a primary particle size of from 5 nm to 20 mm, preferably from 0.01 to 10 mm and in particular from 0.1 to 5 mm, the specified particle sizes being determined by electron microscopy. The melting point of the pigments is preferably above the normal operating temperature for the electro-l0 chemical cell, melting points of above 120°C, in particular of above 150°C having proved particularly beneficial.
In this context the pigments, in terms of their external shape, can be symmetrical, i.e.
have a size ratio height:width:length (aspect ratio) of approximately 1 and be present in the form of spheres, granules, approximately round structures, but also in the form of any type of polyhedron such as e.g. cuboids, tetrahedra, hexahedra, octahedra or as a bipyramid or be distorted or asymmetrical, i.e. have a size ratio height:width:length (aspect ratio) different from 1 and be present e.g. as needles, asymmetric tetrahedra, asymmetric bipyramids, asymmetric hexahedra or octahedra, laminae, disks or fibrous structures. Insofar as the solids are present as asymmetric particles, the above-specified upper limit for the primary particle size in each case refers to the shortest axis.
In the course of the production of the molded articles which can be used as a cathode or anode, the conductive black, if present, is preferably added to the blend II in the form of a masterbatch. The masterbatch is a composition which contains from 20 to 50 wt% of conductive black, from 5 to 30 wt% of polymeric binder IV and from to 75 wt% of plasticizer IV, the amount and composition chosen of the masterbatch being such that, based on the blend II, the amount of conducting salt added in total does not exceed 20 wt%. The masterbatch is preferably prepared by compounding .. CA 02285007 1999-09-22 and melt extrusion of the abovementioned components.
O.Z. 0050/47880 The blends II should comprise, according to the invention, from 1 to 95 wt%, preferably from 25 to 90 wt% and in particular from 30 to 70 wt% of a pigment III
and from 5 to 99 wt%, preferably from 10 to 75 wt% and in particular from 30 to 70 wt% of a polymeric binder N, where the polymeric binder should advantageously have a mean molec-ular weight (number average) of from 5000 to 100,000,000, preferably from 50,000 to 8,000,000.
to The following additional feedstocks are used in producing the molded article or in the mixture I used or the blend II:
Used as the polymeric binders N are thermoplastic and ion-conductive polymers, examples to be mentioned in particular being:
1) Homopolymers, block polymers or copolymers Na (polymers Na) which can be obtained by polymerization of bl) from 5 to 100 wt%, based on the polymer IVa, of a condensation 2o product VI of a) at least one compound VII which is able to react with a carboxylic acid or a sulfonic acid or a derivative or a mixture of two or more of these, and at least 1 mol per mole of the compound VII of a carboxylic acid z5 or sulfonic acid VIII which has at least one free-radical poly-merizable functional group or of a derivative thereof or of a mixture of two or more of these and b2) from 0 to 95 wt%, based on the polymer IVa, of a further compound IX
O.Z. 0050147880 having a mean molecular weight (number average) of at least 5000 comprising polyether segments in the main chain or a side chain.
The polymer Na is preferably obtainable via bl) from 5 to 100 wt%, based on the polymer IVa, of a condensation product VI of a) a polyhydric alcohol VII which contains carbon atoms and l0 oxygen atoms in the main chain, and (~) at least 1 mol per mole of the polyhydric alcohol VII of an a, ~ -unsaturated carboxylic acid VILLI, and b2) from 0 to 95 wt%, based on the polymer Na, of a further 2o compound IX having a mean molecular weight (number average) of at least 5000 comprising polyether segments in the main chain or a side chain.
Suitable, in principle, as the compound VII which is capable of reacting with a carboxylic acid or a sulfonic acid VIII or a derivative or a mixture of two or more thereof are all compounds which satisfy this criterion.
The compound VII is preferentially selected from the group consisting of a mono- or polyhydric alcohol which in its main chain solely comprises carbon 3o atoms; a mono- or polyhydric alcohol which in its main chain, in addition to at least two carbon atoms, has at least one atom which is selected from the group .. CA 02285007 1999-09-22 O.Z. 0050147880 consisting of oxygen, phosphorus and nitrogen; a silicon-containing compound;
an amine having at least one primary amino group; an amine having at least one secondary amino group; an amino alcohol; a mono- or polyhydric thiol; a compound having at least one thiol and at least one hydroxyl group; and a mixture of two or more of these.
Among these, in turn, compounds VII are preferred which have two or more functional groups which are able to react with the carboxylic acid or sulfonic acid.
If compounds VII are used which as the functional group contain amino groups, preference is given to the use of those having secondary amino groups, so that after the condensation/cross-linking either no free NH groups or only small amounts of these are present in the mixture Ia.
To be mentioned individually as preferred compounds are:
mono- or polyhydric alcohols whose main chain consists exclusively of carbon atoms and which have from 1 to 20, preferably from 2 to 20 and in particular from 2 to 10 alcoholic OH groups, in particular dihydric, trihydric and 2o tetrahydric alcohols, preferably having from 2 to 20 carbon atoms, such as e.g.
ethylene glycol, propane-1,2- or -1,3-diol, butane-1,2- or -1,3-diol, butene-1,4-or butyne-1,4-diol, hexane-1,6-diol, neopentyl glycol, dodecane-1,2-diol, glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, hydroquinone, novolak, bisphenol A, an alternative option, however, as follows from the above definition, being the use of monohydric alcohols such as e.g. methanol, ethanol, propanol, n-, sec- or t-butanol etc.; furthermore it is also possible to employ polyhydroxyolefins, preferably those having two terminal hydroxyl groups, such as e.g. a,~-dihydroxybutadiene;
polyester polyols such as those known e.g. from Ullinann's Encyklopddie der technischen Chemie, 4'h edition, vol. 19, pp. 62-65 and obtainable, for example, by the reaction of dihydric alcohols with polybasic, preferably dibasic ~~
O.Z. 0050/47880 polycarboxylic acids;
mono- or polyhydric alcohols which in their main chain, in addition to at least two carbon atoms, contain at least one oxygen atom, preferably polyether alcohols such as e.g. polymerization products of alkylene epoxides, for example isobutylene oxide, propylene oxide, ethylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, tetrahydrofuran, styrene oxide, an additional option being the use of polyether alcohols modified at their terminal groups, such as e.g. polyether alcohols modified by means of NH2 terminal groups; these alcohols preferably have a molecular weight {number average) of 1o from 100 to 5000, more preferably from 200 to 1000 and in particular from to 800; compounds of this type are known per se and are commercially available, for example, under the brands Pluriol~ or Pluronic~ (BASF Aktien-gesellschaft);
alcohols as defined above, in which some or all of the carbon atoms have been replaced by silicon, a particular option in this context being the use of polysiloxanes or alkylene oxide/siloxane copolymers or mixtures of polyether alcohols and polysiloxanes, as described, for example, in EP-B 581 296 and EP-A 525 728, what was said above likewise applying to the molecular weight of these alcohols;
2o alcohols as defined above, in particular polyether alcohols in which some or all the oxygen atoms have been replaced by sulfur atoms, what was said above likewise applying to the molecular weight of these alcohols;
mono- or polyhydric alcohols which, in their main chain, in addition to at least two carbon atoms contain at least one phosphorus atom or at least one nitrogen atom such as e.g. diethanolamine, triethanolamine;
lactones which are derived from compounds of the general formula HO-(CHz)Z-COOH, where z is a number from 1 to 20, such as e.g. ~-caprolactone, (~-propiolactone, Y-butyrolactone or methyl- E -caprolactone;
a silicon-containing compound such as e.g. di- or trichlorosilane, 3o phenyltrichlorosilane, diphenyldichlorosilane, dimethylvinylchlorosilane;
silanols such as e.g. trimethylsilanol;
~
. CA 02285007 1999-09-22 O.Z. 0050/47880 an amine having at least one primary and/or secondary amino group, such as e.g. butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, aniline, phenylenediamine;
polyetherdiamines such as e.g. 4,7-dioxadecane-1,10-diamine, 4,11-dioxatetradecane-1,14-diamine;
a mono- or polyhydric thiol such as e.g. aliphatic thiols such as e.g.
methanethiol, ethanethiol, cyclohexanethiol, dodecanethiol; aromatic thiols such as e.g. thiophenol, 4-chlorothiophenol, 2-mercaptoaniline;
to a compound having at least one thiol and at least one hydroxyl group, such as e.g. 4-hydroxythiophenol and monothio derivatives of the above-defined polyhydric alcohols;
amino alcohols such as e.g. ethanolamine, N-methyl-ethanolamine, N-ethylethanolamine, N-butylethanolamine, 2-amino-1-propanol, 2-amino-1-phenylethanol;
mono- or polyaminopolyols having more than two aliphatically bound hydroxyl groups, such as e.g. tris(hydroxymethyl)methylamine, glucamine, N,N'-bis-(2-hydroxyethyl)ethylenediamine, and mixtures of these.
It is also possible to use mixtures of two or more of the above-described compounds VII.
The abovementioned compounds VII are condensed, according to the invention, with a carboxylic acid or sulfonic acid VIII which has at least one free-radical polymerizable functional group or with a derivative thereof or a mixture of two or more of these, at least one, preferably all of the free groups capable of condensation within the compounds VII being condensed with the compound VIII.
3o Suitable in principle as the carboxylic acid or sulfonic acid VIII within the scope of the present invention are all those carboxylic and sulfonic acids which O.Z. 0050/47880 have at least one free-radical polymerizable functional group, as are their derivatives. In this context, the term "derivatives" as used herein comprises both compounds derived from a carboxylic or sulfonic acid which has been modified at the acid function (such as e.g. esters, acid halides or acid anhydrides) and compounds derived from a carboxylic or sulfonic acid which has been modified on the carbon skeleton of the carboxylic or sulfonic acid, such as e.g. halocarboxylic or halosulfonic acids.
Particular examples to be mentioned of compound VIII are:
to a,~-unsaturated carboxylic acids or a,'Y-unsaturated carboxylic acids or derivatives thereof.
Particularly suitable a,~-unsaturated carboxylic acids in this context are those of the formula R3 ~C=C~
COOH
where Rl, RZ and R3 are hydrogen or Ci-Ca-alkyl, among which in turn acrylic acid and methaclylic acid are preferred; also expediently usable are cinnamic acid, malefic acid, fiunaric acid, itaconic acid or p-vinylbenzoic acid and - derivatives of these, such as e.g. anhydrides such as e.g, malefic or itaconic anhydride;
halides, in particular chlorides, such as e.g. acryloyl or methacryloyl chloride;
esters such as e.g. (cyclo)alkyl (meth)acrylates having up to 20 C atoms in the alkyl radical, such as e.g. methyl (meth)acrylate, ethyl (meth)acrylate, propyl -(meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, trifluoromethyl (meth)acrylate, hexa-fluoropropyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, polypropylene-O.Z. 0050147880 glycol mono(meth)acrylates, polyethylene mono(meth)acrylates, poly(meth)acrylates of polyhydric alcohols, such as e.g. glycerol di(meth)-acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di- or tri(meth)acrylate, diethylene glycol bis(mono-(2-acryloxy)ethyl)carbonate, poly(meth)acrylates of alcohols which themselves in turn have a free-radical polymerizable group, such as e.g. esters from (meth)acrylic acid and vinyl andlor allyl alcohol;
vinyl esters of other aliphatic or aromatic carboxylic acids, such as e.g.
vinyl acetate, vinyl propionate, vinyl butanoate, vinyl hexanoate, vinyl octanoate, 1o vinyl decanoate, vinyl stearate, vinyl palmitate, vinyl crotonate, divinyl adipate, divinyl sebacate, vinyl 2-ethylhexanoate, vinyl trifluoroacetate;
allyl esters of other aliphatic or aromatic carboxylic acids, such as e.g.
allyl acetate, allyl propionate, allyl butanoate, allyl hexanoate, allyl octanoate, allyl decanoate, allyl stearate, allyl palmitate, allyl crotonate, allyl salicylate, allyl lactate, diallyl oxalate, allyl stearate, allyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, allyl cinnamate, diallyl maleate, diallyl phthalate, diallyl isophthalate, triallyl benzene-1,3,5-tricarboxylate, allyl fluoroacetate, allyl perfluorobutyrate, allyl perfluorooctanoate;
~~Y-unsaturated carboxylic acids and derivatives thereof, such as e.g.
2o vinylacetic acid, 2-methylvinylacetic acid, isobutyl 3-butenoate, allyl 3-butenoate, allyl 2-hydroxy-3-butenoate, diketene;
sulfonic acids such as, e.g. vinylsulfonic acid, allyl- and methallylsulfonic acid, and their esters and halides, vinyl benzenesulfonate, 4-vinylbenzene-sulfonamide.
It is also possible for mixtures of two or more of the above-described carboxylic and/or sulfonic acids to be used.
The polymer Na can be obtained by the reaction of from 5 to 100 wt%, preferably from 30 to 70 wt%, based on the polymer IVa, of a condensation O.Z. 0050/47880 product VI and from 0 to 95 wt%, in particular from 30 to 70 wt%, based on the polymer IVa, of a compound IX.
2) Homopolymers, block polymers or copolymers Nb (polymers IVb), obtainable by polymerization of bl) frorn 5 to 75 wt%, based on the polymer IVb, of an unsaturated compound X which is capable of free-radical polymerization and differs from the above carboxylic acid or the sulfonic acid or a derivative 1o thereof, or of a mixture of two or more of these and b2) from 25 to 95 wt%, based on the polymer IVb, of a further compound IX, having a mean molecular weight (number average) of at least 5000 and comprising polyether segments in the main chain or a side chain as a polymeric binder.
Examples to be mentioned in particular of the compound X which can be used 2o for the preparation of the polymer IVb and is capable of free-radical polymer ization include the following:
olefmic hydrocarbons such as e.g. ethylene, propylene, butylene, isobutene, hexene or higher homologs and vinyl cyclohexane;
(meth)acrylonitrile;
halogen-containing olefinic compounds such as e.g. vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, tri-fluoropropene, 1,2-dichloroethylene, 1,2-difluoroethylene and tetrafluoro-ethylene;
vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole, vinylformamide;
phosphonitrile chlorides such as e.g. phosphonitrile dichloride, ~
O.Z. 0050/47880 hexachloro(triphosphazene), and their derivatives partially or completely substituted by alkoxy, phenoxy, amino and fluoroalkoxy groups, i.e.
compounds which can be polymerized to give polyphosphazenes;
aromatic, olefinic compounds such as e.g. styrene, a-methylstyrene;
vinyl ethers such as e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, tetrafluoropropyl vinyl ether.
Of course it is also possible to employ mixtures of the abovementioned l0 compounds X, in which case copolymers are then formed which, depending on the preparation route, contain the monomers in random distribution or result in block copolymers.
These compounds X, like the condensation products VI, are polymerized in a conventional manner well known to those skilled in the art, preferably by free-radical polymerization, the molecular weights obtained being subject to the same points as made below regarding the compound IX.
Potentially suitable, in the first instance, for compound IX are compounds having a mean molecular weight (number average) of at least 5000, preferably from 5000 to 20,000,000, in particular from 100,000 to 6,000,000, which are able to solvate lithium cations and to act as a binder. Examples of suitable compounds IX include polyethers and copolymers which comprise at least 30 wt% of the following structural unit, based on the total weight of the compound IX:
T, 2 ~C-C~~' O-n ~
O.Z. 0050/47880 where R~, R2, R3 and R4 are aryl, alkyl, preferably methyl, or hydrogen, may be identical or different and may include hetero atoms such as oxygen, nitrogen, sulfur or silicon.
Such compounds are described, for example, in: M. B. Armand et al., Fast Ion Transport in Solids, Elsevier, New York, 1979, pp. 131-136, or in FR-A
7832976.
The compound IX may alternatively consist of mixtures of such compounds.
l0 The polymer IVb can be obtained by the reaction of from 5 to 75 wt%, preferably from 30 to 70 wt%, based on the polymer IVb, of a compound X and from 25 to 95 wt%, in particular from 30 to 70 wt%, based on the polymer IVb, of a compound IX;
3) Polycarbonates such as e.g. polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate, polyvinylidene carbonate.
4) Homopolymers, block polymers and copolymers prepared from 2o a) olefinic hydrocarbons such as e.g. ethylene, propylene, butylene, isobutene, propene, hexene or higher homologs, butadiene, cyclopentene, cyclohexene, norbornene, vinylcyclohexane, 1,3-pentadiene, 1,3-, 1,4-, 1,5-hexadiene, isoprene, vinyl norbornene;
b) aromatic hydrocarbons such as e.g. styrene and methylstyrene;
c) acrylic acid or methacrylic acid ester such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl, tetrafluoropropyl acrylate or methacrylate;
d) acrylonitrile, methacrylonitrile, N-methylpyrrolidone, N-3o vinylimidazole, vinyl acetate;
e) vinyl ethers such as e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, O.Z. 0050/47880 hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoro-methyl, hexafluoropropyl, tetrafluoropropyl vinyl ether;
f) halogen-containing olefinic compounds such as vinyl chloride, vinyl fluoride, vinylidene fluoride, vinylidene chloride, hexafluoropropene, trifluoropropene, 1,2-dichloroethene, 1,2-difluoroethene, tetrafluoroethene.
g) 2-vinylpyridine, 4-vinylpyridine, vinylene carbonate.
Within the preparation of the above mentioned polymers, controlling compounds, such as e.g. mercaptane may be used if desired or regarded as being necessary.
5) Polyurethanes, for example obtainable by the reaction of a) organic diisocyanates having from 6 to 30 C atoms, such as e.g.
aliphatic acyclic diisocyanates such as e.g. 1,5-hexamethylene diisocya-nate and 1,6-hexamethylene diisocyanate, aliphatic cyclic diisocyanates such as e.g. 1,4-cyclohexylene diisocyanate, dicyclohexylinethane diisocyanate and isophorone diisocyanate or aromatic diisocyanates such as e.g. 2,4-diisocyanotoluene, 2,6-diisocyanotoluene, m-tetra-2o methylxylene diisocyanate, p-tetramethylxylene diisocyanate, 1,5-diisocyanatotetrahydronaphthalene and 4,4'-diisocyanatodiphenylenemethane or mixtures of such compounds with b) polyhydric alcohols such as e.g. polyesterols, polyetherols and diols.
The polyesterols are expediently predominantly linear polymers having terminal OH groups, preferably those having two or three, in particular two OH
terminal groups. The acid value of the polyesterols is less than 10 and prefer-ably less than 3. The polyesterols can be prepared in a simple manner by 3o esterification of aliphatic or aromatic dicarboxylic acids having from 4 to atoms, preferably from 4 to 6 C atoms, with glycols, preferably glycols having ~
O.Z. 0050/47880 from 2 to 25 C atoms, or by polymerization of lactones having from 3 to 20 C
atoms. Examples of dicarboxylic acids which can be used include glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanoic acid and preferably adipic acid and succinic acid. Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, phthalic acid or mixtures of these dicarboxylic acids with other dicarboxylic acids, e.g. diphenic acid, sebacic acid, succinic acid and adipic acid. The dicarboxylic acids can be used individually or as mixtures.
For the purpose of preparing the polyesterols it may be advantageous for the dicarboxylic acids to be replaced by the corresponding acid derivatives such as to carboxylic acid anhydrides or carboxylic acid chlorides. Examples of suitable glycols are diethylene glycol, 1,5-pentanediol, 1,10-decanediol and 2,2,4-trimethylpentanediol-1,5. Preferentially used are 1,2-ethanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylpropanediol-1,3, 1,4-dimethylolcyclohexane, 1,4-diethanolcyclohexane and ethoxylated or propoxylated products of 2,2-bis-(4-hydroxyphenylene)propane (bisphenol A). Depending on the desired properties of the polyurethanes, the polyols may be used on their own or as a mixture in various quantitative proportions. Suitable as lactones for the preparation of the polyesterols are, e.g. a,a-dimethyl-~-propiolactone, 'Y-butyrolactone and preferably E-caprolactone.
The polyetherols are essentially linear substances which have terminal hydroxyl groups and contain ether bonds. Suitable polyetherols can readily be prepared by polymerization of cyclic ethers such as tetrahydrofuran or by one or more alkylene oxides having from 2 to 4 C atoms in the alkylene radical being reacted with a starter molecule which contains two active hydrogen atoms bound in the alkylene radical. Examples to be mentioned of alkylene oxides include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide, 2,3-butylene oxide. The alkylene oxides can be used singly, alternately in succession or as a mixture. Examples of potentially suitable starter molecules include water, glycols such as ethylene glycol, propylene glycol, 1,4-O.Z. 0050/47880 butanediol and 1,6-hexanediol, amines such as ethylenediamine, hexa-methylenediamine and 4,4'-diaminodiphenylinethane and amino alcohols such as ethanolamine. Suitable polyesterols and polyetherols and their preparation are described, for example, in EP-B 416 386, suitable polycarbonate diols, preferably those based on 1,6-hexanediol, and their preparation are described, for example, in US-A 4 131 731.
Potentially advantageous, in amounts of up to 30 wt%, based on the total mass of the alcohols, are aliphatic diols having from 2 to 20, preferably from 2 to 1o C atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane-diol, 1,5-pentanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, 1,4-dimethylolcyclohexane, neopentyl glycol hydroxypivalate, diethylene glycol, triethylene glycol and methyl diethanolamine or aromatic-aliphatic or aromatic-cycloaliphatic diols having from 8 to 30 C atoms, potentially suitable aromatic structures being heterocyclic ring systems or preferably isocyclic ring systems such as naphthalene and in particular benzene derivatives such as bisphenol A, doubly symmetrically ethoxylated bisphenol A, doubly symmetrically propoxylated bisphenol A, bisphenol A derivatives or bisphenol F derivatives ethoxylated or propoxylated to a higher degree, and mixtures of such compounds.
Potentially advantageous in amounts of up to 5 wt%, based on the total mass of the alcohols, are aliphatic triols having from 3 to 15, preferably from 3 to atoms, such as trimethylolpropane or glycerol, the reaction product of such compounds with ethylene oxide and/or propylene oxide and mixtures of such compounds.
The polyhydric alcohols may carry functional groups, for example neutral 3o groups such as siloxane groups, basic groups such as, in particular, tertiary amino groups or acidic groups or their salts, or groups which are readily O.Z. 0050147880 converted into acidic groups, these functional groups being introduced via a polyhydric alcohol. Preferentially, diol components carrying such groups can be used, such as N-methyldiethanolamine, diethyl N,N-bis(hydroxyethyl)-aminomethylphosphonate or 3-sulfopropyl N,N-bis(hydroxyethyl)-2-aminoacetate or dicarboxylic acids which carry such groups and can be used for the preparation of polyesterols, such as 5-sulfoisophthalic acid.
Acidic groups include, in particular, the phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acid, carboxyl or ammonium group.
Examples of groups which are readily converted into acidic groups include the ester group or salts, preferably of the alkali metals such as lithium, sodium or potassium.
6) The above-described polyesterols per se, in which case care should be taken to ensure that molecular weights in the range of from 10,000 to 2,000,000, preferably from 50,000 to 1,000,000 are obtained.
7) Polyamines, polysiloxanes and polyphosphazenes, in particular of the type 2o already discussed in the context of the description of the polymer Nb.
8) Polyetherols such as those described e.g. in the above discussion of the polymer IVa as compound IX or in the discussion of the polyurethanes.
Suitable for use as the plasticizer V are aprotic solvents, preferably those which solvate Li ions, such as e.g. dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, propylene carbonate; cyclic carbonates of the fomula CnHn+i Oy, n = 2 to 30, m = 3 to 7, such as ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene 3o carbonate, 1,3-butylene carbonate, 1,4-butylene carbonate, 2,3-butylene carbonate;
oligoalkylene oxides such as e.g. dibutyl ether, di-t-butyl ether, dipentyl ether, O.Z. 0050/47880 dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didoceyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-t-butoxy-2-methoxyethane, 1-t-butoxy-1-ethoxyethane, 1,2-dimethoxypropane, 2-methoxyethyl ether, 2-ethoxyethyl ether, diethylene glycol dibutyl ether, dimethylene glycol t-butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 'Y-butyrolactone, dimethylforrnamide; dimethyl- 'Y-butyrolactone, diethyl-1'-butyrolactone, Y-valerolactone, 4,5-dimethyl-1,3-dioxolane-2-one, 4,4-dimethyl-1,3-dioxolane-2-one, 4-ethyl-1,3-dioxolane-2-one, 4-methyl-5-ethyl-1,3-dioxolane-2-one, 4,5-diethyl-1,3-dioxolane-2-one, 4,4-diethyl-1,3-dioxolane-2-one, 1,3-dioxane-2-one, 4-methyl-1,3-dioxane-2-one, S-methyl-1,3-dioxane-2-one, 4,4-dimethyl-1,3-dioxane-2-one, 5,5-dimethyl-1,3-dioxane-2-one, 4,6-dimethyl-1,3-dioxane-2-one, 4,4,6-trimethyl-1,3-dioxane-2-one, 5,5-diethyl-1,3-dioxane-2-one, spiro-(1,3-oxa-2-cyclohexanone)-5',5',1',3'-oxacyclohexane; 4-dimethylethoxysilyl-1,2-butylene carbonate; diester of carboxylic acids of the formula R10COORZOCOOR3 (Rl, R2, R3 = Ct-Czo-hydl'ocarbons), organic ester of the formula Rl-COORz (Rl and R2 = Ci-Czo-hydrocarbons), hydrocarbons of the general formula C~Hzn+z with 7 < n < 50; organic phosphorus compounds, in particular phosphates and phosphonates such as e.g. trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl 2o phosphate, trihexyl phosphate, trioctyl phosphate, tris(2-ethylhexyl) phosphate, tri-decyl phosphate, diethyl n-butyl phosphate, tris(butoxyethyl) phosphate, tris(2-methoxyethyl) phosphate, tris(tetrahydxofuryl) phosphate, tris(1H,1H,SH-octafluoro-pentyl) phosphate, tris(1H,1H-trifluoroethyl) phosphate, tris(2-(diethylamino)ethyl) phosphate, tris(methoxyethoxyethyl)phosphate, tris(methoxy-ethoxy)trifluorphosphazene, tris(methoxycarbonyloxyethyl)phosphate, diethyl ethylphosphonate, dipropyl propylphosphonate, dibutyl butylphosphonate, dihexyl hexylphosphonate, dioctyl octylphosphonate, ethyl dimethyl phosphonoacetate, methyl diethyl phosphonoacetate, triethyl phosphonoacetate, dimethyl (2-oxopropyl)phosphonate, diethyl (2-oxopropyl) phosphonate, dipropyl (2-oxopropyl) 3o phosphonate, ethyl diethoxyphosphinylformate, trimethyl phosphonoacetate, triethyl phosphonoacetate, tripropyl phosphonoacetate, tributyl phosphonoacetate;
organic O.Z. 0050/47880 sulfur compounds such as e.g. sulfates, sulfonates, sulfoxides, sulfones and sulfites, such as e.g. dimethyl sulfite, diethyl sulfite, glycol sulfite, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, tetramethylene sulfone, methylsulfolane, dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, tetramethylene sulfoxide, ethyl methanesulfonate, 1,4-butanediol bis-(methanesulfonate), diethyl sulfate, dipropyl sulfate, dibutyl sulfate, dihexyl sulfate, dioctyl sulfate, S02C1F;
nitrites, such as e.g. acrylonitrile;
dispersants, in particular having a surfactant structure;
1 o and mixtures of these.
Furthermore, in general suitable organic compounds may be used as plasticizer V
such as e.g. acids CnHxFy, wherein n=5 to 30, x,y=2n+2; ethers C"HxFyOZ
wherein n=5 to 30, x+~2n+2, z=1 to 14; ketones CnHXFYO, wherein n=5 tp 30, x+y=2n;
esters C"HxFYOz, wherein n=5 to 30, x+y=2n; carbonates CnHXFy03, wherein n=5 to 30, x+~2n; lactones CnHXFyOz, wherein n=5 to 20, x+y=2n-2; cyclic carbonates C~HxFy03, wherein n=5 to 20, x+y=2n-2; and boric acid esters wherein Rl-R4 = Ci-C2o-hydrocarbons and X = Ci-Cio-hydrocarbons, Si(CH3)z, and n,m = 1,2 R O~ -~R3 O~ 1 ~B-O-R
R-O C O
n R1 O~ /a-R3 Ov B-O-X-O-B ~B-O-B~
R O \D--R4 n~ O > m ~~
O.Z. 0050147880 Rl Ov /~R3 O~
B-O-B ~B-O-X-O-B~
R2 O \O-R4 n ~ O > m particularly trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trimethylen borate, 2-methyl-1,3,2-dioxaborinane, 2-ethyl-1,3,2-dioxaborinane, propyl-1,3,2-dioxaborinane, 2-butyl-1,3,2-dioxaborinane, 2-phenyl-1,3,2-dioxaborinane.
Furthermore, at least one ester of the formulae (E1) to (ES) as shown below, may be used as plasticizer (V):
/ORl B\ OR (E 1 ) \OR
LORI
O=C
\ORZ (E2) - /oRl O=P\ OR2 OR3 (E3) S (-OCH2 CH20CH3)2 (E4) O
O.Z. 0050/47880 R4 O~ /ORl R3 O Sl\OR2 (ES) wherein R', R2, R3, R4 may be the same or different and represent independently from each other a linear or branched Ci-Ca-alkyl group, (-CHz-CHZ-O)n-CH3 wherein n=1 to 3, a C3- to C6-cycloalkyl group, an aromatic hydrocarbon residue, which may be substituted, under the proviso that at least one of the groups R', RZ, R3 or R4 is (-CHz-CHz-O)n-CH3 wherein n=1 to 3.
Within the above-metioned esters of the formulae (E1) to (ES), the phosphoric acid 1 o esters of the formula (E3) are preferably used.
Examples for the group R', RZ and - if present - R3 and/or R4 are methyl, ethyl, n-and iso-propyl, n- and tert.-butyl, cyclopentyl, cyclohexyl and benzyl, as well as (-CHz-CHz-O)"-CH3 wherein n=1 to 3, however, as akeady outlined above, under the proviso that at least one of the groups R~, R2, R3 and R4 is (CHz-CH2-O)"-CH3 wherein n=1 to 3, preferably 1 or 2.
More preferably, esters of the general formulae (E1) to (ES), wherein Rl, RZ
and - if present - R3 and/or R4 are identical and represent -CHa-CHaO-CH3 or (-CHZ-CHz-2o O)z-CH3, are used. Among those, the respective phosphoric acid esters are preferred.
Examples for particular preferably used compounds are those of the formulae (Ela) to (ESa):
~2 ~2~3~3 (E 1 a) ~C ( OCR-I2CH20C'~i3)2 (E2a) _28_ O.Z. 0050/47880 ~P (-~~2 ~2 ~~3~3 (E3a) O S (-OCH2 CH20CH3)2 (E4a) //
O
and Si (-O-CH2 CH2 OCH3)4 (ESa) With respect to their properties, the esters used herein are extraordinarily suitable to be used as plasticizers in films and in general exhibit a viscosity at room temperature of c 10 mPas preferably 5 mPas and particularly < 3 mPas. The exhibt boiling points of in general about 200°C or higher, preferably about 250°C or higher and particularly about 300°C or higher, as rnesured at atmospheric pressure, respectively.
Furthermore, at the tempreature of use of about -50°C to about 150°C, they exhibit a low vapour pressure of about 10-5 to 10°. Due to their boiling points they may be distilled and thus may be obtained in high purity when prepared. Furthermore, at atmospheric pressure these esters are in the liquid state, over a broad temperature range. Generally, they are in the liquid state down to a temperature of about -30°C, preferably down to about -40°C. The esters as disclosed herein, may be used as solvents in electrolyte systems for Li-ion accumulators at at least about 80°C, preferably at at least about 120°C, more preferably at at least about 150°C.
The esters as used according to the invention may also be used in admixture with the 2o above-mentioned plasticizers.
Solvent combinations which exhibit a sufficiently low viscosity, which are capable of strongly dissolving the ions of the conducting salt, which are in the liquid state over a broad temperature range and which are sufficiently electrochemically and chemically stabile and which are hydrolysis resistant are preferred.
~
O.Z. 0050/47880 The esters used according to the present invention may be prepared according to common processes, as e.g. disclosed in K. Mura Kami, Chem. High Polymers (Japan), 7, p. 188-193 (1950) and in H. Steinberg Organoboron Chemistry, chapter 5, J. Wiley & Sons, N.Y. 1964. In general one starts with the acids, acid anhydrids or chorids corresponding to the respective esters, such as boric acid, C(O)Clz, POC13, SOzCIz and SiCla, and reacts those in a known manner with the respective single or polyvalent alcohols or etheroles.
The amount of plasticizer, based on the total weight of the pigment III and the polymeric binder IV is from 1 to 200 wt%, preferably from 2 to 100 wt%, more preferably 2 to 70 wt%.
Suitable as conducting salts are the conducting salts which are generally known and are described, for example, in EP-A 96 629. Particularly suitable in this context are compounds such as e.g. LiPF6, LiAsFb, LiSbFs, LiCIOa, LiC(CF3SOz)3, LiN(CF3SOz)z, LiBFa or LiCF3S03, LiN(SOzC"Fzr,+~)z, LiC[(C~Fzn+i)SOz]3, Li(Cr,Fzn+i)SOz, wherein n=2 to 20, respectively, LiN(SOzF)z, LiAlCla, LiSiFb, (RSOz)"XLl (nX = 10, iS, zN, zP, 3C, 3Si; R = CmFzm+i wherein m=0-10 or Ci-Czo-hydrocarbons) and mixtures of such compounds. LiBFa is preferably used as the 2o conductive salt. Particularly preferred is the combination of the esters of the formulae (Ela) to (E5a) with LiBFa as the conductive salt. Among those, the combination of esters of formula (E3a) and LiBFa as the conductive salt are particularly preferred. These conducting salts are used in amounts of from 0.1 to 50 wt%, preferably from 1 to 10 wt%, in each case based on the mixture.
If required, dispersing resins can be used, to improve dispersion of the pigments, as described in the patent EP 940197.
Potentially suitable as a support material for the molded articles produced according 3o to the invention are the materials usually employed for electrodes, preferably metals such as aluminum and copper. Equally, temporary intermediate supports such as ~
O.Z. 0050/47880 sheets, in particular polyester sheets such as polyethylene terephthalate sheets can be used. Such sheets can advantageously be provided with a parting layer, preferably of polysiloxanes.
Furthermore, the mixtures used according to the invention may, after or during melt extrusion, preferably after the latter, be cross-linked in a manner known per se.
This is effected, for example, by irradiation with ionic or ionizing radiation, electron beam, preferably with an acceleration voltage of between 20 and 2000 kV and a radiation dose of between 5 and 50 Mrad, UV or visible light, with the advantageous option, in the usual way, of adding an initiator such as benzyl dimethyl ketal or 1,3,5-trimethylbenzoyl-triphenylphosphine oxide in amounts of, in particular, at most 1 wt%, based on the polymeric binder and carrying out the cross-linking over a period of, in general, from 0.5 to 15 minutes, advantageously under inert gas such as nitrogen or argon, by thermal free-radical polymerization, preferably at temperatures of above 60°C, with the advantageous option of an initiator such as azo-bis-isobutyronitrile being added in amounts of, in general, at most 5 wt%, preferably from 0.05 to 1 wt%, based on the polymeric binder, by electrochemically induced polymerization or by ionic polymerization, for example by acid-catalyzed cationic polymerization, potentially suitable catalysts in the first instance being acids, preferably Lewis acids such as BFa or, in particular, LiBFa or LiPF6. Lithium ion-containing catalysts such as LiBFa or LiPF6 may, in this case, advantageously remain as a conducting salt within the solid electrolyte or separator.
The present invention further relates to a molded article, preferably a sheet-type molded article which can be obtained by a method, which method comprises the following stage:
I) Compounding and melt extrusion of a mixture I which comprises a blend II
which contains:
~~
O.Z. 0050/47880 a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from 5 nm to 20 mm which is selected from the group consisting of an electrochemically inert solid Illa, a compound IIIb which during charging is a-ble to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IITa with the compound IIIb or the compound Illc, b) from 5 to 99 wt% of at least one polymeric binder IV, and 1o c) from 0 to 200 wt%, based on the total amount of the components a) and b), of at least one plasticizes V, wherein the proportion by weight of the blend II in the mixture I is from 1 to wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder N, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) having an HFP content of from 8 to 25 wt% and, as the plasticizes V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, tris(butoxyethyl)phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
The present invention further relates to a composite body, preferably in the form of a sheet, more preferably in the form of a sheet having a total thickness of from 15 to 1500 mm, in particular having a total thickness of from 50 to 500 mm, which can be obtained by a method, which method comprises the following stages:
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II which contains a solid IIIb or a solid lTIc as defined above, respectively;
~
O.Z. 0050/47880 (II] the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II
which contains a solid IITa, as defined herein, and is free from a solid Illrb or a solid IZIc, and (III) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
The present invention further relates to a composite body which can be obtained by 1o a method, which method comprises the following stages:
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II which contains a solid Illb or a solid IIIc as defined above, respectively;
(II) the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II
which contains a solid IIIa, as defined herein, and is free from a solid ITIb or a solid Illc, and (111) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
The at least one second layer is preferably prepared on a temporary support.
In the process it is possible to employ, according to the invention, customarily used temporary supports such as e.g. a parting sheet made of a polymer or a preferably coated paper such as e.g. a siliconized polyester sheet. This second layer can, however, alternately be prepared on a permanent support such as e.g. a collector electrode or even entirely without a support. In so doing, said layer can be either extruded together with the support or extruded directly onto it.
3o For preparing the composite film, smoothing tools, such as chill-roll devices and devices for preparing tubular films are preferably used.
~
O.Z.0050/47880 The process of bringing together or producing the above-defined layers is effected by processes under atmospheric pressure for the coating or fabrication of sheets, such as e.g. casting or blade coating, and by processing methods under pressure such as e.g. extrusion, coextrusion, laminating, facing, calendering or pressing.
If required, the composite sheet thus produced may be cross-linked or cured by radiation, electrochemically or thermally.
As is implied by the above it is thus readily possible to provide a composite body to comprising the components parting sheet/separator (second layer)/electrode (first layer).
It is further possible, by facing on both sides, to provide a composite body comprising the components anodelseparator/cathode.
The process of charging such composite bodies with an electrolyte and conducting salt can be carried out both before the layers are brought together and, preferably, after this operation, if required after contact has been made with suitable collector electrodes, e.g. a metal foil, and even after the layers have been introduced into a 2o battery jacket, the special microporous structure of the layers, if the mixture according to the invention is used, in particular owing to the presence of the above-defined solid in the separator and possibly in the electrodes, enabling the electrolyte and the conducting salt to be absorbed and the air in the pores to be displaced. The charging operation can be carried out at temperatures of from 0°C to approximately 100°C, depending on the electrolyte employed.
The molded articles are produced by compounding and melt extrusion, preferably at from about 50 to about 250°C.
3o The equipment used for extrusion in this context preferably is in the form of a ~~
O.Z. 0050/47880 plasticating single-screw extruder such as e.g. a Berstorff single-shaft mixing extruder, a Frenkel mixer, a plasticator or a Buss co-kneader, a twin-screw extruder of a corotating or counterrotating type, such as e.g. an extruder with COLOMBO
screws, an extruder with closely meshing ZSK screws, an extruder with Holo-Flite twin screws, a Leistritz kneading pump, an extruder with a Pasquetti twin screw, an extruder with cotruder screws, an extruder of the Kestermann type, an extruder with Mapre twin screws, a GETECHA compounding extruder, an Anger tandem extruder, a Zimmermann-Jansen extruder, a twin-shaft continuous kneader such as e.g. a DSM twin-shaft mixer, an Eck mixtruder, an FCM kneader or a List all-phase 1o appliance or a continuous multishaft extruder such as e.g. a four-screw extruder or a planetary gear extruder or a combination of two or more of these.
Suitable as particularly preferred appliances are single- and twin-screw machines such as e.g. single-shaft mixing extruders (Reifenhauser, Krauss Maffei, Berstorff), corotating or counterrotating closely meshing twin-screw kneaders (Werner and Pfleiderer, Berstorff, APV), multiscrew extruders, Buss co-kneaders or counterrotating, nonmeshing kneaders (Farrel, JSW).
Screws and cylinders of the continuous-operation extrusion plant ZSK 30 are of 2o modular design. To achieve adequate plastication, dispersion and homogenization of the individual components, the process section consists of at most 15 cylinder zones, corresponding to 45 units in length per diameter. Each zone is separately equipped with an electric heater. The casings are cooled with compressed air or water.
The screw consists of a plurality of conveying, plasticating and mixing zones.
A
special configuration of different kneading and mixing elements is required for gentle, homogeneous dispersion of the solids, explicitly of the inorganic pigments, in the polymeric binder.
3o If the molded article according to the invention is to be employed as a solid electrolyte in an electrochemical cell it is advisable to incorporate a dissociable, ~
O.Z. 0050/47880 lithium cation-containing compound, a conducting salt as defined above and further additives such as, in particular, organic solvents, referred to as electrolyte.
These substances can be admixed to the suspension, in part or in their entirety, when the layer is being produced, or can be introduced into the layer after it has been produced.
Potentially suitable organic electrolytes include the esters of formulae (E1) to (ES) and the compounds discussed above in the category "plasticizer V", preference being given to the use of those esters, particularly those of the formula (E3), and the customary organic electrolytes, preferably esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate or mixtures of such compounds.
Solid electrolytes, separators and/or electrodes according to the invention, which are suitable for electrochemical cells, should advantageously have a thickness of from 5 to 500 mm, preferably from 10 to 500 mm, more preferably from 10 to 200 mm and in particular from 20 to 100 mm.
As implied by the above, the present invention also relates to the use of a molded article according to the invention or a composite body according to the invention or of a molded article or composite body produced by means of a method according to the invention for producing a solid electrolyte, a separator, an electrode, in a sensor, an electrochromic window, a display, a capacitor or an ion-conducting foil.
The invention further relates to a separator, a solid electrolyte, an electrode, a sensor, an electrochromic window, a display, a capacitor or an ion-conducting foil comprising a molded article or composite body according to the invention or a molded article or composite body produced according to the invention, and to an 3o electrochemical cell comprising a separator, solid electrolyte or an electrode as defined above or to a combination of two or more of these.
O.Z. 0050/47880 This electrochemical cell can be used, in particular, as a motor vehicle battery, appliance battery or flat-type battery.
Furthermore, the present invention also provides a motor vehicle battery, appliance battery or flat-type battery comprising an electrochemical cell as described above.
EXAMPLES
to To illustrate what happens, in principle, within the method according to the invention, the present application is accompanied by three figures.
Figure 1 shows a schematic depiction of the production of a cathode foil by means of an extruder and an extruder with an ancillary extruder;
Figure 2 shows a schematic depiction of a coextrusion of a mixture used according to the invention, together with a PET sheet;
2o Figure 3 shows a schematic depiction of the production of a cathode (LiMn20a) and an anode foil (MCMB).
First of all, the principles of the production process according to the invention, as they are shown schematically in Figure 1, will be described by way of example relating to a corotating, closely meshing twin-screw kneader ZSK 30 from Werner and Pfleiderer.
The corotating and closely meshing and thus self cleaning extruder (E) consists of a plurality (up to 15) of variable fittable individual zones which can be temperature 3o controlled via heating circuits.
~
Addition of the components:
O.Z. 0050/47880 a) The polymers (P) were homogeneously dispersed, in a fluid mixer, with the pigment and part of the plasticizes. The addition was carried out via a proportioning balance. Where necessary, the extruder was inerted with nitrogen.
b) If required, the plasticizes was added via a proportioning pump in the homogenizing section of the extruder.
to c) The conductive black (LR) was added via an ancillary extruder (SE) in the homogenizing phase. The ancillary extruder was a single- or twin-shaft extruder. If required, a homogeneous melt of polymer, plasticizes and con-ductive black and, where appropriate, dispersing resin was prepared in the ancillary extruder and introduced laterally into the main extruder. The sheet was discharged via a flat-sheet die and calendered. If required, the sheet was coextruded between two sheets (e.g. polyethylene terephthalate (PET)) (Figure 2). The thickness of the battery foils was between 10 and 1000 mm.
2o Among the advantages of the production process according to the invention the following can be mentioned:
1. Solvent can be dispensed with 2. Drying of the battery foils can be dispensed with 3. Extraction and extraction solvent can be dispensed with 4. The sheet can be incorporated into the battery without further pretreatment 5. More homogeneous dispersion of the pigments 6. Better mechanical stability of the films (than sheeting produced via casting technology.
~
Example l: Preparation of a cathode foil 4.910 g of LiMnzOa O.Z. 00501=X7880 1.310 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) 1.030 g of conductive carbon black SuperO P (~~I1VI Carbon) 2.740 g of tributyl phosphate (TBP) Extruder configuration:
Corotating twin-shaft main extruder ZSK30 with 10 variable heatable heating zones.
In the fourth zone a corotating twin-shaft ancillary extruder ZSK30 with 6 variable heatable heating zones was attached.
Preparation:
180 g/h of a blend of 100 parts of Kynar~ 2801 and 5 parts of propylene carbonate and 442 glh of conductive black Super~ P were metered into the first zone of the ancillary extruder ZSK30. In addition, 1075 g/h of propylene. carbonate were 2o pumped into the homogenizing section (zone 2) of the ancillary extruder.
This melt was introduced into the homogenizing section (zone 4) of the main extruder. In addition, 2600 g of a mixture of 15.1 parts of Kynar~ 2801, 81.1 parts of LiMnzOa and 3.8 parts of propylene carbonate were metered into the first zone of the main extruder. The internal temperature in the two extruders was 150°C. Via a heatable flat film die (150°C) having a gap width of 5 mm the melt was discharged and coextruded between two PET sheets and then calendered.
The sheet obtained had the following characteristics:
3o Surface resistance: 140 Ohms ~
Sheet thickness: 100-500 mm Example 2: Preparation of an anode foil Composition:
O.Z. 0050/47880 5600 g of MCMB (Osaka Gas) 1500 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) l0 400 g of conductive black SuperC~ P (M1VIM Carbon) 2500 g of tributyl phosphate (TBP) Extruder configuration: see Example 1 Preparation:
180 g/h of a mixture of 100 parts of Kynar~ 2801 and 5 parts of propylene carbonate and 150 glh of conductive black Super~ P (SP) were metered into the first zone of the ancillary extruder ZSK30. In addition, 841 g/h of propylene 2o carbonate were pumped into the homogenizing section (zone 2) of the ancillary extruder. This melt was introduced into the homogenizing section (zone 4) of the main extruder.
In addition, 2600 g/h of a blend of 15.1 parts of Kynar~ 2801, 80.8 parts of MCMB
and 3.4 parts of propylene carbonate were metered into the first zone of the main extruder. The internal temperature in the two extruders was 150°C.
Via a heatable flat film die (150°C) having a gap width of 5 mm the melt was discharged and coextruded between two PET sheets and then calendered.
The sheet obtained had the following characteristics:
Surface resistance: 80 Ohms Sheet thickness: 50 - 300 mm O.Z. 0050/47880 The preparation of the abovementioned cathode and anode foils is shown schematically in Figure 3.
Example 3: Preparation of a separator foil io 3000 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) 2000 g of Aerosil~ (AE) R 812 (Degussa) 5000 g of tributyl phosphate Preparation:
4500 g/h of a mixture of 30 parts of Kynar~ 2801, 20 parts of Aerosil~ R 812 and 50 parts of tributyl phosphate are metered into a corotating twin-shaft extruder 2o ZSK40 with 10 variable heatable heating zones. The internal temperature in the extruder is 150°C. The melt is discharged via a heatable flat filin die having a gap width of 1 mm and is coextruded between two PET sheets and then calendered.
Sheet thickness: from 20 to 100 mm Example 4 3004 g of polymethacrylate (Luryl~ PMMA G88, BASF) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate Preparation as in Example 3 Example 5 3000 g of polyacrylonitrile (Dralon~ T, Bayer) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate to Preparation as in Example 3 Example 6 3000 g of polyethylene (Lupolen~, BASF) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate Preparation as in Example 3 Example 7 3000 g of polypropylene (Novolen~, BASF) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate Preparation as in Example 3 Example 8 O.Z. 0050/47880 3000 g of poly(vinylidene fluoride)/hexafluoropropene copolymer 3o Kynar~ 2801 (Elf Atochem) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of dibutyl carbonate Preparation as in Example 3 Example 9 O.Z. 0050/47880 3000 g of poly(vinylidene fluoride)Ihexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) 1500 g of Aerosil~ R 812 (Degussa) 1000 g of wollastonite (Tremin~ 8000 EST, Quarzwerke, Frechen) 5000 g of tributyl phosphate Preparation as in Example 3 Example 10 2000 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynalfl 2801 (Elf Atochem) 1000 g of polyethylene oxide) (Polyox~, Union Carbide) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of dibutyl carbonate Preparation as in Example 3.
Example 11 Using the cathode foil according to Example 1, the anode foil according to Example 2 and the separator foil according to Example 3, a composite body having the following structure was fabricated by laminating at a temperature of 140 °C:
Cathode foil/metal lattice foil (aluminum)/cathode foil Separator foil Anode foil/metal lattice foil (copper)/cathode foil.
O.Z. 0050/47880 The composite body was immersed for half an hour in a 1 molar solution of LiPF6 in dimethyl carbonate/ethylene carbonate and then introduced into a flat-type battery jacket. The composite body had good resistance to swelling.
Suitable for use as the plasticizer V are aprotic solvents, preferably those which solvate Li ions, such as e.g. dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, propylene carbonate; cyclic carbonates of the fomula CnHn+i Oy, n = 2 to 30, m = 3 to 7, such as ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene 3o carbonate, 1,3-butylene carbonate, 1,4-butylene carbonate, 2,3-butylene carbonate;
oligoalkylene oxides such as e.g. dibutyl ether, di-t-butyl ether, dipentyl ether, O.Z. 0050/47880 dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didoceyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-t-butoxy-2-methoxyethane, 1-t-butoxy-1-ethoxyethane, 1,2-dimethoxypropane, 2-methoxyethyl ether, 2-ethoxyethyl ether, diethylene glycol dibutyl ether, dimethylene glycol t-butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 'Y-butyrolactone, dimethylforrnamide; dimethyl- 'Y-butyrolactone, diethyl-1'-butyrolactone, Y-valerolactone, 4,5-dimethyl-1,3-dioxolane-2-one, 4,4-dimethyl-1,3-dioxolane-2-one, 4-ethyl-1,3-dioxolane-2-one, 4-methyl-5-ethyl-1,3-dioxolane-2-one, 4,5-diethyl-1,3-dioxolane-2-one, 4,4-diethyl-1,3-dioxolane-2-one, 1,3-dioxane-2-one, 4-methyl-1,3-dioxane-2-one, S-methyl-1,3-dioxane-2-one, 4,4-dimethyl-1,3-dioxane-2-one, 5,5-dimethyl-1,3-dioxane-2-one, 4,6-dimethyl-1,3-dioxane-2-one, 4,4,6-trimethyl-1,3-dioxane-2-one, 5,5-diethyl-1,3-dioxane-2-one, spiro-(1,3-oxa-2-cyclohexanone)-5',5',1',3'-oxacyclohexane; 4-dimethylethoxysilyl-1,2-butylene carbonate; diester of carboxylic acids of the formula R10COORZOCOOR3 (Rl, R2, R3 = Ct-Czo-hydl'ocarbons), organic ester of the formula Rl-COORz (Rl and R2 = Ci-Czo-hydrocarbons), hydrocarbons of the general formula C~Hzn+z with 7 < n < 50; organic phosphorus compounds, in particular phosphates and phosphonates such as e.g. trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl 2o phosphate, trihexyl phosphate, trioctyl phosphate, tris(2-ethylhexyl) phosphate, tri-decyl phosphate, diethyl n-butyl phosphate, tris(butoxyethyl) phosphate, tris(2-methoxyethyl) phosphate, tris(tetrahydxofuryl) phosphate, tris(1H,1H,SH-octafluoro-pentyl) phosphate, tris(1H,1H-trifluoroethyl) phosphate, tris(2-(diethylamino)ethyl) phosphate, tris(methoxyethoxyethyl)phosphate, tris(methoxy-ethoxy)trifluorphosphazene, tris(methoxycarbonyloxyethyl)phosphate, diethyl ethylphosphonate, dipropyl propylphosphonate, dibutyl butylphosphonate, dihexyl hexylphosphonate, dioctyl octylphosphonate, ethyl dimethyl phosphonoacetate, methyl diethyl phosphonoacetate, triethyl phosphonoacetate, dimethyl (2-oxopropyl)phosphonate, diethyl (2-oxopropyl) phosphonate, dipropyl (2-oxopropyl) 3o phosphonate, ethyl diethoxyphosphinylformate, trimethyl phosphonoacetate, triethyl phosphonoacetate, tripropyl phosphonoacetate, tributyl phosphonoacetate;
organic O.Z. 0050/47880 sulfur compounds such as e.g. sulfates, sulfonates, sulfoxides, sulfones and sulfites, such as e.g. dimethyl sulfite, diethyl sulfite, glycol sulfite, dimethyl sulfone, diethyl sulfone, dipropyl sulfone, dibutyl sulfone, tetramethylene sulfone, methylsulfolane, dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, tetramethylene sulfoxide, ethyl methanesulfonate, 1,4-butanediol bis-(methanesulfonate), diethyl sulfate, dipropyl sulfate, dibutyl sulfate, dihexyl sulfate, dioctyl sulfate, S02C1F;
nitrites, such as e.g. acrylonitrile;
dispersants, in particular having a surfactant structure;
1 o and mixtures of these.
Furthermore, in general suitable organic compounds may be used as plasticizer V
such as e.g. acids CnHxFy, wherein n=5 to 30, x,y=2n+2; ethers C"HxFyOZ
wherein n=5 to 30, x+~2n+2, z=1 to 14; ketones CnHXFYO, wherein n=5 tp 30, x+y=2n;
esters C"HxFYOz, wherein n=5 to 30, x+y=2n; carbonates CnHXFy03, wherein n=5 to 30, x+~2n; lactones CnHXFyOz, wherein n=5 to 20, x+y=2n-2; cyclic carbonates C~HxFy03, wherein n=5 to 20, x+y=2n-2; and boric acid esters wherein Rl-R4 = Ci-C2o-hydrocarbons and X = Ci-Cio-hydrocarbons, Si(CH3)z, and n,m = 1,2 R O~ -~R3 O~ 1 ~B-O-R
R-O C O
n R1 O~ /a-R3 Ov B-O-X-O-B ~B-O-B~
R O \D--R4 n~ O > m ~~
O.Z. 0050147880 Rl Ov /~R3 O~
B-O-B ~B-O-X-O-B~
R2 O \O-R4 n ~ O > m particularly trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, trimethylen borate, 2-methyl-1,3,2-dioxaborinane, 2-ethyl-1,3,2-dioxaborinane, propyl-1,3,2-dioxaborinane, 2-butyl-1,3,2-dioxaborinane, 2-phenyl-1,3,2-dioxaborinane.
Furthermore, at least one ester of the formulae (E1) to (ES) as shown below, may be used as plasticizer (V):
/ORl B\ OR (E 1 ) \OR
LORI
O=C
\ORZ (E2) - /oRl O=P\ OR2 OR3 (E3) S (-OCH2 CH20CH3)2 (E4) O
O.Z. 0050/47880 R4 O~ /ORl R3 O Sl\OR2 (ES) wherein R', R2, R3, R4 may be the same or different and represent independently from each other a linear or branched Ci-Ca-alkyl group, (-CHz-CHZ-O)n-CH3 wherein n=1 to 3, a C3- to C6-cycloalkyl group, an aromatic hydrocarbon residue, which may be substituted, under the proviso that at least one of the groups R', RZ, R3 or R4 is (-CHz-CHz-O)n-CH3 wherein n=1 to 3.
Within the above-metioned esters of the formulae (E1) to (ES), the phosphoric acid 1 o esters of the formula (E3) are preferably used.
Examples for the group R', RZ and - if present - R3 and/or R4 are methyl, ethyl, n-and iso-propyl, n- and tert.-butyl, cyclopentyl, cyclohexyl and benzyl, as well as (-CHz-CHz-O)"-CH3 wherein n=1 to 3, however, as akeady outlined above, under the proviso that at least one of the groups R~, R2, R3 and R4 is (CHz-CH2-O)"-CH3 wherein n=1 to 3, preferably 1 or 2.
More preferably, esters of the general formulae (E1) to (ES), wherein Rl, RZ
and - if present - R3 and/or R4 are identical and represent -CHa-CHaO-CH3 or (-CHZ-CHz-2o O)z-CH3, are used. Among those, the respective phosphoric acid esters are preferred.
Examples for particular preferably used compounds are those of the formulae (Ela) to (ESa):
~2 ~2~3~3 (E 1 a) ~C ( OCR-I2CH20C'~i3)2 (E2a) _28_ O.Z. 0050/47880 ~P (-~~2 ~2 ~~3~3 (E3a) O S (-OCH2 CH20CH3)2 (E4a) //
O
and Si (-O-CH2 CH2 OCH3)4 (ESa) With respect to their properties, the esters used herein are extraordinarily suitable to be used as plasticizers in films and in general exhibit a viscosity at room temperature of c 10 mPas preferably 5 mPas and particularly < 3 mPas. The exhibt boiling points of in general about 200°C or higher, preferably about 250°C or higher and particularly about 300°C or higher, as rnesured at atmospheric pressure, respectively.
Furthermore, at the tempreature of use of about -50°C to about 150°C, they exhibit a low vapour pressure of about 10-5 to 10°. Due to their boiling points they may be distilled and thus may be obtained in high purity when prepared. Furthermore, at atmospheric pressure these esters are in the liquid state, over a broad temperature range. Generally, they are in the liquid state down to a temperature of about -30°C, preferably down to about -40°C. The esters as disclosed herein, may be used as solvents in electrolyte systems for Li-ion accumulators at at least about 80°C, preferably at at least about 120°C, more preferably at at least about 150°C.
The esters as used according to the invention may also be used in admixture with the 2o above-mentioned plasticizers.
Solvent combinations which exhibit a sufficiently low viscosity, which are capable of strongly dissolving the ions of the conducting salt, which are in the liquid state over a broad temperature range and which are sufficiently electrochemically and chemically stabile and which are hydrolysis resistant are preferred.
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O.Z. 0050/47880 The esters used according to the present invention may be prepared according to common processes, as e.g. disclosed in K. Mura Kami, Chem. High Polymers (Japan), 7, p. 188-193 (1950) and in H. Steinberg Organoboron Chemistry, chapter 5, J. Wiley & Sons, N.Y. 1964. In general one starts with the acids, acid anhydrids or chorids corresponding to the respective esters, such as boric acid, C(O)Clz, POC13, SOzCIz and SiCla, and reacts those in a known manner with the respective single or polyvalent alcohols or etheroles.
The amount of plasticizer, based on the total weight of the pigment III and the polymeric binder IV is from 1 to 200 wt%, preferably from 2 to 100 wt%, more preferably 2 to 70 wt%.
Suitable as conducting salts are the conducting salts which are generally known and are described, for example, in EP-A 96 629. Particularly suitable in this context are compounds such as e.g. LiPF6, LiAsFb, LiSbFs, LiCIOa, LiC(CF3SOz)3, LiN(CF3SOz)z, LiBFa or LiCF3S03, LiN(SOzC"Fzr,+~)z, LiC[(C~Fzn+i)SOz]3, Li(Cr,Fzn+i)SOz, wherein n=2 to 20, respectively, LiN(SOzF)z, LiAlCla, LiSiFb, (RSOz)"XLl (nX = 10, iS, zN, zP, 3C, 3Si; R = CmFzm+i wherein m=0-10 or Ci-Czo-hydrocarbons) and mixtures of such compounds. LiBFa is preferably used as the 2o conductive salt. Particularly preferred is the combination of the esters of the formulae (Ela) to (E5a) with LiBFa as the conductive salt. Among those, the combination of esters of formula (E3a) and LiBFa as the conductive salt are particularly preferred. These conducting salts are used in amounts of from 0.1 to 50 wt%, preferably from 1 to 10 wt%, in each case based on the mixture.
If required, dispersing resins can be used, to improve dispersion of the pigments, as described in the patent EP 940197.
Potentially suitable as a support material for the molded articles produced according 3o to the invention are the materials usually employed for electrodes, preferably metals such as aluminum and copper. Equally, temporary intermediate supports such as ~
O.Z. 0050/47880 sheets, in particular polyester sheets such as polyethylene terephthalate sheets can be used. Such sheets can advantageously be provided with a parting layer, preferably of polysiloxanes.
Furthermore, the mixtures used according to the invention may, after or during melt extrusion, preferably after the latter, be cross-linked in a manner known per se.
This is effected, for example, by irradiation with ionic or ionizing radiation, electron beam, preferably with an acceleration voltage of between 20 and 2000 kV and a radiation dose of between 5 and 50 Mrad, UV or visible light, with the advantageous option, in the usual way, of adding an initiator such as benzyl dimethyl ketal or 1,3,5-trimethylbenzoyl-triphenylphosphine oxide in amounts of, in particular, at most 1 wt%, based on the polymeric binder and carrying out the cross-linking over a period of, in general, from 0.5 to 15 minutes, advantageously under inert gas such as nitrogen or argon, by thermal free-radical polymerization, preferably at temperatures of above 60°C, with the advantageous option of an initiator such as azo-bis-isobutyronitrile being added in amounts of, in general, at most 5 wt%, preferably from 0.05 to 1 wt%, based on the polymeric binder, by electrochemically induced polymerization or by ionic polymerization, for example by acid-catalyzed cationic polymerization, potentially suitable catalysts in the first instance being acids, preferably Lewis acids such as BFa or, in particular, LiBFa or LiPF6. Lithium ion-containing catalysts such as LiBFa or LiPF6 may, in this case, advantageously remain as a conducting salt within the solid electrolyte or separator.
The present invention further relates to a molded article, preferably a sheet-type molded article which can be obtained by a method, which method comprises the following stage:
I) Compounding and melt extrusion of a mixture I which comprises a blend II
which contains:
~~
O.Z. 0050/47880 a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from 5 nm to 20 mm which is selected from the group consisting of an electrochemically inert solid Illa, a compound IIIb which during charging is a-ble to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IITa with the compound IIIb or the compound Illc, b) from 5 to 99 wt% of at least one polymeric binder IV, and 1o c) from 0 to 200 wt%, based on the total amount of the components a) and b), of at least one plasticizes V, wherein the proportion by weight of the blend II in the mixture I is from 1 to wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder N, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) having an HFP content of from 8 to 25 wt% and, as the plasticizes V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, tris(butoxyethyl)phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
The present invention further relates to a composite body, preferably in the form of a sheet, more preferably in the form of a sheet having a total thickness of from 15 to 1500 mm, in particular having a total thickness of from 50 to 500 mm, which can be obtained by a method, which method comprises the following stages:
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II which contains a solid IIIb or a solid lTIc as defined above, respectively;
~
O.Z. 0050/47880 (II] the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II
which contains a solid IITa, as defined herein, and is free from a solid Illrb or a solid IZIc, and (III) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
The present invention further relates to a composite body which can be obtained by 1o a method, which method comprises the following stages:
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II which contains a solid Illb or a solid IIIc as defined above, respectively;
(II) the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined above, said mixture comprising a blend II
which contains a solid IIIa, as defined herein, and is free from a solid ITIb or a solid Illc, and (111) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
The at least one second layer is preferably prepared on a temporary support.
In the process it is possible to employ, according to the invention, customarily used temporary supports such as e.g. a parting sheet made of a polymer or a preferably coated paper such as e.g. a siliconized polyester sheet. This second layer can, however, alternately be prepared on a permanent support such as e.g. a collector electrode or even entirely without a support. In so doing, said layer can be either extruded together with the support or extruded directly onto it.
3o For preparing the composite film, smoothing tools, such as chill-roll devices and devices for preparing tubular films are preferably used.
~
O.Z.0050/47880 The process of bringing together or producing the above-defined layers is effected by processes under atmospheric pressure for the coating or fabrication of sheets, such as e.g. casting or blade coating, and by processing methods under pressure such as e.g. extrusion, coextrusion, laminating, facing, calendering or pressing.
If required, the composite sheet thus produced may be cross-linked or cured by radiation, electrochemically or thermally.
As is implied by the above it is thus readily possible to provide a composite body to comprising the components parting sheet/separator (second layer)/electrode (first layer).
It is further possible, by facing on both sides, to provide a composite body comprising the components anodelseparator/cathode.
The process of charging such composite bodies with an electrolyte and conducting salt can be carried out both before the layers are brought together and, preferably, after this operation, if required after contact has been made with suitable collector electrodes, e.g. a metal foil, and even after the layers have been introduced into a 2o battery jacket, the special microporous structure of the layers, if the mixture according to the invention is used, in particular owing to the presence of the above-defined solid in the separator and possibly in the electrodes, enabling the electrolyte and the conducting salt to be absorbed and the air in the pores to be displaced. The charging operation can be carried out at temperatures of from 0°C to approximately 100°C, depending on the electrolyte employed.
The molded articles are produced by compounding and melt extrusion, preferably at from about 50 to about 250°C.
3o The equipment used for extrusion in this context preferably is in the form of a ~~
O.Z. 0050/47880 plasticating single-screw extruder such as e.g. a Berstorff single-shaft mixing extruder, a Frenkel mixer, a plasticator or a Buss co-kneader, a twin-screw extruder of a corotating or counterrotating type, such as e.g. an extruder with COLOMBO
screws, an extruder with closely meshing ZSK screws, an extruder with Holo-Flite twin screws, a Leistritz kneading pump, an extruder with a Pasquetti twin screw, an extruder with cotruder screws, an extruder of the Kestermann type, an extruder with Mapre twin screws, a GETECHA compounding extruder, an Anger tandem extruder, a Zimmermann-Jansen extruder, a twin-shaft continuous kneader such as e.g. a DSM twin-shaft mixer, an Eck mixtruder, an FCM kneader or a List all-phase 1o appliance or a continuous multishaft extruder such as e.g. a four-screw extruder or a planetary gear extruder or a combination of two or more of these.
Suitable as particularly preferred appliances are single- and twin-screw machines such as e.g. single-shaft mixing extruders (Reifenhauser, Krauss Maffei, Berstorff), corotating or counterrotating closely meshing twin-screw kneaders (Werner and Pfleiderer, Berstorff, APV), multiscrew extruders, Buss co-kneaders or counterrotating, nonmeshing kneaders (Farrel, JSW).
Screws and cylinders of the continuous-operation extrusion plant ZSK 30 are of 2o modular design. To achieve adequate plastication, dispersion and homogenization of the individual components, the process section consists of at most 15 cylinder zones, corresponding to 45 units in length per diameter. Each zone is separately equipped with an electric heater. The casings are cooled with compressed air or water.
The screw consists of a plurality of conveying, plasticating and mixing zones.
A
special configuration of different kneading and mixing elements is required for gentle, homogeneous dispersion of the solids, explicitly of the inorganic pigments, in the polymeric binder.
3o If the molded article according to the invention is to be employed as a solid electrolyte in an electrochemical cell it is advisable to incorporate a dissociable, ~
O.Z. 0050/47880 lithium cation-containing compound, a conducting salt as defined above and further additives such as, in particular, organic solvents, referred to as electrolyte.
These substances can be admixed to the suspension, in part or in their entirety, when the layer is being produced, or can be introduced into the layer after it has been produced.
Potentially suitable organic electrolytes include the esters of formulae (E1) to (ES) and the compounds discussed above in the category "plasticizer V", preference being given to the use of those esters, particularly those of the formula (E3), and the customary organic electrolytes, preferably esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate or mixtures of such compounds.
Solid electrolytes, separators and/or electrodes according to the invention, which are suitable for electrochemical cells, should advantageously have a thickness of from 5 to 500 mm, preferably from 10 to 500 mm, more preferably from 10 to 200 mm and in particular from 20 to 100 mm.
As implied by the above, the present invention also relates to the use of a molded article according to the invention or a composite body according to the invention or of a molded article or composite body produced by means of a method according to the invention for producing a solid electrolyte, a separator, an electrode, in a sensor, an electrochromic window, a display, a capacitor or an ion-conducting foil.
The invention further relates to a separator, a solid electrolyte, an electrode, a sensor, an electrochromic window, a display, a capacitor or an ion-conducting foil comprising a molded article or composite body according to the invention or a molded article or composite body produced according to the invention, and to an 3o electrochemical cell comprising a separator, solid electrolyte or an electrode as defined above or to a combination of two or more of these.
O.Z. 0050/47880 This electrochemical cell can be used, in particular, as a motor vehicle battery, appliance battery or flat-type battery.
Furthermore, the present invention also provides a motor vehicle battery, appliance battery or flat-type battery comprising an electrochemical cell as described above.
EXAMPLES
to To illustrate what happens, in principle, within the method according to the invention, the present application is accompanied by three figures.
Figure 1 shows a schematic depiction of the production of a cathode foil by means of an extruder and an extruder with an ancillary extruder;
Figure 2 shows a schematic depiction of a coextrusion of a mixture used according to the invention, together with a PET sheet;
2o Figure 3 shows a schematic depiction of the production of a cathode (LiMn20a) and an anode foil (MCMB).
First of all, the principles of the production process according to the invention, as they are shown schematically in Figure 1, will be described by way of example relating to a corotating, closely meshing twin-screw kneader ZSK 30 from Werner and Pfleiderer.
The corotating and closely meshing and thus self cleaning extruder (E) consists of a plurality (up to 15) of variable fittable individual zones which can be temperature 3o controlled via heating circuits.
~
Addition of the components:
O.Z. 0050/47880 a) The polymers (P) were homogeneously dispersed, in a fluid mixer, with the pigment and part of the plasticizes. The addition was carried out via a proportioning balance. Where necessary, the extruder was inerted with nitrogen.
b) If required, the plasticizes was added via a proportioning pump in the homogenizing section of the extruder.
to c) The conductive black (LR) was added via an ancillary extruder (SE) in the homogenizing phase. The ancillary extruder was a single- or twin-shaft extruder. If required, a homogeneous melt of polymer, plasticizes and con-ductive black and, where appropriate, dispersing resin was prepared in the ancillary extruder and introduced laterally into the main extruder. The sheet was discharged via a flat-sheet die and calendered. If required, the sheet was coextruded between two sheets (e.g. polyethylene terephthalate (PET)) (Figure 2). The thickness of the battery foils was between 10 and 1000 mm.
2o Among the advantages of the production process according to the invention the following can be mentioned:
1. Solvent can be dispensed with 2. Drying of the battery foils can be dispensed with 3. Extraction and extraction solvent can be dispensed with 4. The sheet can be incorporated into the battery without further pretreatment 5. More homogeneous dispersion of the pigments 6. Better mechanical stability of the films (than sheeting produced via casting technology.
~
Example l: Preparation of a cathode foil 4.910 g of LiMnzOa O.Z. 00501=X7880 1.310 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) 1.030 g of conductive carbon black SuperO P (~~I1VI Carbon) 2.740 g of tributyl phosphate (TBP) Extruder configuration:
Corotating twin-shaft main extruder ZSK30 with 10 variable heatable heating zones.
In the fourth zone a corotating twin-shaft ancillary extruder ZSK30 with 6 variable heatable heating zones was attached.
Preparation:
180 g/h of a blend of 100 parts of Kynar~ 2801 and 5 parts of propylene carbonate and 442 glh of conductive black Super~ P were metered into the first zone of the ancillary extruder ZSK30. In addition, 1075 g/h of propylene. carbonate were 2o pumped into the homogenizing section (zone 2) of the ancillary extruder.
This melt was introduced into the homogenizing section (zone 4) of the main extruder. In addition, 2600 g of a mixture of 15.1 parts of Kynar~ 2801, 81.1 parts of LiMnzOa and 3.8 parts of propylene carbonate were metered into the first zone of the main extruder. The internal temperature in the two extruders was 150°C. Via a heatable flat film die (150°C) having a gap width of 5 mm the melt was discharged and coextruded between two PET sheets and then calendered.
The sheet obtained had the following characteristics:
3o Surface resistance: 140 Ohms ~
Sheet thickness: 100-500 mm Example 2: Preparation of an anode foil Composition:
O.Z. 0050/47880 5600 g of MCMB (Osaka Gas) 1500 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) l0 400 g of conductive black SuperC~ P (M1VIM Carbon) 2500 g of tributyl phosphate (TBP) Extruder configuration: see Example 1 Preparation:
180 g/h of a mixture of 100 parts of Kynar~ 2801 and 5 parts of propylene carbonate and 150 glh of conductive black Super~ P (SP) were metered into the first zone of the ancillary extruder ZSK30. In addition, 841 g/h of propylene 2o carbonate were pumped into the homogenizing section (zone 2) of the ancillary extruder. This melt was introduced into the homogenizing section (zone 4) of the main extruder.
In addition, 2600 g/h of a blend of 15.1 parts of Kynar~ 2801, 80.8 parts of MCMB
and 3.4 parts of propylene carbonate were metered into the first zone of the main extruder. The internal temperature in the two extruders was 150°C.
Via a heatable flat film die (150°C) having a gap width of 5 mm the melt was discharged and coextruded between two PET sheets and then calendered.
The sheet obtained had the following characteristics:
Surface resistance: 80 Ohms Sheet thickness: 50 - 300 mm O.Z. 0050/47880 The preparation of the abovementioned cathode and anode foils is shown schematically in Figure 3.
Example 3: Preparation of a separator foil io 3000 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) 2000 g of Aerosil~ (AE) R 812 (Degussa) 5000 g of tributyl phosphate Preparation:
4500 g/h of a mixture of 30 parts of Kynar~ 2801, 20 parts of Aerosil~ R 812 and 50 parts of tributyl phosphate are metered into a corotating twin-shaft extruder 2o ZSK40 with 10 variable heatable heating zones. The internal temperature in the extruder is 150°C. The melt is discharged via a heatable flat filin die having a gap width of 1 mm and is coextruded between two PET sheets and then calendered.
Sheet thickness: from 20 to 100 mm Example 4 3004 g of polymethacrylate (Luryl~ PMMA G88, BASF) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate Preparation as in Example 3 Example 5 3000 g of polyacrylonitrile (Dralon~ T, Bayer) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate to Preparation as in Example 3 Example 6 3000 g of polyethylene (Lupolen~, BASF) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate Preparation as in Example 3 Example 7 3000 g of polypropylene (Novolen~, BASF) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of tributyl phosphate Preparation as in Example 3 Example 8 O.Z. 0050/47880 3000 g of poly(vinylidene fluoride)/hexafluoropropene copolymer 3o Kynar~ 2801 (Elf Atochem) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of dibutyl carbonate Preparation as in Example 3 Example 9 O.Z. 0050/47880 3000 g of poly(vinylidene fluoride)Ihexafluoropropene copolymer Kynar~ 2801 (Elf Atochem) 1500 g of Aerosil~ R 812 (Degussa) 1000 g of wollastonite (Tremin~ 8000 EST, Quarzwerke, Frechen) 5000 g of tributyl phosphate Preparation as in Example 3 Example 10 2000 g of poly(vinylidene fluoride)/hexafluoropropene copolymer Kynalfl 2801 (Elf Atochem) 1000 g of polyethylene oxide) (Polyox~, Union Carbide) 2000 g of Aerosil~ R 812 (Degussa) 5000 g of dibutyl carbonate Preparation as in Example 3.
Example 11 Using the cathode foil according to Example 1, the anode foil according to Example 2 and the separator foil according to Example 3, a composite body having the following structure was fabricated by laminating at a temperature of 140 °C:
Cathode foil/metal lattice foil (aluminum)/cathode foil Separator foil Anode foil/metal lattice foil (copper)/cathode foil.
O.Z. 0050/47880 The composite body was immersed for half an hour in a 1 molar solution of LiPF6 in dimethyl carbonate/ethylene carbonate and then introduced into a flat-type battery jacket. The composite body had good resistance to swelling.
Claims (13)
1. A method for producing a molded article, preferably a sheet-type molded article, which method comprises the following stage:
I) Compounding and melt extrusion of a mixture I which comprises a blend II which contains:
a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from 5 nm to 20 mm which is selected from the group consisting of an electrochemically inert solid IIIa, a compound IIIb which during charging is able to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IIIa with the compound IIIb or the compound IIIc, b) from 5 to 99 wt% of at least one polymeric binder IV, and c) from 0 to 200 wt%, based on the total amount of the components a) and b), at least one plasticizer V, wherein the proportion by weight of the blend II in the mixture I is from 1 to 100 wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder IV, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) having an HFP content of from 8 to 25 wt% and, as the plasticizer V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, tris(butoxyethyl) phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
I) Compounding and melt extrusion of a mixture I which comprises a blend II which contains:
a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from 5 nm to 20 mm which is selected from the group consisting of an electrochemically inert solid IIIa, a compound IIIb which during charging is able to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IIIa with the compound IIIb or the compound IIIc, b) from 5 to 99 wt% of at least one polymeric binder IV, and c) from 0 to 200 wt%, based on the total amount of the components a) and b), at least one plasticizer V, wherein the proportion by weight of the blend II in the mixture I is from 1 to 100 wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder IV, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) having an HFP content of from 8 to 25 wt% and, as the plasticizer V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, tris(butoxyethyl) phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
2. A method as claimed in claim 1, wherein the pigment III is a solid IIIa which is selected from the group consisting of an inorganic solid, preferably an inorganic basic solid, selected from the group consisting of oxides, mixed oxides, silicates, sulfates, carbonates, phosphates, nitrides, amides, imides and carbides of the elements of the Ist, IInd, IIIrd or IVth main group or the IVth subgroup of the Periodic Table of the Elements; a polymer selected from the group consisting of polyethylene, polypropylene, polystyrene, poly(tetrafluoroethylene), poly(vinylidene fluoride); polyamides; polyimides;
and a solid dispersion containing a polymer of this type; and a mixture of two or more thereof.
and a solid dispersion containing a polymer of this type; and a mixture of two or more thereof.
3. A method as claimed in claim 1 or 2, wherein the pigment III is a compound IIIb which, during charging, is able to give off lithium ions and which is selected from the group consisting of LiCoO2, LiNiO2, LiNi x Co y O2, LiNi x Co y Al z O2(O<x,y,z~1), Li x MnO2 (0<x~1), Li x Mn2O4 (0<x~2), Li x MoO2 (0<x~2), Li x MnO3 (0<x~1), Li x MnO2 (0<x~2), Li x Mn2O4 (0<x~2), Li x V2O4 (0<x~2.5), Li x V2O3 (0<x~3.5), Li x VO2 (0<x~1), Li x WO2 (0<x~1), Li x WO3 (0<x~1), Li x TiO2 (0<x~1), Li x Ti2O4 (0<x~2), Li x RuO2 (0<x~1), Li x Fe2O3 (0<x~2), Li x Fe3O4 (0<x~2), Li x Cr2O3 (0<x~3), Li x Cr3O4 (0<x~3.8), Li x (0<x~1.8), Li x Ta2S2 (0<x~1), Li x FeS (0<x~1), Li x FeS2 (0<x~1), Li x NbS2 (0<x~2.4), Li x MoS2 (0<x~3), Li x TiS2 (0<x~2), Li x ZrS2 (0<x~2), Li x NbSe2 (0<x~3), Li x VSe2 (0<x~1), Li x NiPS2 (0<x~1.5), Li x FePS2 (0<x~1.5), LiNi x B i-x O2 (0 < x < 1), LiNiXAh-XO2 (0 < x < 1), LiNiXMgi-XO2 (0 < x <
1), LiNi x Co 1-x VO4 (1~ x ~0), LiNi x Co y MnzO2 (x+y+z = 1), LiFeO2, LiCrTiO4, Li a M b L c O d (1,15 ~ a > 0; 1,3 ~ b+c ~ 0,8; 2,5 ~ d ~1,7; M = Ni, Co, Mn;
L =
Ti, Mn, Cu, Zn, alkaline earth metals, LiCu x II Cu y III Mn(2-(x+y))O4 (2 >
x+y ~
0), LiCrTiO4, LiGa x Mn 2-x O4 (0,1~ x~0), polycarbonsulfides of the general structure: -[C(S x)] n-, V2O5, a mixture of two or more thereof, and a mixture of the compound IIIb with the solid IIIa; and the mixture I additionally contains from 0.1 to 20 wt%, based on the blend II, of conductive black.
1), LiNi x Co 1-x VO4 (1~ x ~0), LiNi x Co y MnzO2 (x+y+z = 1), LiFeO2, LiCrTiO4, Li a M b L c O d (1,15 ~ a > 0; 1,3 ~ b+c ~ 0,8; 2,5 ~ d ~1,7; M = Ni, Co, Mn;
L =
Ti, Mn, Cu, Zn, alkaline earth metals, LiCu x II Cu y III Mn(2-(x+y))O4 (2 >
x+y ~
0), LiCrTiO4, LiGa x Mn 2-x O4 (0,1~ x~0), polycarbonsulfides of the general structure: -[C(S x)] n-, V2O5, a mixture of two or more thereof, and a mixture of the compound IIIb with the solid IIIa; and the mixture I additionally contains from 0.1 to 20 wt%, based on the blend II, of conductive black.
4. A method as claimed in claim 1 or 2, wherein the pigment III is a compound IIIc which, during charging, is able to take up lithium ions and which is selected from the group consisting of lithium, a lithium-containing metal alloy, micronized carbon black, natural and synthetic graphite, synthetically graphitized carbon dust, a carbon fiber, titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, titanium carbonate, molybdenum carbonate, zinc carbonate, Li x M y SiO z (1> x~ 0,1 > y ~ 0, z > 0), Sn2BPO4, polypyrroles, polyanilines, polyacetylenes, polyphenylenes, lithium metal compounds Li x M, wherein M = Sn, Bi, Sb, Zn, Cd, Pb and 5 ~ x ~ 0;
Li-Sn-Cd, CdO, PbO, a mixture of two or more thereof, and a mixture of the compound IIIc with the solid IIIa; and the mixture I additionally contains up to 20 wt%, based on the blend II, of conductive black.
Li-Sn-Cd, CdO, PbO, a mixture of two or more thereof, and a mixture of the compound IIIc with the solid IIIa; and the mixture I additionally contains up to 20 wt%, based on the blend II, of conductive black.
5. A method as claimed in any of claims 1 to 4, wherein the mixture I is cross-linked during or after the melt extrusion.
6. A method as claimed in any one of the preceding claims, wherein the mixture is melt-extruded in an apparatus selected from the group consisting of a plasticating single-screw extruder, a twin-extruder of the corotating type, a twin-screw extruder of the counterrotating type, a twin-shaft continuous kneader and a continuous multishaft extruder and a combination of two or more thereof.
7. A method for producing a composite body, which method comprises the following stages:
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIb or a solid IIIc as defined in claim 3 and 4, respectively;
(II) the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIa, as defined in claim 2, and is free from a solid IIIb or a solid IIIc, and;
(III) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIb or a solid IIIc as defined in claim 3 and 4, respectively;
(II) the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIa, as defined in claim 2, and is free from a solid IIIb or a solid IIIc, and;
(III) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
8. A molded article, preferably a sheet-like molded article which can be obtained by a method, which method comprises the following stage:
I) Compounding and melt extrusion of a mixture I which comprises a blend II which contains:
a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from 5 nm to 20 mm which is selected from the group consisting of an electrochemically inert solid IIIa, a compound IIIb which during charging is able to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IIIa with the compound IIIb or the compound IIIc, b) from 5 to 99 wt% of at least one polymeric binder IV, and c) from 0 to 200 wt%, based on the total amount of the components a) and b), of at least one plasticizer V, wherein the proportion by weight of the blend II in the mixture I is from 1 to 100 wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder IV, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) having an HFP content of from 8 to 25 wt% and, as the plasticizer V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, tris(butoxyethyl) phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
I) Compounding and melt extrusion of a mixture I which comprises a blend II which contains:
a) from 1 to 95 wt% of at least one pigment III having a primary particle size of from 5 nm to 20 mm which is selected from the group consisting of an electrochemically inert solid IIIa, a compound IIIb which during charging is able to give off lithium ions, and a compound IIIc which during charging is able to take up lithium ions, and a mixture of the solid IIIa with the compound IIIb or the compound IIIc, b) from 5 to 99 wt% of at least one polymeric binder IV, and c) from 0 to 200 wt%, based on the total amount of the components a) and b), of at least one plasticizer V, wherein the proportion by weight of the blend II in the mixture I is from 1 to 100 wt%, and wherein mixtures I comprising blends II containing, as the polymeric binder IV, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP) having an HFP content of from 8 to 25 wt% and, as the plasticizer V, a compound selected from the group consisting of dibutyl phthalate, dimethyl phthalate, diethyl phthalate, tris(butoxyethyl) phosphate, propylene carbonate, ethylene carbonate, trimethyl trimellitate and mixtures thereof are excluded.
9. A composite body which can be obtained by a method, which method comprises the following stages:
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIb or a solid IIIc as defined in claim 3 and 4, respectively;
(II) the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIa, as defined in claim 2, and is free from a solid IIIb or a solid IIIc, and;
(III) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
(I) the preparation of at least one first layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIb or a solid IIIc as defined in claim 3 and 4, respectively;
(II) the preparation of at least one second layer by compounding and melt extrusion of a mixture I as defined in claim 1, said mixture comprising a blend II which contains a solid IIIa, as defined in claim 2, and is free from a solid IIIb or a solid IIIc, and;
(III) a subsequent bringing together of the at least one first layer and the at least one second layer by a conventional facing method.
10. Use of a molded article according to claim 8 or a molded article, prepared according to the method according to any of claims 1 to 6 or a composite body according to claim 9 or a composite body prepared according to a process according to claim 7 for the manufacture of a solid electrolyte, a separator, an electrode, in a sensor, an electrochromic window, a display, a capacitor or an ion-conducting film.
11. A separator, solid electrolyte, electrode, sensor, electrochromic window, display, capacitor or ion-conducting foil comprising a molded article as claimed in claim 8 or a molded article produced by means of a method as claimed in any one of claims 1 to 6, or a composite body as claimed in claim 9 or a composite body produced by means of a method as claimed in claim 7.
12. Electrochemical cell comprising a separator, solid electrolyte or electrode as claimed in claim 11 or a combination of two or more thereof.
13. Use of an electrochemical cell as claimed in claim 12 as a motor vehicle battery, appliance battery or flat-type battery.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19713072.0 | 1997-03-27 | ||
DE19713072A DE19713072A1 (en) | 1997-03-27 | 1997-03-27 | Process for the production of moldings for lithium ion batteries |
PCT/EP1998/001763 WO1998044576A1 (en) | 1997-03-27 | 1998-03-25 | Method for producing shaped bodies for lithium ion batteries |
Publications (1)
Publication Number | Publication Date |
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CA2285007A1 true CA2285007A1 (en) | 1998-10-08 |
Family
ID=7824913
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002285007A Abandoned CA2285007A1 (en) | 1997-03-27 | 1998-03-25 | Method for producing shaped bodies for lithium ion batteries |
Country Status (13)
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EP (1) | EP0970529B1 (en) |
JP (1) | JP2001516496A (en) |
KR (1) | KR20010005630A (en) |
CN (1) | CN1257612A (en) |
AU (1) | AU7210498A (en) |
BR (1) | BR9808983A (en) |
CA (1) | CA2285007A1 (en) |
DE (2) | DE19713072A1 (en) |
ES (1) | ES2183353T3 (en) |
RU (1) | RU99122673A (en) |
TW (1) | TW368760B (en) |
WO (1) | WO1998044576A1 (en) |
ZA (1) | ZA982550B (en) |
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1997
- 1997-03-27 DE DE19713072A patent/DE19713072A1/en not_active Withdrawn
-
1998
- 1998-03-25 RU RU99122673/09A patent/RU99122673A/en not_active Application Discontinuation
- 1998-03-25 WO PCT/EP1998/001763 patent/WO1998044576A1/en not_active Application Discontinuation
- 1998-03-25 AU AU72104/98A patent/AU7210498A/en not_active Abandoned
- 1998-03-25 JP JP54113098A patent/JP2001516496A/en not_active Withdrawn
- 1998-03-25 DE DE59805317T patent/DE59805317D1/en not_active Expired - Fee Related
- 1998-03-25 CA CA002285007A patent/CA2285007A1/en not_active Abandoned
- 1998-03-25 BR BR9808983-8A patent/BR9808983A/en not_active Application Discontinuation
- 1998-03-25 EP EP98919152A patent/EP0970529B1/en not_active Expired - Lifetime
- 1998-03-25 ES ES98919152T patent/ES2183353T3/en not_active Expired - Lifetime
- 1998-03-25 KR KR1019997008697A patent/KR20010005630A/en not_active Application Discontinuation
- 1998-03-25 CN CN98805452A patent/CN1257612A/en active Pending
- 1998-03-26 ZA ZA9802550A patent/ZA982550B/en unknown
- 1998-03-27 TW TW087104598A patent/TW368760B/en active
Cited By (2)
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US20120141868A1 (en) * | 2009-08-28 | 2012-06-07 | Tosoh Corporation | Zeolite for treatment of nonaqueous electrolytic solution and treatment method of nonaqueous electrolytic solution |
US9084980B2 (en) * | 2009-08-28 | 2015-07-21 | Tosoh Corporation | Zeolite for treatment of nonaqueous electrolytic solution and treatment method of nonaqueous electrolytic solution |
Also Published As
Publication number | Publication date |
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WO1998044576A1 (en) | 1998-10-08 |
ZA982550B (en) | 1999-09-27 |
JP2001516496A (en) | 2001-09-25 |
DE59805317D1 (en) | 2002-10-02 |
BR9808983A (en) | 2000-08-01 |
ES2183353T3 (en) | 2003-03-16 |
DE19713072A1 (en) | 1998-10-01 |
TW368760B (en) | 1999-09-01 |
CN1257612A (en) | 2000-06-21 |
EP0970529A1 (en) | 2000-01-12 |
EP0970529B1 (en) | 2002-08-28 |
KR20010005630A (en) | 2001-01-15 |
RU99122673A (en) | 2001-08-27 |
AU7210498A (en) | 1998-10-22 |
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