WO2012156903A1 - Electrochemical cells comprising polyimides - Google Patents
Electrochemical cells comprising polyimides Download PDFInfo
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- WO2012156903A1 WO2012156903A1 PCT/IB2012/052411 IB2012052411W WO2012156903A1 WO 2012156903 A1 WO2012156903 A1 WO 2012156903A1 IB 2012052411 W IB2012052411 W IB 2012052411W WO 2012156903 A1 WO2012156903 A1 WO 2012156903A1
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 57
- 229920001721 polyimide Polymers 0.000 title claims abstract description 57
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 45
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 32
- 229920000768 polyamine Polymers 0.000 claims abstract description 27
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 26
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000007859 condensation product Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910052566 spinel group Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 3
- -1 polyethylene Polymers 0.000 description 26
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 15
- 239000011572 manganese Substances 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 125000005462 imide group Chemical group 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910013884 LiPF3 Inorganic materials 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 4
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000003950 cyclic amides Chemical class 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 2
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 2
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 2
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 2
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 2
- SGNWZFDRXBVNKA-UHFFFAOYSA-N 3-phenylcyclohexa-3,5-diene-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)C(C(=O)O)(C(O)=O)C=CC=C1C1=CC=CC=C1 SGNWZFDRXBVNKA-UHFFFAOYSA-N 0.000 description 2
- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-UHFFFAOYSA-N 0.000 description 2
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 2
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 2
- SOFROPJAVRFBFI-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)CC1=CC=C(C(O)=O)C(C(O)=O)=C1 SOFROPJAVRFBFI-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000002847 impedance measurement Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 2
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 2
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- 230000000737 periodic effect Effects 0.000 description 2
- YXXLZRRIAHYCCY-UHFFFAOYSA-N phenanthrene-1,3,9,10-tetracarboxylic acid Chemical compound C1=CC=C2C3=CC(C(=O)O)=CC(C(O)=O)=C3C(C(O)=O)=C(C(O)=O)C2=C1 YXXLZRRIAHYCCY-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 2
- YKWDNEXDHDSTCU-UHFFFAOYSA-N pyrrolidine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1NC(C(O)=O)C(C(O)=O)C1C(O)=O YKWDNEXDHDSTCU-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical class CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YFIAVMMGSRDLLG-UHFFFAOYSA-N tert-butyl 3-benzylpiperazine-1-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCNC1CC1=CC=CC=C1 YFIAVMMGSRDLLG-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/345—Polycarboxylic acids having at least three carboxylic acid groups having three carboxylic acid groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
- H01M4/52—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
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention is directed towards an electrochemical cell comprising
- separator (D) at least one separator positioned between anode (A) and cathode (B), as component (D), characterized in that separator (D) is manufactured from at least one polyimide selected from branched condensation products of
- the present invention is directed towards separators for electrochemical cells. Furthermore, the present invention is directed towards a method for manufacturing inventive separators.
- Batteries and electrochemical cells with non-aqueous electrolytes are currently of great interest. Many components are of significance, such as the electrodes and the electrolyte. However, particular attention will be paid to the separator which physically separates the anode and the cathode, thereby preventing short circuits.
- the separator should allow Lithium ions to pass.
- a separator should have the necessary mechanical properties to effectively separate anode and cathode from each other.
- inventive cells comprise
- (A) at least one anode as component (A), briefly also referred to as anode (A),
- cathode (B) at least one cathode as component (B), briefly also referred to as cathode (B),
- component (C) at least one non-aqueous electrolyte as component (C), briefly also referred to as elec- trolyte (C),
- separator (D) at least one separator positioned between anode (A) and cathode (B), as component (D) or separator (D), characterized in that separator (D) is manufactured from at least one polyimide selected from branched condensation products of
- (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
- inventive cells can be selected from alkali metal containing cells.
- inventive cells are selected from lithium-ion containing cells.
- the charge transport is effected by Li + ions.
- the electrode where during discharging a net negative charge occurs is called the anode.
- Anode (A) can be selected from anodes being based on various active materials.
- Suitable ac- tive materials are metallic lithium, carbon-containing materials such as graphite, graphene, charcoal, expanded graphite, furthermore lithium titanate (Li4Ti 5 0i2), tin oxide (Sn02), and nanocrystalline silicium.
- anode (A) is selected from graphite anodes and lithium titanate anodes.
- Anode (A) can further comprise a current collector.
- Suitable current collectors are, e.g., metal wires, metal grids, metal gaze and preferably metal foils such as copper foils.
- Anode (A) can further comprise a binder. Suitable binders can be selected from organic
- Suitable organic (co)polymers may be halogenated or halogen-free.
- Examples are polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, styrene- butadiene copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride- hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-chlorofluoroethylene copolymers, ethyl- ene-acrylic acid copolymers
- Suitable binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
- the average molecular weight M w of binder may be selected within wide limits, suitable examples being 20,000 g/mol to 1 ,000,000 g/mol.
- anode (A) can have a thickness in the range of from 15 to 200 ⁇ , preferably from 30 to 100 ⁇ , determined without the current collector.
- Inventive cells further comprise a cathode (B).
- Cathode (B) can be, e. g., air (or oxygen). In a preferred embodiment, however, cathode (B) contains a solid active material.
- Solid active materials for cathode (B) can be selected from phosphates with olivine structure such as lithium iron phosphates (LiFeP0 4 ) and lithium manganese phosphate (LiMnP0 4 ) which can have a stoichiometric or non-stoichiometric composition and which can be doped or not doped.
- phosphates with olivine structure such as lithium iron phosphates (LiFeP0 4 ) and lithium manganese phosphate (LiMnP0 4 ) which can have a stoichiometric or non-stoichiometric composition and which can be doped or not doped.
- active material for cathode (B) can be selected from lithium containing transition metal spinels and lithium transition metal oxides with a layered crystal structure.
- cathode (B) contains at least one material selected from lithium containing transition metal spinels and lithium transition metal oxides with a layered crystal structure, respectively.
- lithium-containing metal spinels are selected from those of the general formula (I) the integers being defined as follows:
- M 1 is selected from one or more out of Al, Mg, Ca, Na, B, Mo, W and transition metals of the first row of the transition metals in the periodic table of the elements.
- M 1 is selected from the group consisting of Ni, Co, Cr, Zn, and Al. Even more preferably, M 1 is defined to be Ni.
- lithium containing metal spinels are selected from LiNio,5Mni, 5 04-d and LiM ⁇ C .
- lithium transition metal oxides with a layered crystal structure are selected from compounds of general formula (II) the integer being defined as follows: 0 ⁇ t ⁇ 0.3 and M 2 selected from one or more elements from Al, Mg, B, Mo, W, Na, Ca and transition metals of the first row of the transition metals in the periodic table of the elements, at least one element being manganese.
- At least 30 mole-% of M 2 are selected from man- ganese, preferably at least 35 mole-%, in each time with respect to the complete amount of M 2 .
- M 2 is selected from combinations of Ni, Co and Mn not containing significant amounts of additional elements. In a different embodiment of the present invention M 2 is selected from combinations of Ni, Co and Mn containing significant amounts of at least one additional element, for example in the range of from 1 to 10 mole-% Al, Ca or Na.
- lithium transition metal oxides with a lay- ered crystal structure are selected from compounds of general formula
- Li(i + x)[NieCOfMn g M 3 h](i-x)02 (HI) the integers being defined as follows: x a number in the range of from zero to 0.2, e a number in the range of from 0.2 to 0.6, f a number in the range of from 0.1 to 0.5, g a number in the range of from 0.2 to 0.6, h a number in the range of from zero to 0.1 , and: e + f + g + h 1 ,
- M 3 selected from Al, Mg, V, Fe, Cr, Zn, Cu, Ti and Mo.
- M 2 in formula (II) is selected from Nio,33Coo,33Mno,33, Nio,5Coo,2Mn 0 ,3, Nio,4Coo,3Mn 0 ,4, Ni 0 ,4Coo,2Mn 0 ,4 und Ni 0 ,45Coo,ioMn 0 ,45.
- Cathode (B) can further comprise a current collector.
- Suitable current collectors are, e.g., metal wires, metal grids, metal gaze and preferably metal foils such as aluminum foils.
- Cathode (B) can further comprise a binder.
- Suitable binders can be selected from organic (co)polymers. Suitable organic (co)polymers may be halogenated or halogen-free. In general, the same binders used for anode (A) can also be employed for cathode (B).
- Preferred binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvi- nyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
- cathode (B) can have a thickness in the range of from 15 to 200 ⁇ , preferably from 30 to 100 ⁇ , determined without the current collector.
- Cathode (B) can further comprise electrically conductive carbonaceous material.
- Electrically conductive carbonaceous material can be selected, for example, from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances. In the context of the present invention, electrically conductive, carbonaceous material can also be referred to as carbon for short.
- electrically conductive carbonaceous material is carbon black.
- Carbon black may, for example, be selected from lamp black, furnace black, flame black, thermal black, acetylene black and industrial black.
- Carbon black may comprise impurities, for example hydrocarbons, especially aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups.
- sulfur- or iron- containing impurities are possible in carbon black.
- electrically conductive carbonaceous material is partially oxidized carbon black.
- Electrolyte (C) in the context of the present invention can encompass at least one salt, preferably a lithium salt, and at least one non-aqueous solvent.
- nonaqueous solvent may be liquid or solid at room temperature, preferably selected from polymers, cyclic or noncyclic ethers, cyclic and noncyclic acetals and cyclic or noncyclic organic carbonates.
- suitable polymers are especially polyalkylene glycols, preferably poly-Ci-C4- alkylene glycols and especially polyethylene glycols. These polyethylene glycols may comprise up to 20 mol% of one or more Ci-C4-alkylene glycols in copolymerized form.
- the polyalkylene glycols are preferably polyalkylene glycols double-capped by methyl or ethyl.
- the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol.
- the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be up to 5,000,000 g/mol, preferably up to 2,000,000 g/mol.
- noncyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2- dimethoxyethane, 1 ,2-diethoxyethane, preference being given to 1 ,2-dimethoxyethane.
- suitable cyclic ethers are tetrahydrofuran and 1 ,4-dioxane.
- noncyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1 ,1 -dimethoxyethane and 1 ,1 -diethoxyethane.
- suitable cyclic acetals are 1 ,3-dioxane and especially 1 ,3-dioxolane.
- suitable noncyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
- suitable cyclic organic carbonates are compounds of the general formulae (IV) and (V) in which R 1 , R 2 and R 3 may be the same or different and are selected from hydrogen and C1-C4- alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, where R 2 and R 3 are preferably not both tert-butyl.
- R 1 is methyl and R 2 and R 3 are each hydrogen, or R 1 , R 2 and R 3 are each hydrogen.
- Another preferred cyclic organic carbonate is vinylene carbonate, formula (VI).
- the solvent(s) is (are) preferably used in what is known as the anhydrous state, i.e. with a water content in the range from 1 ppm to 0.1 % by weight, determinable, for example, by Karl Fischer titration.
- Electrolyte further comprises one or more conductive salts.
- Suitable conductive salts are especially lithium salts.
- suitable lithium salts are LiPF6, LiBF 4 , UCIO4, LiAsF6, UCF3SO3, LiC(C n F2n+iS02)3, LiPFw(C n F2n+i)6-w, lithium imides such as LiN(C n F2n+iS02)2, where n is an integer in the range from 1 to 20, LiN(S02F)2, Li2SiFe, LiSbF6, LiAICU, and salts of the general formula (CnF2n+iS02)mXLi, where m is defined as follows:
- m 3 when X is selected from carbon and silicon.
- Preferred conductive salts are selected from LiC(CF 3 S0 2 )3, LiN(CF 3 S0 2 )2, LiPF 6 , LiBF 4 , LiCI0 4 , and LiPF3(CF2CF3)3, particular preference being given to LiPF6, LiPF3(CF 2 CF3)3 and
- the concentration of conductive salt in electrolyte is in the range of from 0.01 M to 5 M, preferably 0.5 M to 1.5 M.
- Inventive electrochemical cells further comprise at least one separator (D), said separator being positioned between anode (A) and cathode (B).
- separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to either a major part of one surface of anode (A) or cathode (B). In one embodiment of the present invention, separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to both a major part of one surface of anode (A) and cathode (B).
- separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to one surface of anode (A) or of cathode (B).
- separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to one surface of both anode (A) and of cathode (B).
- separator (D) has a thickness in the range of from 10 ⁇ to 100 ⁇ , preferably 15 ⁇ to 35 ⁇ .
- the specific ionic conductivity at room temperature of separator (D) in liquid electrolyte is in the range of from 10 "6 S/cm to 10 "3 S/cm, determined by impedance measurements of sandwich cells with separator/electrolyte combinations.
- Separator (D) is manufactured from at least one polyimide, said polyimide being characterized below.
- To be manufactured in the context of the separator means that the separator is manufac- tured using at least one branched polyimide, preferably as the main component of separator and even more preferably as sole component.
- separator further contains one or more inorganic particles (E).
- Inorganic particles can be selected, e. g., from oxides of Ti, Zr, Si or Al, non- stoichiometric or stoichiometric, preferred is Si0 2 .
- Polyimide from which separator (D) is manufactured is a branched polyimide and is selected from condensation products of
- (b1 ) at least one polyamine having on average more than two amino groups per molecule, and preferably, also referred to as polyamine (b1 ), and preferably from (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule, also referred to as polyisocyanate (b2).
- Said polyimide is briefly referred to as branched polyimide.
- Branched polyimide can have a molecular weight M w in the range from 1 ,000 to 200,000 g/mol; preference is given to 2,000 to 20,000 g/mol.
- Branched polyimide can have at least two imide groups per molecule; preference is given to at least 3 imide groups per molecule.
- branched polyimide can have up to 1 ,000 imide groups per molecule, preferably up to 660 per molecule.
- Branched polyimide can be composed of structurally and molecularly uniform molecules. However, preference is given to branched polyimides being mixtures of molecularly and structurally differing molecules, for example, visible from the polydispersity M w /M n of at least 1 .4, preferably Mw Mn of 1.4 to 50, preferably 1 .5 to 10.
- the polydispersity can be determined by known methods, in particular by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- a suitable standard is, for example, poly(methyl methacrylate) (PMMA).
- polyimide in addition to imide groups which form the polymer backbone, comprises, terminally or in side chains, in addition at least three, preferably at least six, more preferably at least ten, terminal or side-chain functional groups.
- Func- tional groups in branched polyimide are preferably anhydride or acid groups and/or free or capped NCO groups.
- Branched polyimides preferably have no more than 500 terminal or side- chain functional groups, preferably no more than 100.
- AlkyI groups such as, for example, methyl groups are therefore not a branching of a molecule of branched polyimide.
- polycarboxylic acids (a) aliphatic, or preferably aromatic, polycarboxylic acids are selected that have at least three COOH groups per molecule, or the respective anhydrides, preferably if they are present in low-molecular weight, that is to say non-polymeric, form.
- Such polycarboxylic acids having three COOH groups in which two carboxylic acids groups are present as an- hydride and the third as a free carboxylic acid are also comprised.
- polycarboxylic acid (a) a polycarboxylic acid having at least 4 COOH groups per molecule, or the respective anhydride, is selected.
- polycarboxylic acids (a) and anhydrides thereof are 1 ,2,3-benzenetricarboxylic acid and 1 ,2,3-benzenetricarboxylic dianhydride, 1 ,3,5-benzenetricarboxylic acid (trimesic acid), preferably 1 ,2,4-benzenetricarboxylic acid (trimellitic acid), trimellitic anhydride and, in particular, 1 ,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) and 1 , 2,4, 5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride), 3,3',4,4"-benzophenonetetracarboxylic acid, 3,3',4,4"- benzophenonetetracarboxylic dianhydride,
- polycarboxylic acids (a) and anhydrides thereof are mellophanic acid and mello- phanic anhydride, 1 ,2,3,4-benzenetetracarboxylic acid and 1 ,2,3,4-benzenetetracarboxylic di- anhydride, 3,3,4,4-biphenyltetracarboxylic acid and 3,3,4,4-biphenyltetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic acid and 2,2,3,3-biphenyltetracarboxylic dianhydride, 1 ,4,5,8- naphthalenetetracarboxylic acid and 1 ,4,5, 8-naphthalenetetracarboxylic dianhydride, 1 ,2,4,5- naphthalenetetracarboxylic acid and 1 ,2,4,5-naphthalenetetracarboxylic dianhydride, 2,3,6,7- naphthalenete
- anhydrides from US 2,155,687 or US 3,277,1 17 are used for synthesizing a branched polyimide.
- Polycarboxylic acid (a) or its respective anhydride can be reacted with at least one compound (b), selected from
- polyamine (b1 ) at least one polyamine having on average more than two amino groups per molecule, also referred to as polyamine (b1 ), and preferably,
- polyisocyanate (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule, also referred to as polyisocyanate (b2).
- polycarboxylic acid (a) or its respective anhydride will be reacted
- Polyamines (b1 ) can be aliphatic, cycloaliphatic or preferably aromatic. In polyamine (b1 ) only primary amino groups (Nhb-groups) will be taken into account. Tertiary and secondary amino groups - if present - will not be taken into consideration when determining the number of amino groups in polyamine (b1 ).
- Polyamine (b1 ) has on average more than two amino groups per molecule, preferably on average at least 2.5, more preferably on average at least 3.0.
- polyamines (b1 ) are selected from mixtures from diamines and triamines.
- polyamine (b1 ) bears on average a maximum of 8, preferably on average a maximum of 6 amine groups per molecule.
- Aromatic triamines and mixtures of aromatic or aliphatic diamines and aromatic triamines are particularly preferred examples for polyamines (b1 ).
- Examples for aliphatic diamines to be present in said mixtures of mixtures of aromatic or aliphatic diamines and aromatic triamines as polyamines (b1 ) are ethylene diamine, 1 ,3-propylene diamine, diethylenetriamine, tetraethylenepentamine, and triethylenetetramine.
- Suitable aromatic triamines that can be selected as polyamines (b1 ) - alone or as a mixture with at least one aromatic diamine - are chosen from triamines in which the Nhb groups are attached to one or preferable to at least two aromatic rings, said different aromatic rings being so-called isolated aromatic rings, conjugated aromatic rings, or fused aromatic rings.
- triamines with Nhb-groups attached to different conjugated or isolated aromatic rings are selected.
- Examples are 1 ,3,5-tri(4-aminophenoxy) benzene, 1 ,3,5-tri(3-methy 1 ,4-aminophenoxy) benzene, 1 ,3,5-tri(3 -methoxy,4-aminophenoxy) benzene, 1 ,3,5-tri(2-methyl,4-aminophenoxy) benzene, 1 ,3,5 -tri(2-methoxy,4-aminophenoxy) benzene, and 1 ,3,5-tri(3-ethyl,4- aminophenoxy)benzene.
- triamines are 1 ,3,5-tri(4-aminophenylamino) benzene, 1 ,3,5-tri(3-methyl,4- aminophenylamino) benzene, 1 ,3,5-tri(3-methoxy,4-aminophenylamino) benzene, 1 ,3,5-tri(2- methyl,4-aminophenylamino) benzene, 1 ,3, 5-tri(2-methoxy,4-aminophenylamino) benzene, and 1 ,3,5-tri(3-ethyl,4-aminophenylamino) benzene.
- R 5 , R 6 - being different or preferably identical and selected from hydrogen, Ci-C4-alkyl,
- COOCHs COOC 2 H 5 , CN, CF3, or 0-CH 3 ;
- X 1 , X 2 - being different or preferably identical and selected from single bonds, Ci-C4-alkylene groups, N-H, and oxygen, preferable -CH2- or oxygen.
- polyamine (b1 ) is selected from 3,5-di(4-aminophenoxy)aniline, 3,5-di(3- methyl-1 ,4-aminophenoxy)aniline, 3,5-di(3-methoxy-4-aminophenoxy)aniline, 3,5-di(2-methyl-4- aminophenoxy)aniline, 3,5-di(2-methoxy-4-aminophenoxy)aniline, and 3 ,5-d i (3-ethyl-4- aminophenoxy)aniline.
- examples are triamines according to formula (VIII)
- R 7 selected from hydrogen, Ci-C 4 -alkyl, COOCH 3 , COOC2H5, CN, CF 3 , or 0-CH 3 ;
- R 8 selected from hydrogen or methyl and the other integers being defined as above.
- Polyisocyanate (b2) can be selected from any polyisocyanates that on average have more than two isocyanate groups per molecule, which can be capped or preferably free. Preference is given to trimeric or oligomeric diisocyanates, for example oligomeric hexamethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric tolylene diisocyanate, preferably trimeric tol- ylene diisocyanate, oligomeric diphenylmethane diisocyanate - hereinafter also termed poly- mer-MDI - and mixtures of the abovementioned polyisocyanates.
- trimeric or oligomeric diisocyanates for example oligomeric hexamethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric tolylene diisocyanate, preferably trimeric tol- ylene diisocyanate, oligomeric diphenylme
- polyisocyanate (b2) having more than two isocyanate groups per molecule is a mixture of at least one diisocyanate and at least one triisocy- anate, or a polyisocyanate having at least 4 isocyanate groups per molecule.
- polyisocyanate (b2) has on average at least 2.2, preferably at least on average 2.5, particularly preferably at least on average 3.0, isocyanate groups per molecule.
- polyisocyanate (b2) bears on average a maximum of 8, preferably on average a maximum of 6 isocyanate groups per molecule.
- polyisocyanate (b2) is selected from oligomeric hexamethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate, and mixtures of the abovementioned polyisocyanates.
- Polyisocyanate (b2) can, in addition to urethane groups, also have one or more other functional groups, for example urea, allophanate, biuret, carbodiimide, amide, ester, ether, uretonimine, uretdione, isocyanurate or oxazolidine groups.
- polyamine (b1 ) and polycarboxylic acid (a) are condensed with one another - preferably in the presence of a catalyst - an imide group is formed under elimination of H2O.
- R * is the polyamine (b1 ) radical that is not specified further in the above reaction equation, and n is a number greater than or equal to 1 , for example 1 in the case of a tricarboxylic acid or 2 in the case of a tetracarboxylic acid.
- polyisocyanate (b2) and polycarboxylic acid (a) are condensed with one another - preferably in the presence of a catalyst - an imide group is formed with the elimination of CO2 and H2O. If, instead of polycarboxylic acid (a), the corresponding anhydride is used, an imide group is formed with elimination of CO2.
- R ** is the polyisocyanate (b2) radical that is not specified further in the above reaction equation
- polyisocyanate (b2) is used in a mixture with at least one diisocyanate, for example with tolylene diisocyanate, hexamethylene diisocyanate or with isophorone diisocyanate.
- polyisocyanate (b2) is used in a mixture with the corresponding diisocyanate, for example trimeric HDI with hexamethylene diisocyanate or trimeric isophorone diisocyanate with isophorone diisocyanate or polymeric diphenylmethane diisocyanate (polymer MDI) with diphenylmethane diisocyanate.
- polycarboxylic acid (a) is used in a mixture with at least one dicarboxylic acid or with at least one dicarboxylic anhydride, for example with phthalic acid or phthalic anhydride.
- Preferred synthesis methods for making branched polyimides comprise reacting with one another
- water and Bransted bases are suitable, for example alkalimetal alco- holates, in particular alkanolates of sodium or potassium, for example sodium methanolate, so- dium ethanolate, sodium phenolate, potassium methanolate, potassium ethanolate, potassium phenolate, lithium methanolate, lithium ethanolate and lithium phenolate.
- alkalimetal alco- holates in particular alkanolates of sodium or potassium, for example sodium methanolate, so- dium ethanolate, sodium phenolate, potassium methanolate, potassium ethanolate, potassium phenolate, lithium methanolate, lithium ethanolate and lithium phenolate.
- polyisocyanate (b2) and polycarboxylic acid (a) or anhydride (a) can be used in a quantitative ratio such that the molar fraction of NCO groups to COOH groups is in the range from 1 : 3 to 3 : 1 , preferably 1 : 2 to 2 : 1 .
- one anhydride group of the formula CO-O-CO counts as two COOH groups.
- catalyst can be used in the range from 0.005 to 0.1 % by weight, based on the sum of polyisocyanate (b2) and polycarboxylic acid (a) or polyisocyanate (b2) and anhydride (a). Preference is given to 0.01 to 0.05% by weight of catalyst.
- a synthesis method for making branched polyimides can be carried out at temperatures in the range from 50 to 200°C, preferably 50 to 140°C, particularly preferably 50 to 100°C.
- a synthesis method for making branched polyimides can be carried out at atmospheric pressure. However, the synthesis is also possible under pressure, for example at pressures in the range from 1 .1 to 10 bar.
- a synthesis method for making branched polyimides can be carried out in the presence of a solvent or solvent mixture.
- suitable solvents are N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl sulphones, xylene, phenol, cresol, ketones such as, for example, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetophenone, in addition mono- and dichlorobenzene, ethylene glycol monoethyl ether acetate and mixtures of two or more of the abovementioned mixtures.
- the solvent or solvents can be present during the entire synthesis time or only during part of the synthesis.
- the reaction can be carried out, for example, for a time period of 10 minutes to 24 hours.
- the synthesis method for making branched polyimides is carried out under inert gas, for example under argon or under nitrogen.
- water-sensitive Bransted base is used as catalyst, it is preferred to dry inert gas and solvent. If water is used as catalyst, the drying of solvent and inert gas can be dispensed with.
- NCO end groups of branched polyimide can be blocked with a blocking agent (c), for example with secondary amine, for example with dimethylamine, di-n-butylamine or with diethylamine.
- inventive electrochemical cells can contain additives such as wetting agents, corrosion inhibitors, or protective agents such as agents to protect any of the electrodes or agents to protect the salt(s).
- inventive electrochemical cells can have a disc-like shape. In another embodiment, inventive electrochemical cells can have a prismatic shape.
- inventive electrochemical cells can include a housing that can be from steel or aluminium. In one embodiment of the present invention, inventive electrochemical cells are combined to stacks including electrodes that are laminated. In one embodiment of the present invention, inventive electrochemical cells are selected from pouch cells.
- Inventive electrochemical cells have overall advantageous properties. They have a long dura- tion with very low loss of capacity, good cycling stability, and a reduced tendency towards short circuits after longer operation and/or repeated cycling.
- a further aspect of the present invention refers to batteries containing at least one inventive electrochemical cell, for example two or more.
- inventive batteries have advantageous proper- ties. They have a long duration with very low loss of capacity, good cycling stability, and high temperature stability.
- a further aspect of the present invention is the use of inventive electrochemical cells or inventive batteries according for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and stationary applications such as energy storage devices for power plants.
- a further aspect of the present invention is a method of making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equip- ment, remote car locks, and stationary applications such as energy storage devices for power plants by employing at least one inventive battery or at least one inventive electrochemical cell.
- a further aspect of the present invention is the use of polyimides selected from branched condensation products of
- (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule
- a further aspect of the present invention is a separator, comprising at least one polyimide, se- lected from branched condensation products of
- (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
- Polyisocyanate (b2) and polycarboxylic acids (a) have been defined above.
- inventive separator (D) has a thickness in the range of from 10 ⁇ to 100 ⁇ , preferably 15 ⁇ to 35 ⁇ .
- the specific ionic conductivity at room temperature of inventive separator (D) in liquid electrolyte is in the range of from 10 -6 S/cm to 10 "3 S/cm, determined by impedance measurements of sandwich cells with separator/electrolyte combina- tions.
- a further aspect of the present invention is a method for manufacturing inventive separators.
- Said inventive method comprises making a film of branched polyimide.
- one dissolves at least one branched polyimide in a suitable solvent or mixture of solvents and then applies said solution to a flat surface, for example to a glass surface or to a metal foil, e. g., an aluminum foil, or to a plastics foil such as a polyethylene terephthalate film (PET foil). Then one removes the solvent or solvents, respectively.
- the inventive separator can be removed from the flat surface, for example mechani- cally.
- suitable solvents are, e. g., cyclic or non-cyclic amides, ketones, and cyclic and non-cyclic ethers.
- cyclic amides are N-methylpyrrolidone (NMP) and N-ethylpyrrolidone (NEP).
- NMP N-methylpyrrolidone
- NEP N-ethylpyrrolidone
- non-cyclic amides are ⁇ , ⁇ -dimethylformamide and ⁇ , ⁇ -dimethylacetamide.
- ketones are acetone, methylethylketone, methyl isobutyl ketone (MIBK), and cyclohex- anone.
- ethers are 1 ,2-dimethoxyethane, di-n-butyl ether, tetrahydrofurane and preferably anisole.
- Solutions of at least one branched polyimide can have a solids content in the range of from 5 to 50 % by weight, preferably 15 to 30 % by weight.
- Application of the solution to a flat surface can be performed by spraying, blade coating, spin coating, drop casting, or dip coating.
- Removal of the solvent(s) can be achieved by evaporating the solvent(s) or allowing to evaporate, for example by heating, or via reduction of pressure, or via using a gas stream. Removal of the separator from the flat surface can be achieved by mere mechanical means, or it can be supported by softening, e.g., by allowing to rest in a solvent with poor solution ability, such as water. In another embodiment, inventive separators can be made by applying a solution of
- (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
- Inventive separators (D) have overall advantageous properties. They help to secure a long duration of electrochemical cells with very low loss of capacity, good cycling stability, and a reduced tendency towards short circuits after longer operation and/or repeated cycling. They can help batteries to have a long duration with very low loss of capacity, good cycling stability, and high temperature stability.
- Polymer-MDI polymeric 4, 4'-diphenylmethane diisocyanate
- NCO NCO content, determined by IR spectroscopy unless expressly mentioned otherwise, it is indicated in % by weight. The molecular weights were determined by gel permeation chromatography (GPC using a re- fractometer as detector). The standard used was polymethyl methacrylate (PMMA). The solvents used were ⁇ , ⁇ -dimethylacetamide (DMAc) or tetrahydrofurane (THF), if not stated otherwise.
- PMMA polymethyl methacrylate
- DMAc ⁇ , ⁇ -dimethylacetamide
- THF tetrahydrofurane
- inventive separator (D.1 ) Branched polyimide (BP.1 ) (3 g) was dissolved in 10 g NMP as solvent and warmed to 80°C. The 30% solution so obtained was applied at 80°C with a doctor blade method to a glass plate. The solvent-containing film had a thickness of 50 ⁇ . The NMP was allowed to evaporate for 10 minutes at 80°C. The film was then - together with the glass plate - placed into a water bath having room temperature for 1 hour. Then, a film was be removed manually which was dried over a period of 24 hours under vacuum at 80°C. Inventive separator (D.1 ) was so obtained.
- inventive separator (D.1 ) was 10 -5 S/cm, determined in a 1 M solution of LiPF3(CF2CFs)3 in a 1 :1 (by weight) mixture of ethylene carbonate/dimethyl carbonate.
- Figure I shows an exploded view of inventive electrochemical cell (EC. 1 ).
- Cathode LiNio.8Coo.15Alo.05O2, on aluminium foil as current collector.
- cathode (B.1 ) As cathode (B.1 ), a nickel manganese spinel electrode was used which had been manufactured as follows. 85% LiMni, 5 Nio,504
- the paste so obtained was applied to an aluminium foil (thickness of the aluminium foil: 20 ⁇ ) with a knife blade. Then, the aluminium foil so coated was dried in a drying cabinet at 120°C under vacuum. The thickness of the dried coating was 30 ⁇ . Then round segments were punched out, diameter: 12 mm.
- inventive electrochemical cell (EC.1 ) was charged with a constant current to a voltage of 4.2 V followed by a final charging with constant voltage at 4.2 V. Then, inventive electrochemical cell (EC.1 ) was discharged at constant current to a voltage of 3 V. Three such cycles with 0.1 C and, thereafter, 20 cycles with 0.5 C were determined. The capacity was determined to be 90 to 100 mA-h.
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Abstract
Electrochemical cell comprising (A) at least one anode as component (A), (B) at least one cathode as component (B), (C) at least one non-aqueous electrolyte as component (C), (D) at least one separator positioned between anode (A) and cathode (B), as component (D), characterized in that separator (D) is manufactured from at least one polyimide selected from branched condensation products of (a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or an anhydride or ester thereof, and (b) and at least one compound, selected from (b1) at least one polyamine having on average more than two amino groups per molecule and (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
Description
Electrochemical Cells Comprising Polyimides
Description
The present invention is directed towards an electrochemical cell comprising
(A) at least one anode as component (A),
(B) at least one cathode as component (B),
(C) at least one none-aqueous electrolyte as component (C),
(D) at least one separator positioned between anode (A) and cathode (B), as component (D), characterized in that separator (D) is manufactured from at least one polyimide selected from branched condensation products of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or an anhydride or ester thereof, and
(b) at least one compound, selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate
groups per molecule.
Furthermore, the present invention is directed towards separators for electrochemical cells. Furthermore, the present invention is directed towards a method for manufacturing inventive separators.
Batteries and electrochemical cells with non-aqueous electrolytes are currently of great interest. Many components are of significance, such as the electrodes and the electrolyte. However, particular attention will be paid to the separator which physically separates the anode and the cathode, thereby preventing short circuits.
On one hand, the separator should allow Lithium ions to pass. On the other hand, a separator should have the necessary mechanical properties to effectively separate anode and cathode from each other.
Longevity is still an issue for lithium ion batteries. Sometimes, it has been observed that batteries produce short circuits after a number of cycles such as 40 or 50 cycles.
It was therefore an objective to provide electrochemical cells that do not suffer from short circuits after longer operation, such as after repeated cycling. It was further an objective to provide components for electrochemical cells that do not suffer from short circuits after longer operation. Furthermore, it was an objective to provide a method for manufacturing batteries that do not suffer from short circuits after longer operation.
Accordingly, the above electrochemical cells were found, hereinafter also referenced as inventive cells.
Inventive cells comprise
(A) at least one anode as component (A), briefly also referred to as anode (A),
(B) at least one cathode as component (B), briefly also referred to as cathode (B),
(C) at least one non-aqueous electrolyte as component (C), briefly also referred to as elec- trolyte (C),
(D) at least one separator positioned between anode (A) and cathode (B), as component (D) or separator (D), characterized in that separator (D) is manufactured from at least one polyimide selected from branched condensation products of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or a re- spective anhydride or ester thereof,
(b) at least one compound, selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
Inventive cells can be selected from alkali metal containing cells. Preferably, inventive cells are selected from lithium-ion containing cells. In lithium-ion containing cells, the charge transport is effected by Li+ ions.
In the context with the present invention, the electrode where during discharging a net negative charge occurs is called the anode.
Anode (A) can be selected from anodes being based on various active materials. Suitable ac- tive materials are metallic lithium, carbon-containing materials such as graphite, graphene, charcoal, expanded graphite, furthermore lithium titanate (Li4Ti50i2), tin oxide (Sn02), and nanocrystalline silicium.
In a special embodiment of the present invention, anode (A) is selected from graphite anodes and lithium titanate anodes.
Anode (A) can further comprise a current collector. Suitable current collectors are, e.g., metal wires, metal grids, metal gaze and preferably metal foils such as copper foils. Anode (A) can further comprise a binder. Suitable binders can be selected from organic
(co)polymers. Suitable organic (co)polymers may be halogenated or halogen-free. Examples are polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, styrene- butadiene copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride- hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, ethylene-chlorofluoroethylene copolymers, ethyl-
ene-acrylic acid copolymers, optionally at least partially neutralized with alkali metal salt or ammonia, ethylene-methacrylic acid copolymers, optionally at least partially neutralized with alkali metal salt or ammonia, ethylene-(meth)acrylic ester copolymers, polysulphones, polyimides and polyisobutene.
Suitable binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvinyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene. The average molecular weight Mw of binder may be selected within wide limits, suitable examples being 20,000 g/mol to 1 ,000,000 g/mol.
In one embodiment of the present invention, anode (A) can have a thickness in the range of from 15 to 200 μηη, preferably from 30 to 100 μηη, determined without the current collector.
Inventive cells further comprise a cathode (B). Cathode (B) can be, e. g., air (or oxygen). In a preferred embodiment, however, cathode (B) contains a solid active material.
Solid active materials for cathode (B) can be selected from phosphates with olivine structure such as lithium iron phosphates (LiFeP04) and lithium manganese phosphate (LiMnP04) which can have a stoichiometric or non-stoichiometric composition and which can be doped or not doped.
In one embodiment of the present invention, active material for cathode (B) can be selected from lithium containing transition metal spinels and lithium transition metal oxides with a layered crystal structure. In such cases, cathode (B) contains at least one material selected from lithium containing transition metal spinels and lithium transition metal oxides with a layered crystal structure, respectively. In one embodiment of the present invention, lithium-containing metal spinels are selected from those of the general formula (I)
the integers being defined as follows:
0.9 < a < 1 .3, preferably 0.95 < a < 1 .15,
0 < b < 0.6, for example 0.0 or 0.5, wherein, if M1 = Ni, 0.4 < b < 0.55,
-0.1 < d < 0.4, preferably 0 < d < 0.1 ,
M1 is selected from one or more out of Al, Mg, Ca, Na, B, Mo, W and transition metals of the first row of the transition metals in the periodic table of the elements. In a preferred embodi- ment, M1 is selected from the group consisting of Ni, Co, Cr, Zn, and Al. Even more preferably, M1 is defined to be Ni.
In one embodiment of the present invention, lithium containing metal spinels are selected from LiNio,5Mni,504-d and LiM^C .
In one embodiment of the present invention, lithium transition metal oxides with a layered crystal structure are selected from compounds of general formula (II)
the integer being defined as follows: 0 < t < 0.3 and M2 selected from one or more elements from Al, Mg, B, Mo, W, Na, Ca and transition metals of the first row of the transition metals in the periodic table of the elements, at least one element being manganese.
In one embodiment of the present invention, at least 30 mole-% of M2 are selected from man- ganese, preferably at least 35 mole-%, in each time with respect to the complete amount of M2.
In one embodiment of the present invention M2 is selected from combinations of Ni, Co and Mn not containing significant amounts of additional elements. In a different embodiment of the present invention M2 is selected from combinations of Ni, Co and Mn containing significant amounts of at least one additional element, for example in the range of from 1 to 10 mole-% Al, Ca or Na.
In a particular embodiment of the present invention, lithium transition metal oxides with a lay- ered crystal structure are selected from compounds of general formula
Li(i+x)[NieCOfMngM3h](i-x)02 (HI) the integers being defined as follows: x a number in the range of from zero to 0.2,
e a number in the range of from 0.2 to 0.6, f a number in the range of from 0.1 to 0.5, g a number in the range of from 0.2 to 0.6, h a number in the range of from zero to 0.1 , and: e + f + g + h = 1 ,
M3 selected from Al, Mg, V, Fe, Cr, Zn, Cu, Ti and Mo.
In one embodiment of the present invention, M2 in formula (II) is selected from Nio,33Coo,33Mno,33, Nio,5Coo,2Mn0,3, Nio,4Coo,3Mn0,4, Ni0,4Coo,2Mn0,4 und Ni0,45Coo,ioMn0,45.
Cathode (B) can further comprise a current collector. Suitable current collectors are, e.g., metal wires, metal grids, metal gaze and preferably metal foils such as aluminum foils.
Cathode (B) can further comprise a binder. Suitable binders can be selected from organic (co)polymers. Suitable organic (co)polymers may be halogenated or halogen-free. In general, the same binders used for anode (A) can also be employed for cathode (B).
Preferred binders are especially polyvinyl alcohol and halogenated (co)polymers, for example polyvinyl chloride or polyvinylidene chloride, especially fluorinated (co)polymers such as polyvi- nyl fluoride and especially polyvinylidene fluoride and polytetrafluoroethylene.
In one embodiment of the present invention, cathode (B) can have a thickness in the range of from 15 to 200 μηη, preferably from 30 to 100 μηη, determined without the current collector. Cathode (B) can further comprise electrically conductive carbonaceous material.
Electrically conductive carbonaceous material can be selected, for example, from graphite, carbon black, carbon nanotubes, graphene or mixtures of at least two of the aforementioned substances. In the context of the present invention, electrically conductive, carbonaceous material can also be referred to as carbon for short.
In one embodiment of the present invention, electrically conductive carbonaceous material is carbon black. Carbon black may, for example, be selected from lamp black, furnace black, flame black, thermal black, acetylene black and industrial black. Carbon black may comprise impurities, for example hydrocarbons, especially aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups. In addition, sulfur- or iron- containing impurities are possible in carbon black.
In one variant, electrically conductive carbonaceous material is partially oxidized carbon black.
Inventive electrochemical cells further comprise at least one electrolyte (C). Electrolyte (C) in the context of the present invention can encompass at least one salt, preferably a lithium salt, and at least one non-aqueous solvent.
In one embodiment of the present invention, nonaqueous solvent may be liquid or solid at room temperature, preferably selected from polymers, cyclic or noncyclic ethers, cyclic and noncyclic acetals and cyclic or noncyclic organic carbonates.
Examples of suitable polymers are especially polyalkylene glycols, preferably poly-Ci-C4- alkylene glycols and especially polyethylene glycols. These polyethylene glycols may comprise up to 20 mol% of one or more Ci-C4-alkylene glycols in copolymerized form. The polyalkylene glycols are preferably polyalkylene glycols double-capped by methyl or ethyl.
The molecular weight Mw of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g/mol.
The molecular weight Mw of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be up to 5,000,000 g/mol, preferably up to 2,000,000 g/mol.
Examples of suitable noncyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1 ,2- dimethoxyethane, 1 ,2-diethoxyethane, preference being given to 1 ,2-dimethoxyethane. Examples of suitable cyclic ethers are tetrahydrofuran and 1 ,4-dioxane.
Examples of suitable noncyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1 ,1 -dimethoxyethane and 1 ,1 -diethoxyethane. Examples of suitable cyclic acetals are 1 ,3-dioxane and especially 1 ,3-dioxolane.
Examples of suitable noncyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate. Examples of suitable cyclic organic carbonates are compounds of the general formulae (IV) and (V)
in which R1, R2 and R3 may be the same or different and are selected from hydrogen and C1-C4- alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, where R2 and R3 are preferably not both tert-butyl.
In particularly preferred embodiments, R1 is methyl and R2 and R3 are each hydrogen, or R1, R2 and R3 are each hydrogen. Another preferred cyclic organic carbonate is vinylene carbonate, formula (VI).
The solvent(s) is (are) preferably used in what is known as the anhydrous state, i.e. with a water content in the range from 1 ppm to 0.1 % by weight, determinable, for example, by Karl Fischer titration.
Electrolyte further comprises one or more conductive salts. Suitable conductive salts are especially lithium salts. Examples of suitable lithium salts are LiPF6, LiBF4, UCIO4, LiAsF6, UCF3SO3, LiC(CnF2n+iS02)3, LiPFw(CnF2n+i)6-w, lithium imides such as LiN(CnF2n+iS02)2, where n is an integer in the range from 1 to 20, LiN(S02F)2, Li2SiFe, LiSbF6, LiAICU, and salts of the general formula (CnF2n+iS02)mXLi, where m is defined as follows:
m = 1 when X is selected from oxygen and sulfur,
m = 2 when X is selected from nitrogen and phosphorus, and
m = 3 when X is selected from carbon and silicon.
The integer w is a number in the range of from 1 to 6, preferably w = 3.
Preferred conductive salts are selected from LiC(CF3S02)3, LiN(CF3S02)2, LiPF6, LiBF4, LiCI04, and LiPF3(CF2CF3)3, particular preference being given to LiPF6, LiPF3(CF2CF3)3 and
LiN(CF3S02)2. In one embodiment of the present invention, the concentration of conductive salt in electrolyte is in the range of from 0.01 M to 5 M, preferably 0.5 M to 1.5 M.
Inventive electrochemical cells further comprise at least one separator (D), said separator being positioned between anode (A) and cathode (B).
In one embodiment of the present invention, separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to either a major part of one surface of anode (A) or cathode (B). In one embodiment of the present invention, separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to both a major part of one surface of anode (A) and cathode (B).
In a preferred embodiment of the present invention, separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to one surface of anode (A) or of cathode (B).
In another preferred embodiment of the present invention, separator (D) is positioned between anode (A) and cathode (B) in a way that it is like a layer to one surface of both anode (A) and of cathode (B).
In one embodiment of the present invention, separator (D) has a thickness in the range of from 10 μηη to 100 μηη, preferably 15 μηη to 35 μηη.
In one embodiment of the present invention, the specific ionic conductivity at room temperature of separator (D) in liquid electrolyte is in the range of from 10"6 S/cm to 10"3 S/cm, determined by impedance measurements of sandwich cells with separator/electrolyte combinations.
Separator (D) is manufactured from at least one polyimide, said polyimide being characterized below. To be manufactured in the context of the separator means that the separator is manufac- tured using at least one branched polyimide, preferably as the main component of separator and even more preferably as sole component.
In one embodiment of the present invention, separator further contains one or more inorganic particles (E). Inorganic particles can be selected, e. g., from oxides of Ti, Zr, Si or Al, non- stoichiometric or stoichiometric, preferred is Si02.
Polyimide from which separator (D) is manufactured is a branched polyimide and is selected from condensation products of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or anhydride or ester thereof, and
(b) at least one compound, selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule, and preferably, also referred to as polyamine (b1 ), and preferably from (b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule, also referred to as polyisocyanate (b2).
Said polyimide is briefly referred to as branched polyimide.
Branched polyimide can have a molecular weight Mw in the range from 1 ,000 to 200,000 g/mol; preference is given to 2,000 to 20,000 g/mol.
Branched polyimide can have at least two imide groups per molecule; preference is given to at least 3 imide groups per molecule.
In one embodiment of the present invention, branched polyimide can have up to 1 ,000 imide groups per molecule, preferably up to 660 per molecule.
In one embodiment of the present invention, stating the isocyanate groups or the COOH groups per molecule in each case denotes the mean value (number-average). Branched polyimide can be composed of structurally and molecularly uniform molecules. However, preference is given to branched polyimides being mixtures of molecularly and structurally differing molecules, for example, visible from the polydispersity Mw/Mn of at least 1 .4, preferably Mw Mn of 1.4 to 50, preferably 1 .5 to 10. The polydispersity can be determined by known methods, in particular by gel permeation chromatography (GPC). A suitable standard is, for example, poly(methyl methacrylate) (PMMA).
In one embodiment of the present invention, polyimide, in addition to imide groups which form the polymer backbone, comprises, terminally or in side chains, in addition at least three, preferably at least six, more preferably at least ten, terminal or side-chain functional groups. Func- tional groups in branched polyimide are preferably anhydride or acid groups and/or free or capped NCO groups. Branched polyimides preferably have no more than 500 terminal or side- chain functional groups, preferably no more than 100.
AlkyI groups such as, for example, methyl groups are therefore not a branching of a molecule of branched polyimide.
As polycarboxylic acids (a), aliphatic, or preferably aromatic, polycarboxylic acids are selected that have at least three COOH groups per molecule, or the respective anhydrides, preferably if they are present in low-molecular weight, that is to say non-polymeric, form. Such polycarboxylic acids having three COOH groups in which two carboxylic acids groups are present as an- hydride and the third as a free carboxylic acid are also comprised.
In a preferred embodiment of the present invention, as polycarboxylic acid (a), a polycarboxylic acid having at least 4 COOH groups per molecule, or the respective anhydride, is selected. Examples of polycarboxylic acids (a) and anhydrides thereof are 1 ,2,3-benzenetricarboxylic acid and 1 ,2,3-benzenetricarboxylic dianhydride, 1 ,3,5-benzenetricarboxylic acid (trimesic acid), preferably 1 ,2,4-benzenetricarboxylic acid (trimellitic acid), trimellitic anhydride and, in particular, 1 ,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) and 1 , 2,4, 5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride), 3,3',4,4"-benzophenonetetracarboxylic acid, 3,3',4,4"- benzophenonetetracarboxylic dianhydride, in addition benzenehexacarboxylic acid (mellitic acid) and anhydrides of mellitic acid.
Other suitable polycarboxylic acids (a) and anhydrides thereof are mellophanic acid and mello- phanic anhydride, 1 ,2,3,4-benzenetetracarboxylic acid and 1 ,2,3,4-benzenetetracarboxylic di- anhydride, 3,3,4,4-biphenyltetracarboxylic acid and 3,3,4,4-biphenyltetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic acid and 2,2,3,3-biphenyltetracarboxylic dianhydride, 1 ,4,5,8- naphthalenetetracarboxylic acid and 1 ,4,5, 8-naphthalenetetracarboxylic dianhydride, 1 ,2,4,5- naphthalenetetracarboxylic acid and 1 ,2,4,5-naphthalenetetracarboxylic dianhydride, 2,3,6,7- naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 ,4,5,8- decahydronaphthalenetetracarboxylic acid and 1 ,4,5,8-decahydronaphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1 ,2,3,5,6,7-hexahydronaphthalene-1 ,2,5,6-tetracarboxylic acid and 4,8-dimethyl-1 ,2,3,5,6,7-hexahydronaphthalene-1 ,2,5,6-tetracarboxylic dianhydride, 2,6- dichloronaphthalene-1 ,4,5,8-tetracarboxylic acid and 2,6-dichloronaphthalene-1 ,4,5,8- tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1 ,4,5,8-tetracarboxylic acid and 2,7- dichloronaphthalene-1 ,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-
1 ,4,5,8-tetracarboxylic acid and 2, 3, 6, 7-tetrachloronaphthalene-1 ,4,5,8-tetracarboxylic dianhydride, 1 ,3,9,10-phenanthrenetetracarboxylic acid and 1 ,3,9,10-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid and 3,4,9, 10-perylenetetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)methane and bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane and bis(3,4-dicarboxyphenyl)methane dianhydride, 1 ,1 - bis(2,3-dicarboxyphenyl)ethane and 1 ,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1 ,1 - bis(3,4-dicarboxyphenyl)ethane and 1 ,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2- bis(2,3-dicarboxyphenyl)propane and 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,3- bis(3,4-dicarboxyphenyl)propane and 2,3-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4- carboxyphenyl)sulfone and bis(3,4-carboxyphenyl)sulfone dianhydride, bis(3,4-carboxyphenyl) ether and bis(3,4-carboxyphenyl) ether dianhydride, ethylenetetracarboxylic acid and ethylene- tetracarboxylic dianhydride, 1 ,2,3, 4-butanetetracarboxylic acid and 1 ,2,3,4-
butanetetracarboxylic dianhydride, 1 ,2,3,4-cyclopentanetetracarboxylic acid and 1 ,2,3,4,- cyclopentanetetracarboxylic dianhydride, 2,3,4,5-pyrrolidinetetracarboxylic acid and 2,3,4,5- pyrrolidinetetracarboxylic dianhydride, 2,3,5,6-pyrazinetetracarboxylic acid and 2,3,5,6- pyrazinetetracarboxylic dianhydride, 2,3,4,5-thiophenetetracarboxylic acid and 2,3,4,5- thiophenetetracarboxylic dianhydride.
In one embodiment of the present invention, anhydrides from US 2,155,687 or US 3,277,1 17 are used for synthesizing a branched polyimide. Polycarboxylic acid (a) or its respective anhydride can be reacted with at least one compound (b), selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule, also referred to as polyamine (b1 ), and preferably,
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule, also referred to as polyisocyanate (b2).
Preferably, polycarboxylic acid (a) or its respective anhydride will be reacted
either with at least one polyamine (b1 )
or preferably with at least one polyisocyanate (b2).
Polyamines (b1 ) can be aliphatic, cycloaliphatic or preferably aromatic. In polyamine (b1 ) only primary amino groups (Nhb-groups) will be taken into account. Tertiary and secondary amino groups - if present - will not be taken into consideration when determining the number of amino groups in polyamine (b1 ).
Polyamine (b1 ) has on average more than two amino groups per molecule, preferably on average at least 2.5, more preferably on average at least 3.0.
In one embodiment, polyamines (b1 ) are selected from mixtures from diamines and triamines.
In one embodiment of the present invention, polyamine (b1 ) bears on average a maximum of 8, preferably on average a maximum of 6 amine groups per molecule.
Aromatic triamines and mixtures of aromatic or aliphatic diamines and aromatic triamines are particularly preferred examples for polyamines (b1 ).
Examples for aliphatic diamines to be present in said mixtures of mixtures of aromatic or aliphatic diamines and aromatic triamines as polyamines (b1 ) are ethylene diamine, 1 ,3-propylene diamine, diethylenetriamine, tetraethylenepentamine, and triethylenetetramine.
Suitable aromatic triamines that can be selected as polyamines (b1 ) - alone or as a mixture with at least one aromatic diamine - are chosen from triamines in which the Nhb groups are attached
to one or preferable to at least two aromatic rings, said different aromatic rings being so-called isolated aromatic rings, conjugated aromatic rings, or fused aromatic rings.
Preferably, triamines with Nhb-groups attached to different conjugated or isolated aromatic rings are selected.
Examples are 1 ,3,5-tri(4-aminophenoxy) benzene, 1 ,3,5-tri(3-methy 1 ,4-aminophenoxy) benzene, 1 ,3,5-tri(3 -methoxy,4-aminophenoxy) benzene, 1 ,3,5-tri(2-methyl,4-aminophenoxy) benzene, 1 ,3,5 -tri(2-methoxy,4-aminophenoxy) benzene, and 1 ,3,5-tri(3-ethyl,4- aminophenoxy)benzene.
Further examples for triamines are 1 ,3,5-tri(4-aminophenylamino) benzene, 1 ,3,5-tri(3-methyl,4- aminophenylamino) benzene, 1 ,3,5-tri(3-methoxy,4-aminophenylamino) benzene, 1 ,3,5-tri(2- methyl,4-aminophenylamino) benzene, 1 ,3, 5-tri(2-methoxy,4-aminophenylamino) benzene, and 1 ,3,5-tri(3-ethyl,4-aminophenylamino) benzene.
Examples are triamines according to formula (VII)
R5, R6 - being different or preferably identical and selected from hydrogen, Ci-C4-alkyl,
COOCHs, COOC2H5, CN, CF3, or 0-CH3;
X1, X2 - being different or preferably identical and selected from single bonds, Ci-C4-alkylene groups, N-H, and oxygen, preferable -CH2- or oxygen.
In one embodiment, polyamine (b1 ) is selected from 3,5-di(4-aminophenoxy)aniline, 3,5-di(3- methyl-1 ,4-aminophenoxy)aniline, 3,5-di(3-methoxy-4-aminophenoxy)aniline, 3,5-di(2-methyl-4- aminophenoxy)aniline, 3,5-di(2-methoxy-4-aminophenoxy)aniline, and 3 ,5-d i (3-ethyl-4- aminophenoxy)aniline.
In one embodiment, examples are triamines according to formula (VIII)
R7 selected from hydrogen, Ci-C4-alkyl, COOCH3, COOC2H5, CN, CF3, or 0-CH3; R8 selected from hydrogen or methyl and the other integers being defined as above.
Polyisocyanate (b2) can be selected from any polyisocyanates that on average have more than two isocyanate groups per molecule, which can be capped or preferably free. Preference is given to trimeric or oligomeric diisocyanates, for example oligomeric hexamethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric tolylene diisocyanate, preferably trimeric tol- ylene diisocyanate, oligomeric diphenylmethane diisocyanate - hereinafter also termed poly- mer-MDI - and mixtures of the abovementioned polyisocyanates. For example, what is termed trimeric hexamethylene diisocyanate, in many cases, is not present as pure trimeric diisocyanate, but as polyisocyanate having a medium functionality of 3.6 to 4 NCO groups per molecule. The same applies to oligomeric tetramethylene diisocyanate and oligomeric isophorone diisocyanate. In one embodiment of the present invention, polyisocyanate (b2) having more than two isocyanate groups per molecule is a mixture of at least one diisocyanate and at least one triisocy- anate, or a polyisocyanate having at least 4 isocyanate groups per molecule.
In one embodiment of the present invention, polyisocyanate (b2) has on average at least 2.2, preferably at least on average 2.5, particularly preferably at least on average 3.0, isocyanate groups per molecule.
In one embodiment of the present invention, polyisocyanate (b2) bears on average a maximum of 8, preferably on average a maximum of 6 isocyanate groups per molecule.
In one embodiment of the present invention, polyisocyanate (b2) is selected from oligomeric hexamethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate, and mixtures of the abovementioned polyisocyanates.
Polyisocyanate (b2) can, in addition to urethane groups, also have one or more other functional groups, for example urea, allophanate, biuret, carbodiimide, amide, ester, ether, uretonimine, uretdione, isocyanurate or oxazolidine groups. When polyamine (b1 ) and polycarboxylic acid (a) are condensed with one another - preferably in the presence of a catalyst - an imide group is formed under elimination of H2O.
In the above formulae, R** is the polyisocyanate (b2) radical that is not specified further in the above reaction equation, and n is a number greater than or equal to 1 , for example 1 in the case
of a tricarboxylic acid or 2 in the case of a tetracarboxylic acid, and optionally, (HOOC)n can be replaced with a C(=0)-0-C(=0) moiety.
In an embodiment of the present invention, polyisocyanate (b2) is used in a mixture with at least one diisocyanate, for example with tolylene diisocyanate, hexamethylene diisocyanate or with isophorone diisocyanate. In a particular variant, polyisocyanate (b2) is used in a mixture with the corresponding diisocyanate, for example trimeric HDI with hexamethylene diisocyanate or trimeric isophorone diisocyanate with isophorone diisocyanate or polymeric diphenylmethane diisocyanate (polymer MDI) with diphenylmethane diisocyanate.
In one embodiment of the present invention, polycarboxylic acid (a) is used in a mixture with at least one dicarboxylic acid or with at least one dicarboxylic anhydride, for example with phthalic acid or phthalic anhydride. Some synthesis methods for making branched polyimides are described below.
Preferred synthesis methods for making branched polyimides comprise reacting with one another
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or anhy- dride or ester thereof,
(b) at least one compound, selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule,
in the presence of a catalyst.
As catalysts, in particular water and Bransted bases are suitable, for example alkalimetal alco- holates, in particular alkanolates of sodium or potassium, for example sodium methanolate, so- dium ethanolate, sodium phenolate, potassium methanolate, potassium ethanolate, potassium phenolate, lithium methanolate, lithium ethanolate and lithium phenolate.
For carrying out the synthesis method for making branched polyimides, polyisocyanate (b2) and polycarboxylic acid (a) or anhydride (a) can be used in a quantitative ratio such that the molar fraction of NCO groups to COOH groups is in the range from 1 : 3 to 3 : 1 , preferably 1 : 2 to 2 : 1 . In this case, one anhydride group of the formula CO-O-CO counts as two COOH groups.
In an embodiment of the present invention, catalyst can be used in the range from 0.005 to 0.1 % by weight, based on the sum of polyisocyanate (b2) and polycarboxylic acid (a) or polyisocyanate (b2) and anhydride (a). Preference is given to 0.01 to 0.05% by weight of catalyst.
In an embodiment of the present invention, a synthesis method for making branched polyimides can be carried out at temperatures in the range from 50 to 200°C, preferably 50 to 140°C, particularly preferably 50 to 100°C. In an embodiment of the present invention, a synthesis method for making branched polyimides can be carried out at atmospheric pressure. However, the synthesis is also possible under pressure, for example at pressures in the range from 1 .1 to 10 bar.
In an embodiment of the present invention, a synthesis method for making branched polyimides can be carried out in the presence of a solvent or solvent mixture. Examples of suitable solvents are N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl sulphones, xylene, phenol, cresol, ketones such as, for example, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetophenone, in addition mono- and dichlorobenzene, ethylene glycol monoethyl ether acetate and mixtures of two or more of the abovementioned mixtures. In this case, the solvent or solvents can be present during the entire synthesis time or only during part of the synthesis.
The reaction can be carried out, for example, for a time period of 10 minutes to 24 hours. In a preferred embodiment of the present invention, the synthesis method for making branched polyimides is carried out under inert gas, for example under argon or under nitrogen.
If water-sensitive Bransted base is used as catalyst, it is preferred to dry inert gas and solvent. If water is used as catalyst, the drying of solvent and inert gas can be dispensed with.
In a variant of the synthesis method for making branched polyimides, NCO end groups of branched polyimide can be blocked with a blocking agent (c), for example with secondary amine, for example with dimethylamine, di-n-butylamine or with diethylamine. In one embodiment of the present invention, inventive electrochemical cells can contain additives such as wetting agents, corrosion inhibitors, or protective agents such as agents to protect any of the electrodes or agents to protect the salt(s).
In one embodiment of the present invention, inventive electrochemical cells can have a disc-like shape. In another embodiment, inventive electrochemical cells can have a prismatic shape.
In one embodiment of the present invention, inventive electrochemical cells can include a housing that can be from steel or aluminium. In one embodiment of the present invention, inventive electrochemical cells are combined to stacks including electrodes that are laminated.
In one embodiment of the present invention, inventive electrochemical cells are selected from pouch cells.
Inventive electrochemical cells have overall advantageous properties. They have a long dura- tion with very low loss of capacity, good cycling stability, and a reduced tendency towards short circuits after longer operation and/or repeated cycling.
A further aspect of the present invention refers to batteries containing at least one inventive electrochemical cell, for example two or more. Inventive batteries have advantageous proper- ties. They have a long duration with very low loss of capacity, good cycling stability, and high temperature stability.
A further aspect of the present invention is the use of inventive electrochemical cells or inventive batteries according for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks, and stationary applications such as energy storage devices for power plants. A further aspect of the present invention is a method of making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equip- ment, remote car locks, and stationary applications such as energy storage devices for power plants by employing at least one inventive battery or at least one inventive electrochemical cell.
A further aspect of the present invention is the use of polyimides selected from branched condensation products of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or an anhydride or ester thereof,
(b) at least one compound, selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule
as or for manufacturing of separators in electrochemical cells.
A further aspect of the present invention is a separator, comprising at least one polyimide, se- lected from branched condensation products of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or an anhydride or ester thereof,
(b) and at least one compound, selected from
(b1 ) at least one polyamine having on average more than two amino groups per mole- cule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
Polyisocyanate (b2) and polycarboxylic acids (a) have been defined above.
In one embodiment of the present invention, inventive separator (D) has a thickness in the range of from 10 μηη to 100 μηη, preferably 15 μηη to 35 μηη.
In one embodiment of the present invention, the specific ionic conductivity at room temperature of inventive separator (D) in liquid electrolyte is in the range of from 10-6 S/cm to 10"3 S/cm, determined by impedance measurements of sandwich cells with separator/electrolyte combina- tions.
A further aspect of the present invention is a method for manufacturing inventive separators. Said inventive method comprises making a film of branched polyimide. In one embodiment of the inventive method, one dissolves at least one branched polyimide in a suitable solvent or mixture of solvents and then applies said solution to a flat surface, for example to a glass surface or to a metal foil, e. g., an aluminum foil, or to a plastics foil such as a polyethylene terephthalate film (PET foil). Then one removes the solvent or solvents, respectively. Afterwards, the inventive separator can be removed from the flat surface, for example mechani- cally.
Examples for suitable solvents are, e. g., cyclic or non-cyclic amides, ketones, and cyclic and non-cyclic ethers. Examples for cyclic amides are N-methylpyrrolidone (NMP) and N-ethylpyrrolidone (NEP). Examples for non-cyclic amides are Ν,Ν-dimethylformamide and Ν,Ν-dimethylacetamide. Examples for ketones are acetone, methylethylketone, methyl isobutyl ketone (MIBK), and cyclohex- anone. Examples for ethers are 1 ,2-dimethoxyethane, di-n-butyl ether, tetrahydrofurane and preferably anisole.
Solutions of at least one branched polyimide can have a solids content in the range of from 5 to 50 % by weight, preferably 15 to 30 % by weight.
Application of the solution to a flat surface can be performed by spraying, blade coating, spin coating, drop casting, or dip coating.
Removal of the solvent(s) can be achieved by evaporating the solvent(s) or allowing to evaporate, for example by heating, or via reduction of pressure, or via using a gas stream. Removal of the separator from the flat surface can be achieved by mere mechanical means, or it can be supported by softening, e.g., by allowing to rest in a solvent with poor solution ability, such as water.
In another embodiment, inventive separators can be made by applying a solution of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or an anhydride or ester thereof,
(b) and at least one compound, selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
to a flat surface, and allow to in situ form at least one branched polyimide. Then the solvent(s) is/are removed.
Inventive separators (D) have overall advantageous properties. They help to secure a long duration of electrochemical cells with very low loss of capacity, good cycling stability, and a reduced tendency towards short circuits after longer operation and/or repeated cycling. They can help batteries to have a long duration with very low loss of capacity, good cycling stability, and high temperature stability.
The present invention will be illustrated by non-limiting working examples. Working examples General remarks:
Polycarboxylic acid (a.1 ): dianhydride of 1 ,2,4,5-benzene tricarboxylic acid
Polyisocyanate (b2.1 ): polymeric 4, 4'-diphenylmethane diisocyanate ("Polymer-MDI"), average of 2.7 isocyanate groups per molecule, dynamic viscosity: 195 mPa-s at 25°C, commercially availabe as Lupranat® M20W.
Polyisocyanate (b2.2): Isocyanurate from hexamethylendiisocyanate, average of 3,6 isocyanate groups per molecule.
"NCO": NCO content, determined by IR spectroscopy unless expressly mentioned otherwise, it is indicated in % by weight. The molecular weights were determined by gel permeation chromatography (GPC using a re- fractometer as detector). The standard used was polymethyl methacrylate (PMMA). The solvents used were Ν,Ν-dimethylacetamide (DMAc) or tetrahydrofurane (THF), if not stated otherwise.
Percentages are % by weight unless expressly mentioned otherwise.
1.1 Synthesis of branched polyimide BP.1
An amount of 100 g of (a.1 ) (0.46 mole), dissolved in 1400 ml of acetone, were placed in a 4 liter four-neck flask having a dropping funnel, reflux condenser, internal thermometer and Teflon stirrer, and 0.1 g of water was added. Then, 465 g (1 .38 mole) of polyisocyanate (b2.1 ) were added dropwise at 20°C. The mixture was heated with stirring to 55°C. The mixture was stirred for a further seven hours under reflux at 55°C. Then, the temperature was slowly raised to 135°C and the acetone was distilled off. The molecular weight and the NCO content were determined from an aliquot. Branched polyimide BP.1 was obtained.
Mn: 3,050 g/mol, Mw: 8,800 g/mol (in DM Ac)
NCO: 20 %
1.2 Synthesis of branched polyimide BP.2 An amount of 100 g of (a.1 ) (0.46 mole), dissolved in 1400 ml of acetone, were placed in a 4 liter four-neck flask having a dropping funnel, reflux condenser, internal thermometer and Teflon stirrer, and 0.1 g of water was added. Then, 400 g (1 .19 mole) of polyisocyanate (b2.1 ) were added dropwise at 20°C. The mixture was heated with stirring to 55°C. The mixture was stirred for a further six hours under reflux at 55°C. The molecular weight and the NCO content were determined from an aliquot.
Mn = 3,300 g/mol, Mw= 4,820 g/mol (in DMAc)
NCO: 27.8% (measured according to DIN EN ISO 1 1909)
Then the sample was diluted by addition of 350 g from a 1 :1 mixture of 2,4'- diphenylmethandiisocyanate and 4,4'-diphenylmethandiisocyanate. The acetone was then distilled off over a time of one hour at normal pressure. At the end of the distillation the temperature was raised to 70°C, the pressure was reduced to 200 mbar and the residue was stripped by using a nitrogen stream. Branched polyimide BP.2 was obtained.
Mn = 2,380 g/mol, Mw = 3,000 g/mol, Mw/Mn = 1 .3 (in DMAc)
NCO: 29.4% (measured according to DIN EN ISO 1 1909) 1.3 Synthesis of branched polyimide BP.3
An amount of 33 g of (a.1 ) (0.15 mole), dissolved in 467 ml of acetone, were placed in a 4 liter four-neck flask having a dropping funnel, reflux condenser, internal thermometer and Teflon stirrer, and 0.05 g of water was added. Then, 50 g (0.075 mole) of polyisocyanate (b2.2) were added dropwise at 20°C. The mixture was heated with stirring to 55°C. The mixture was stirred for a further six hours under reflux at 55°C. Branched polyimide BP.3 was obtained. The molecular weight and the NCO content were determined from an aliquot. The acetone was then
distilled off over a time of one hour at normal pressure. At the end of the distillation the temperature was raised to 70°C, the pressure was reduced to 200 mbar and the residue was stripped by using a nitrogen stream. Branched polyimide BP.3 was obtained. Mw: 2,166 g/mol (in THF)
1.4 Synthesis of branched polyimide BP.4
An amount of 100 g of (a.1 ) (0.46 mole), dissolved in 300 g N-methylpyrrolidone (NMP), were placed in a 2 liter four-neck flask having a dropping funnel, reflux condenser, internal thermometer and Teflon stirrer, and 0.1 g of water was added. The mixture was heated with stirring to 80°C. Then, 142 g (0.22 mole) of polyisocyanate (b2.2) were added dropwise at 80°C within a time range of six hours. The mixture was heated with stirring for further ten hours at 80°C. The mixture was cooled down to room temperature and an aliquot of the branched polyimide BP.4 so obtained was analyzed.
Mn: 1 ,013 g/mol, Mw: 3,877 g/mol, Mw/Mn: 3.8 (in THF)
1.5 Synthesis of branched polyimide BP.5
An amount of 100 g of (a.1 ) (0.46 mole), dissolved in 300 g NMP, were placed in a 2 liter four- neck flask having a dropping funnel, reflux condenser, internal thermometer and Teflon stirrer, and 0.05 g of water was added. The mixture was heated with stirring to 80°C. Then, 142 g (0.22 mole) of polyisocyanate (b2.2) were added dropwise at 80°C within a time range of one hour. The mixture was heated with stirring for further four hours at 80°C. Then, 38 g of polyisocyanate (b2.1 ) were added to the reaction mixture within a time range of 1 hour at 80°C. The mixture was cooled down to room temperature and an aliquot of the branched polyimide BP.5 so obtained was analyzed. Mn: 591 g/mol, Mw: 2,549 g/mol, Mw/Mn: 4.3 (in THF)
NCO: 7.92% (measured according to DIN EN ISO 1 1909)
1.6 Synthesis of branched polyimide BP.6 An amount of 100 g of (b.1 ) (0.46 mole), dissolved in 300 g NMP, were placed in a 2 liter four- neck flask having a dropping funnel, reflux condenser, internal thermometer and Teflon stirrer, and 0.1 g of NaOCH3 was added. The mixture was heated with stirring to 80°C. Then, 142 g (0.22 mole) of polyisocyanate (b2.2) were added dropwise at 80°C within a time range of one hour. The mixture was heated with stirring for further ten hours at 80°C. The mixture was cooled down to room temperature and an aliquot of the residue so obtained was analyzed.
NCO 6.8 % (measured according to DIN EN ISO 1 1909)
Then, 1 17 g of di-n-butylamine (c.1 ) were added at room temperature over a time range of 1 17 g and the reaction mixture was further heated for two hours. Then the branched polyimide BP.6 was isolated via precipitation in water followed by drying at 80°C under reduced pressure. The branched polyimide BP.6 so obtained was analyzed via GPC
Mn: 5,820 g/mol, Mw: 57,900 g/mol, Mw/Mn: 10 (in DM Ac)
I I . Manufacture of inventive separator (D.1 ) Branched polyimide (BP.1 ) (3 g) was dissolved in 10 g NMP as solvent and warmed to 80°C. The 30% solution so obtained was applied at 80°C with a doctor blade method to a glass plate. The solvent-containing film had a thickness of 50 μηη. The NMP was allowed to evaporate for 10 minutes at 80°C. The film was then - together with the glass plate - placed into a water bath having room temperature for 1 hour. Then, a film was be removed manually which was dried over a period of 24 hours under vacuum at 80°C. Inventive separator (D.1 ) was so obtained.
The specific electric conductivity of inventive separator (D.1 ) was 10-5 S/cm, determined in a 1 M solution of LiPF3(CF2CFs)3 in a 1 :1 (by weight) mixture of ethylene carbonate/dimethyl carbonate.
III. Test of inventive separator (D.1 ) in a lithium ion battery
An inventive electrochemical cell (EC.1 ) according to figure 1 was assembled.
Figure I shows an exploded view of inventive electrochemical cell (EC. 1 ).
The labels in figure 1 mean:
1 , 1 ' Dies
2, 2' Nuts
3, 3' Sealing ring - two in each case, the second sealing ring in each case, which is somewhat smaller, not being shown here
4 Coil spring
5 Nickel output conductor
6 Housing Anode: graphite on copper foil as current collector with a thickness of 36 to 38 μηη.
Cathode: LiNio.8Coo.15Alo.05O2, on aluminium foil as current collector.
1 M solution of LiPF3(CF2CFs)3 in a 1 :1 (by weight) mixture of ethylene carbonate/dimethyl carbonate
As cathode (B.1 ), a nickel manganese spinel electrode was used which had been manufactured as follows.
85% LiMni,5Nio,504
6% PVdF, commercially available as Kynar Flex® 2801 of Arkema Group,
6% carbon black, BET surface 62 m2/g, commercially available as„Super P Li" by Timcal, 3% graphite, commercially available as KS6 by Timcal,
were mixed in a container with a lid. Under stirring, an amount of NMP was added until a viscous lump-free paste was obtained. Stirring was performed over a time of 16 hours.
The paste so obtained was applied to an aluminium foil (thickness of the aluminium foil: 20 μηη) with a knife blade. Then, the aluminium foil so coated was dried in a drying cabinet at 120°C under vacuum. The thickness of the dried coating was 30 μηη. Then round segments were punched out, diameter: 12 mm.
Inventive electrochemical cell (EC.1 ) was charged with a constant current to a voltage of 4.2 V followed by a final charging with constant voltage at 4.2 V. Then, inventive electrochemical cell (EC.1 ) was discharged at constant current to a voltage of 3 V. Three such cycles with 0.1 C and, thereafter, 20 cycles with 0.5 C were determined. The capacity was determined to be 90 to 100 mA-h.
Claims
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
Electrochemical cell according to claim 1 , wherein, as polycarboxylic acid (a), a polycarboxylic acid having at least 4 COOH groups per molecule, or the respective anhydride or ester, is selected.
3. Electrochemical cell according to claim 1 or 2, wherein polyisocyanate (b2) is selected from oligomeric hexamethylene diisocyanate, oligomeric tetramethylene diisocyanate, oligomeric isophorone diisocyanate, oligomeric diphenylmethane diisocyanate, oligomeric tolylene diisocyanate and mixtures of the abovementioned polyisocyanates.
4. Electrochemical cell according to any of claims 1 to 3, wherein separator (D) has a thickness in the range of from 1 to 100 μηη.
5. Electrochemical cell according to any of claims 1 to 4, characterized in that it is a lithium- ion containing cell.
6. Electrochemical cell according to any of claims 1 to 5, characterized in that anode (A) is selected from graphite anodes and lithium titanate anodes.
7. Electrochemical cell according to any of claims 1 to 6, characterized in that cathode (B) contains at least one material selected from lithium containing transition metal spinels and lithium transition metal oxides with a layered crystal structure.
8. Electrochemical cell according to any one of claims 1 to 7, wherein polyimide has a poly- dispersity Mw/Mn of at least 1 .4.
9. Electrochemical cell according to any of the claims 1 to 8 wherein lithium transition metal oxides with a layered crystal structure are selected from those of general formula
Li(i+x)[NieCOfMngM2h](i-x)02, the integers being defined as follows: x a number in the range of from zero to 0.2, e a number in the range of from 0.2 to 0.6, f a number in the range of from 0.1 to 0.5, g a number in the range of from 0.2 to 0.6, h a number in the range of from zero to 0.2, and: e + f + g + h = 1 ,
M2 selected from Al, Mg, V, Fe, Cr, Zn, Cu, Ti and Mo.
10. Electrochemical cell according to any of the claims 1 to 9 characterized in that cathode (B) contains a material based on electrically conductive carbon.
1 1 . Battery containing at least one electrochemical cell according to any of the preceding claims.
12. Use of electrochemical cells according to any of claims 1 to 10 or a battery according to claim 1 1 for making or operating cars, computers, personal digital assistants, mobile telephones, watches, camcorders, digital cameras, thermometers, calculators, laptop BIOS, communication equipment or remote car locks.
13. Use of polyimides selected from branched condensation products of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or an anhydride or ester thereof, and
(b) at least one compound selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule,
as or for manufacturing of separators in electrochemical cells.
Separator, comprising at least one polyimide, selected from branched condensation products of
(a) at least one polycarboxylic acid having at least 3 COOH groups per molecule or an anhydride or ester thereof, and
(b) at least one compound selected from
(b1 ) at least one polyamine having on average more than two amino groups per molecule and
(b2) at least one polyisocyanate having on average more than two isocyanate groups per molecule.
Separator according to claim 14, further comprising one or more inorganic particl
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014510921A JP2014517467A (en) | 2011-05-19 | 2012-05-15 | Electrochemical cell containing polyimide |
| EP12786192.0A EP2710651A4 (en) | 2011-05-19 | 2012-05-15 | Electrochemical cells comprising polyimides |
| CN201280022033.5A CN103503195A (en) | 2011-05-19 | 2012-05-15 | Electrochemical cells comprising polyimides |
| KR1020137033797A KR20140045427A (en) | 2011-05-19 | 2012-05-15 | Electrochemical cells comprising polyimides |
| US14/112,554 US20140045070A1 (en) | 2011-05-19 | 2012-05-15 | Electrochemical cells comprising polyimides |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11166678.0 | 2011-05-19 | ||
| EP11166678 | 2011-05-19 |
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| WO2012156903A1 true WO2012156903A1 (en) | 2012-11-22 |
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| PCT/IB2012/052411 WO2012156903A1 (en) | 2011-05-19 | 2012-05-15 | Electrochemical cells comprising polyimides |
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|---|---|
| US (1) | US20140045070A1 (en) |
| EP (1) | EP2710651A4 (en) |
| JP (1) | JP2014517467A (en) |
| KR (1) | KR20140045427A (en) |
| CN (1) | CN103503195A (en) |
| WO (1) | WO2012156903A1 (en) |
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| EP2835856A4 (en) * | 2012-04-02 | 2015-03-11 | Nissan Motor | Electrolyte solution for lithium ion secondary batteries, and lithium ion secondary battery |
| US8987357B2 (en) | 2011-05-27 | 2015-03-24 | Basf Se | Thermoplastic molding composition |
| WO2015074913A1 (en) | 2013-11-21 | 2015-05-28 | Basf Se | Cross-linked polymeric materials based on polyimides, production and use thereof |
| US9653750B2 (en) | 2014-02-19 | 2017-05-16 | Sion Power Corporation | Electrode protection using a composite comprising an electrolyte-inhibiting ion conductor |
| US9676915B2 (en) | 2012-12-17 | 2017-06-13 | Basf Se | Porous branched/highly branched polyimides |
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| US11135564B2 (en) * | 2017-03-23 | 2021-10-05 | Aspen Aerogels, Inc. | Porous polymer compositions for the synthesis of monolithic bimodal microporous/macroporous carbon compositions useful for selective CO2 sequestration |
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Also Published As
| Publication number | Publication date |
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| US20140045070A1 (en) | 2014-02-13 |
| EP2710651A1 (en) | 2014-03-26 |
| JP2014517467A (en) | 2014-07-17 |
| CN103503195A (en) | 2014-01-08 |
| KR20140045427A (en) | 2014-04-16 |
| EP2710651A4 (en) | 2015-01-21 |
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