WO2014147648A1 - High-ionic conductivity electrolyte compositions comprising semi-interpenetrating polymer networks and their composites - Google Patents
High-ionic conductivity electrolyte compositions comprising semi-interpenetrating polymer networks and their composites Download PDFInfo
- Publication number
- WO2014147648A1 WO2014147648A1 PCT/IN2014/000174 IN2014000174W WO2014147648A1 WO 2014147648 A1 WO2014147648 A1 WO 2014147648A1 IN 2014000174 W IN2014000174 W IN 2014000174W WO 2014147648 A1 WO2014147648 A1 WO 2014147648A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- semi
- oxide
- component
- ionic conductivity
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 153
- 239000003792 electrolyte Substances 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 53
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 239000002114 nanocomposite Substances 0.000 claims abstract description 38
- 229920000570 polyether Polymers 0.000 claims abstract description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 30
- 239000002086 nanomaterial Substances 0.000 claims abstract description 23
- -1 polytetramethylene Polymers 0.000 claims description 112
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 16
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 6
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 6
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 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 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 6
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 229910002588 FeOOH Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
- 235000019414 erythritol Nutrition 0.000 claims description 3
- 229940009714 erythritol Drugs 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010881 fly ash Substances 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 229960005150 glycerol Drugs 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 claims description 3
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 claims description 3
- 239000000845 maltitol Substances 0.000 claims description 3
- 235000010449 maltitol Nutrition 0.000 claims description 3
- 229940035436 maltitol Drugs 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002776 polycyclohexyl methacrylate Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 3
- SSGHNQPVSRJHEO-UHFFFAOYSA-N selenocyanogen Chemical compound N#C[Se][Se]C#N SSGHNQPVSRJHEO-UHFFFAOYSA-N 0.000 claims description 3
- 208000027409 severe congenital neutropenia 7 Diseases 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 229960002920 sorbitol Drugs 0.000 claims description 3
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 37
- 230000015572 biosynthetic process Effects 0.000 abstract description 21
- 239000007784 solid electrolyte Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 239000005518 polymer electrolyte Substances 0.000 description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000004971 Cross linker Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 229920002521 macromolecule Polymers 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 208000014117 bile duct papillary neoplasm Diseases 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 230000006870 function Effects 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000033001 locomotion Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 238000004626 scanning electron microscopy Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000037427 ion transport Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- WGZCUXZFISUUPR-UHFFFAOYSA-N acetonitrile;oxolane Chemical compound CC#N.C1CCOC1 WGZCUXZFISUUPR-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 238000000348 solid-phase epitaxy Methods 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 2
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- VAANUEHPYNAMQR-UHFFFAOYSA-N 5-amino-2-(4-aminophenyl)cyclohexa-2,4-diene-1,1-disulfonic acid Chemical compound OS(=O)(=O)C1(S(O)(=O)=O)CC(N)=CC=C1C1=CC=C(N)C=C1 VAANUEHPYNAMQR-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 229910052768 actinide Chemical class 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920005605 branched copolymer Polymers 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009750 centrifugal casting Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002593 electrical impedance tomography Methods 0.000 description 1
- 229920001746 electroactive polymer Polymers 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 150000002083 enediols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000013627 low molecular weight specie Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000679 poly(dimethylsiloxane-co-methylphenylsiloxane) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 201000006681 severe congenital neutropenia Diseases 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/145—Liquid electrolytic capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the invention relates to high-ionic conductivity electrolyte compositions.
- the invention particularly relates to high-ionic conductivity electrolyte compositions of semi-interpenetrating polymer networks and their nanocomposites as quasi-solid/solid .electrolyte matrix for energy generation, storage and delivery devices, in particular for hybrid solar cells, rechargeable batteries, capacitors, electrochemical systems and flexible devices.
- Electrolytes remain an integral component of these next generation devices.
- Current rechargeable Li-ion batteries and third generation DSSCs/Q-DSSCs cell configurations have a liquid or gel electrolyte along with a separator between the anode and cathode.
- the device performance and life-time is dominated by the functioning and stability of the electrolytes under operational conditions.
- Most of the present day devices use multiple layers of an inert porous polymeric (polyolefin) separator membrane with defined porosity as described in U.S. Pat. No.
- PEs contrast sharply compared to the usual electrolyte materials with respect to the mode of charge transport and the value of ionic conductivity; however, for electrochemical applications the flexibility offered by the polymer electrolyte is important.
- lightweight, shape-conforming, compliant, polymer electrolyte-based systems could find widespread application as energy generation and storage/delivery devices.
- polymeric matrix as an electrolyte medium was first conceived in 1973 with the complex forming capability of poly(ethylene oxide) (PEO) and alkali metal salts, (see Fenton et al., Polymer 1973, 14, 589; Wright PV, Br. Polym. J. 1975, 7, 319; J. Polym. Sci. polym. Phys. Ed.
- PEO poly(ethylene oxide)
- alkali metal salts see Fenton et al., Polymer 1973, 14, 589; Wright PV, Br. Polym. J. 1975, 7, 319; J. Polym. Sci. polym. Phys. Ed.
- an ideal polymer host must satisfy the criteria such as (i) a high concentration of sequential polar groups on the polymer chain with sufficient electron donor power to form coordinate bonds with cations thereby achieving effective salt salvation; (ii) preferably have a low glass transition temperature where in low barriers to bond rotation thermodynamically allows facile segmental reorientation of the polymer chain, and (iii) suitable distance between the coordination sites to allow flexibility to the polymer segment.
- poly(ethylene oxide) is the most widely studied one.
- the inorganic salt containing poly(ethylene oxide) is a representative starting system to design solid polymer electrolytes of high ionic conductivity.
- Poly (ethylene oxide) has attracted special attention owing to its low glass transition temperature (T g ⁇ -60 °C) and its ability to solvate a wide range of salts.
- Blending of poly(ethylene oxide) with suitable polymers is the simplest of the alternatives to improve the dimensional stability and/or mechanical strength.
- Various polymers such as poly(2-vinylpyridine), poly(acrylonitrile), poly(vinlylacetate), poly(methylmethacrylate), nafion and polyurethanes have been used to prepare blends (see MacCallum et al., In Polymer Electrolyte Reviews-1; MacCallum, JR; Vincent, CA; Eds. Elsevier Applied Science: New York, 1987; Vol.
- oligo(oxyethylene)-based . amorphous polymers with low crystallinity has been achieved by chemical modification such as grafting and copolymerization.
- poly(siloxane)s with pendant oligo(oxyethylene) side chains and poly[bis((methoxyethoxy) ethoxy)phosphazene] complexed with lithium salts exhibit high ionic conductivity.
- a major drawback of such amorphous polymer/salt complexes is the lack of dimensional stability. This problem was addressed by synthesizing block copolymers where the low T g ionic conductive block is reinforced by a high T g non-conducting block. While these new polymer electrolytes are promising materials, the fact that their preparation requires nontrivial synthetic processes presents a drawback.
- Amorphous linear polymers are inconvenient because they tend to flow at elevated temperatures, which is serious drawback with potential commercial applications where long term dimensional stability is required.
- Cheradame et. al. provided the solution to this problem by the synthesis of network polymers consisting of crosslinked poly(ether glycols) (see Killis et al., J. Polym. Sci., Polym. Phys. Ed. 1981 , 19, 1073; Levesque et al., Makromol. Chem. Rapid Commun. 1983, 4, 497; Killis et al., Solid State Ionics 1984, 14, 231 ). Polymer electrolytes with superior mechanical stability without sacrificing high ionic conductivity could possibly be achieved by controlling the degree of crosslinking of these network systems.
- Gray pointed out that it is important to control the cross-linking in polymer electrolytes with network structures: at low level of cross-links the network is not stable and at high level of cross-links the material is very rigid, which adversely affects the ion mobility.
- the formation of polymer networks is suggested to be the most effective strategy to achieve low degree of crystallinity as well as good dimensional stability. If the degree of crosslinking is kept low or if flexible crosslinks are employed, segmental chain motion is not significantly impaired and salt complexes of these network polymers have conductivities that are superior to those of the crystalline linear polymers.
- IPNs interpenetrating polymer networks
- IPNs as polymer matrix for electrolytes.
- the gelation and phase separation can be controlled at will, it is especially convenient to achieve homogeneous dispersion of nano- and micro-structured fillers/components to yield polymer- nanocomposites.
- a semi- IPN prepared from an insulating derivative of a natural polymer, cellulose acetobutyrate (CAB), an a conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) showed promise for application as polymeric actuators (see Randriamahazaska et al., Synthetic Metals 2002, 128 , 197).
- Feasibility of a similar conducting semi-IPNs based on a poly(ethylene oxide) network and poly(3,4-ethylenedioxythiophene) in actuator design was demonstrated by Vidal et al.( see Vidal et al., Journal of Applied Polymer Science, 2003, 90, 3569).
- IPN interpenetrating polymer network
- PEO-PU/PVP polyethylene oxide-polyurethane/poly (4- vinylpyridine)
- PEO-PU/PAN polyethylene oxide-polyurethane/poly (acrylonitrile)
- IPNs formed by combining poly(ethylene oxide)/polybutadiene (PEO/PB) prepared by free radical copolymerization of poly(ethylene glycol) dimethacrylate andmethacrylate, and polyaddition of hydroxy functionalized polybutadiene doped with Lithium perchlorate (see Gauthier et al., Polymer 2007, 48, 7476).
- PEO/PB poly(ethylene oxide)/polybutadiene
- a new solid polymer electrolyte based on semi-IPNs of crosslinked poly(glycidyl methacrylate-co-acrylonitrile)/poly(ethylene oxide) (P(GMA-co-AN)/PEO) was synthesized with diethylenetriamine (DETA) as the crosslinking agent and characterized (see Luo et al., J. Appl. Polym. Sci., 2008, 708, 2095).
- DETA diethylenetriamine
- a new monomer and Poly(PEG200 maleate) was synthesized as a crosslinkable prepolymer and the semi-IPN gel electrolytes were prepared by means of thermal polymerization (see Li et al., J. Appl. Polym. Sci., 2008, 708, 39). Choi et al.
- a semi-IPN polymer alloy electrolyte composed of non-cross-linkable siloxane-based polymer and crosslinked 3D network polymer, was prepared by Noda et al. (see Noda et al., Electrochimica Acta , 2004, 50, 243).
- Such polymer alloy electrolyte showed quite high ionic conductivity with EC/PC plasticization (more than 0 "4 S cm “1 at 25 °C and 10 "5 S cm “1 at -10 °C) yet appreciable mechanical strength as a separator film and a wide electrochemical stability window.
- crosslinkable compounds such as PEGDMA helped incorporation and entrapment of poly(siloxane-g-ethylene oxide)s are in the network using semi-IPN approach to improve the flexibility (see Oh et al., Electrochimica Acta , 2003, 48, 2215).
- a comblike poly(siloxane-g-allyl cyanide) as a base material for an IPN type polymer electrolyte was also reported with electrolyte ionic conductivity of 1.05x10 "5 Scm "1 at 30 °C, which is appreciably higher than that of unplasticized PEO polymers doped with lithium salts (see Min et al., J. Appl. Polym. Sci. 2008, 707, 1609).
- Hybrid inorganic/organic polymer electrolyte membranes for potential fuel cell applications were prepared by centrifugal casting from solutidhs of sulfonated polyetheretherketone (SPEEK) (DS 64%) and polyethoxysiloxane (PEOS) in dimethylacetamide, following the concept of a semi-interpenetrating network by Colicchio and coworkers (see Colicchio et al., Fuel Cells 06, 2006, 3-4, 225).
- Woo et al. and Chen et al. prepared a proton exchange membrane using polymer blends of polyvinyl alcohol) and poly(styrene sulfonic acid-co-maleic acid) (i.e.
- a porous inert separator material can be impregnated with an organic, long chained, uncured, polymerizable composition and subsequently taken through polymerization and curing stages to obtain a maultilayered gelled polymer system as described in U.S. Pat. No. 5,658,685, 1997; U.S. Pat. No. 5,681 ,357, 1997; U.S. Pat. No. 5,688,293, 1997; U.S. Pat. No. 5,716,421 , 1998; U.S. Pat. No. 5,837,015, 1998; U.S. Pat. No. 5,853,916, 1998, U.S. Pat. No. 5,952, 120, 1999 and U.S. Pat. No. 5,856,039, 1999.
- lid/quasi- solid polymer electrolytes have however remained elusive until very recently. Examples of the few important patents in the recent years, some of them which are licensed to start-ups or filed by corporate giants are U.S. Pat. No. 0263725 Al , 2009; U.S. Pat. No. 0075176 A1 , 2009; U.S. Pat. No. 0239918 A1 , 2010; U.S. Pat. No. 0269674 A1 , 2009; U.S. Pat. No. 0075232 A1 , 2010; U.S. Pat. No. 0255369 A1 , 2010; U.S. Pat. No.
- the main objective of the present- invention is to create high-ionic conductivity electrolyte compositions.
- Another objective of the present invention is to create high-ionic conductivity electrolyte compositions with semi-interpenetrating polymer networks (semi-IPN) and their nanocomposites as quasi-solid / solid electrolyte matrices suitable for use in next generation electrochemical devices.
- Yet another objective of the present invention relates to electrolyte compositions comprised of polyether polymers, semi-interpenetrating polymer networks, surface-functionalized nanoparticles, salts / redox couples with enhanced ionic conductivity, low crystallinity, thermal stability, non-volatility to yield homogeneous semi-IPNs and their nanocomposites as electrolytes, and methods of making them.
- the present invention provides a high-ionic conductivity electrolyte composition
- a high-ionic conductivity electrolyte composition comprising: a polymer network with polyether backbone,
- the polymer networks forming component-l is selected from the group consisting of di- or multi-end functionalized hydroxyl, amine or carboxyl groups terminated polyether backbone, methylenediphenylene diisocyanate (MDI), polymeric methylenediphenylene diisocyanate (p-MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), dicyclohexanemethylene diisocyanate (H 12 MDI), isophoronediisocyanate (IPDI), xylene diisocyanate, hydrogenated xylene diisocyanate, Desmodur-N, glycerol, erythritol, pentaerythritol, xylitol, sorbitol, catechol, ascorbic acid, catechol, dopamine, alizarin, gallic acid, dihydroxy benzoic acid, maltitol, trigly
- the polyether backbone is selected from the group consisting of di-hydroxyl, di-amine or di-carboxyl terminated compound of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG).
- PEG polyethylene glycol
- PPG polypropylene glycol
- PTMG polytetramethylene glycol
- the polyether backbone used as the building block have purity in the range of 80-90%.
- the polyether backbone used has an average molecular weight in the range of 4,000 - 10,000 Daltons.
- the . second and/or third component of the semi-IPN matrix is selected from the group consisting of polyethylene glycol dimethylether, polypropylene glycol dimethylether, polytetramethylene glycol dimethylether, polyethelene glycol diacrylate, polyethelene glycol dimethacrylate, polystyrene, polymethylmethacrylate, polyvinylpyridine, polyvinylcyclohexane, polyamide, polyimide, polyethylene, polypropylene, polyolefins, polyacrylonitrile, polybutadine, polypyrrole, polysiloxanes, polyvinylidene fluoride, poly(t-butylvinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), Poly(t-butyl vinyl eher), polyphosphazene, copolymers containing ethylene oxide, styrene, methyacrylate, vinylpyridine, polyvinylcyclo
- the electrolyte salts is selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium bistrifluorosulfonimide (LiN(CF 3 S0 2 ) 2 ), lithium trifluorosulfonate (LiCF 3 S0 3 ), lithium perchlorate (LiCI0 4 ), lithium iodide (Lil), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF 4 ), Li(CF 3 S0 2 ) 3 C, LiN(S0 2 CF2CF 3 ) 2 , LiB(C 2 0 4 ) 2 , sodium perchlorate (NaCI0 4 ), sodium iodide (Nal), sodium thiocyanate (NaSCN), sodium tetrafluoroborate (NaBF 4 ), potassium perchlorate (KCI0 4 ), .
- LiPF 6 lithium hexafluorophosphate
- potassium iodide Kl
- potassium thiocyanate Kl
- the redox pair is selected from the group consisting of l 3 7l " , Br Br 2 , SCN7(SCN) 2 , SeCN7(SeCN) 2 or Co(ll)/Co(lll).
- the nanostructured materials is selected from the group consisting of titanium dioxide (Ti0 2 ), zinc oxide (ZnO), silicon dioxide (Si0 2 ), tin oxide (SnO, Sn0 2 ), aluminium oxide (Al 2 0 3 ), zirconium oxide (Zr0 2 ), iron oxide (FeO, Fe 2 0 3 , Fe 3 0 , FeOOH), cerium oxide (Ce0 2 ), vanadium oxide (V 2 0 5 ), manganese oxide
- Mn0 2 magnesium oxide
- MgO magnesium oxide
- NiO nickel oxide
- Nb 2 0 5 chromium oxide
- Pr 2 0 3 lead oxide
- PbO lead oxide
- CaO calcium oxide
- CaP0 4 calcium phosphate
- CdS cadmium sulfide
- blends or core-shell morphologies of metal oxides such as Si0 2 /Al 2 0 3 ,
- Ceramic metal oxides such as anatase-Ti0 2 , rutile-Ti0 2 , brookite-Ti0 2 , alpha-AI 2 0 3 , beta- Al 2 0 3 , gamma-AI 2 0 3 and mixed metal oxides such as ferrites, titanates, zirconates, zeolites, layered double hydroxides, fumed silica, organosilicates, clay, fly-ash.
- ceramic metal oxides such as anatase-Ti0 2 , rutile-Ti0 2 , brookite-Ti0 2 , alpha-AI 2 0 3 , beta- Al 2 0 3 , gamma-AI 2 0 3 and mixed metal oxides such as ferrites, titanates, zirconates, zeolites, layered double hydroxides, fumed silica, organosilicates, clay, fly-ash.
- Figure - 1 is a simplified schematic illustration of the 3D-crosslinked polymer networks that forms the component-l of the present invention.
- Figure - 2 is a simplified schematic illustration of the 3D-crosslinked polymer networks that constitutes the component-l interpenetrated in juxtaposition with a linear or branched oligomer / polymer that forms component-ll and/or component-Ill to yield a matrix of bi- or tri- component semi-interpenetrating polymer networks discussed in the embodiments of the present invention.
- Figure - 3 is a simplified schematic representation of the 3D-matrix of bi- or tri- component semi- interpenetrating polymer networks as illustrated in Figure-2 with interspersed nanostructured materials to obtain the nanocomposites discussed in the embodiments of the present invention.
- Figure - 4 is a simplified schematic view of another embodiment of the present invention depicting the 3D-matrix of bi- or tri- component semi-interpenetrating polymer networks as illustrated in Figure-2 with interspersed surface functionalized nanostructured materials to obtain the desired nanocomposites.
- the present invention relates to the application of binary or ternary component semi- interpenetrating polymer networks and their nanocomposites to create a homogeneous polymer / polymer-nanocomposite matrix that serves as a non-volatile quasi-solid/solid electrolyte with enhanced ionic conductivity, low crystallinity, thermal stability, and film forming capability.
- the binary- or ternary- component semi-interpenetrating polymer networks electrolyte composition comprises of: a) a polymer networks with polyether backbone (Component-I); b) a low molecular weight linear, branched, hyper branched polymer or any binary combination of such polymers with preferably non-reactive end groups, Component-ll and/or component-Ill (for formation of ternary semi-IPN system); c) an electrolyte salt and/or a redox pair; and d) optionally, a bare or surface modified nanostructured material to form a nanocomposite matrix.
- -Polyethylene glycol MW > 1000
- the present invention utilizes select chemistry to modify the polymeric architectures, forming nanocomposites, tailor morphology, reduce crystallinity, thermal and dimensional stability, enhance film forming capability, reduce/limit the use of plasticizers prone to leakage and evaporation, and promote the ionic charge transport capability of polyether systems to address the gaps and bottlenecks.
- -Polyether backbone applied in the present invention should have a purity of more than 90%, and an average molecular weight in the range of 200 - 35,000 Daltons, preferably in the range of 400 - 15,000 Daltons, and more preferably in the range of 4,000 - 10,000 Daltons.
- the oligomers, macromonomers or polymers in the networks of component-l can be selected from end functionalized di- or multi-(hydroxyl, amine or carboxyl groups) terminated polyether backbone
- the hydroxyl, amine or carboxyl containing organic compound mentioned above can contain one or more hydroxyl, amine or carboxyl groups or can be a mixture of the compounds with different amounts of hydroxyl, amine or carboxyl groups.
- the hydroxyl, amine or carboxyl terminated compound can be selected but is not limited to from the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), their block copolymers or branched/graft copolymers or combinations thereof.
- the cross linker in the networks of component-l can be selected from the range of organic molecules that contains multi-(hydroxyl, amine, carboxyl groups or any combination thereof).
- the cross linker can be selected from but is not limited to from a group of organic molecules containing polyols, polyacids, polyamines or combination of one or more functional groups such glycerol, erythritol, pentaerythritol, xylitol, sorbitol, catechol, ascorbic acid, catechol, dopamine, alizarin, gallic acid, dihydroxy benzoic acid, maltitol, triglycerides such as castor oil, etc. combinations of these and so on.
- glycerol erythritol, pentaerythritol, xylitol
- sorbitol catechol, ascorbic acid, catechol, dopamine, alizarin, gallic acid, dihydroxy benzoic acid, maltitol, triglycerides such as castor oil, etc. combinations of these and so on.
- polyether-urethane linkages, polyether- urea linkages or polyether-carboxyl linkages of the semi-IPN network in the present invention can be obtained by any methods known to the persons having ordinary skill in the art, for example, by polymerizing a hydroxyl, amine or carboxyl containing compound with an isocyanate containing compound.
- the mole ratio of the hydroxyl, amine and/or carboxyl containing compounds to that of the isocyanate containing compound is 1.0 : 0.6 to 1.0 : 5.0, preferably 1.0 : 1.0 to 1.0 : 3.0, and more preferably 1.0 : 1.1 to 1.0 : 2.5
- the isocyanate containing compound can contain two or more isocyanate groups or a mixture of compounds with different amounts of isocyanate groups.
- the isocyanate containing compound can be selected but is not limited to from the group consisting of methylenediphenylene diisocyanate (MDI), polymeric methylenediphenylene diisocyanate (p-MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), dicyclohexanemethylene diisocyanate (H 12 MDI), isophoronediisocyanate (IPDI), xylene diisocyanate, hydrogenated xylene diisocyanate, Desmodur-N, and so on.
- MDI methylenediphenylene diisocyanate
- p-MDI polymeric methylenediphenylene diisocyanate
- TDI toluene diisocyanate
- HMDI hexamethylene diisocyanate
- H 12 MDI dicyclohexanemethylene diisocyanate
- IPDI isophoronediisocyanate
- FIG. 1 is a simplified schematic illustration of an exemplary 3D-crosslinked polymer networks 100 that consists of an arrangement showing a first monomeric unit 110, a second monomeric unit 120 and a third monomeric unit 130 covalently bonded together to form the component-l of the present invention.
- the first monomer 110 represents the multi-functional groups (hydroxyl-, amine- or carboxyl-terminated) carrying organic moieties used as the crosslinker, the typical functionality depicted in the present illustration being 3.
- 120 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-l and 130 illustrates the di- isocyanate containing compound that covalently links the crosslinker 110 to the polyether backbone 120.
- the arrangements shown is merely representative and alternate arrangements, random repeats of the building blocks and combinations to achieve the polymer networks of component-l 100 are possible.
- the electrolyte composition of the present invention have a linear, branched or hyperbranched component or any combination thereof entangled within the polymer network (Component-l) to create a binary or ternary semi-interpenetrating polymer (semi-IPNs) matrix.
- Figure - 2 is a simplified schematic illustration of the 3D-crosslinked polymer networks that constitutes the component-l interpenetrated in juxtaposition with a linear or branched oligomer / polymer that forms component-ll and/or component-Ill to yield a matrix of bi- or tri- component semi-interpenetrating polymer networks 200 discussed in the embodiments of the present invention.
- the bi- or tri- component semi-interpenetrating polymer networks 200 consists of a first monomeric unit 210, a second monomeric unit 220 and a third monomeric unit 230 covalently bonded together to form the component-l of the present invention.
- the first monomer 210 represents the multi-functional groups (hydroxyl-, amine- or carboxyl-terminated) carrying organic moieties used as the crosslinker, the typical functionality depicted in the present illustration being 3.
- 220 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-l and 230 illustrates the di- isocyanate containing compound that covalently links the cross linker 210 to the polyether backbone 220.
- a second linear or branched oligomer / polymer or a combination of two linear oligomers/polymers or one linear and one branched oligomer/polymer or two branched oligomer/polymers 240 (Component-ll and/or Component-Ill) interpenetrate in juxtaposition of the host polymer networks (Component-l) to yield a matrix of bi- or tri- component semi-interpenetrating polymer networks 200.
- the second and/or third component of semi-IPN matrix in the present invention is a oligomeric or low molecular weight linear, branched or hyper branched polymer with preferably non-reactive end groups (Component-ll and/or Component-Ill).
- the oligomeric or low molecular weight linear, branched or hyper branched polymer of the present invention can be selected from a group but is not limited to, such as polyethylene glycol dimethylether, polypropylene glycol dimethylether, polytetramethylene glycol dimethylether, polyethelene glycol diacrylate, polyethelene glycol dimethacrylate, polystyrene, polymethylmethacrylate, polyvinylpyridine, polyvinylcyclohexane, polyamide, polyimide, polyethylene, polypropylene, polyolefins, polyacrylonitrile, polybutadine, polypyrrole, polysiloxanes, polyvinylidene fluoride, poly(t-butylvinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), Poly(t-butyl vinyl eher), polyphosphazene, copolymers containing ethylene oxide, styren
- the oligomer or low molecular weight polymer should also preferentially possess low glass transition temperature, significant chemical and electrochemical stability; possibly also have the salt-solvation capability and considerable miscibility with the parent polymer network (Component-I) matrix.
- the purity of the oligomer or low molecular weight linear branched or hyper branched polymer should be preferably more than 90%, and an average molecular weight in the range of 200 - 5,000 Daltons, preferably in the range of 200 - 2,000 Daltons, and more preferably in the range of 4,00 - 1 ,000 Daltons.
- Preference for the polymeric Component-I I used to form the semi-IPN is polyethylene glycol dimethylether (PEGDME).
- electrolyte salt that can be used in the semi-IPN electrolyte matrix. Any electrolyte salt that includes the ion identified as the desirable charge carrier for the applications envisaged can be used. As a thumb rule, it is especially convenient to choose electrolyte salts that have a higher dissociation constant, low lattice energy, and ease of solvation with the semi-IPN matrix. Suitable examples of electrolyte salts that can be selected from the group but are not , limited to includes alkali metal salts, such as, Li, Na, K cations with preferential larger anions.
- lithium salts include, but are not limited to, lithium hexafluorophosphate (LiPF 6 ), lithium bistrifluorosulfonimide (LiN(CF 3 S0 2 ) 2 ), lithium trifluorosulfonate (LiCF 3 S0 3 ), lithium perchlorate (LiCI0 4 ), lithium iodide (Lil), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBFneig), Li(CF 3 S0 2 ) 3 C, LiN(S0 2 CF 2 CF 3 ) 2 , LiB(C 2 0 4 ) 2 , and mixtures thereof.
- LiPF 6 lithium hexafluorophosphate
- LiN(CF 3 S0 2 ) 2 lithium bistrifluorosulfonimide
- LiCF 3 S0 3 S0 3 lithium perchlorate
- LiCI0 4 lithium iodide
- LiSCN lithium thiocyanate
- LiBFneig lithium
- useful sodium salts include, but are not limited to, sodium perchlorate (NaCI0 4 ), sodium iodide (Nal), sodium thiocyanate (NaSCN), sodium tetrafluoroborate (NaBF 4 ), and so on.
- useful potassium salts include, but are not limited to, potassium perchlorate (KCI0 4 ), potassium iodide (Kl), potassium thiocyanate (KSCN), and so on.
- Electrolyte salts are not limited to alkali metal cation and can also include other cations with multiple valancy if desired, such as, transition metal cations of Mg, Cu, Co, Ni, Fe, rare earth metal salts of lanthanide and actinide series, such as Eu, Ru, Gd, La, and so on.
- transition metal cations of Mg, Cu, Co, Ni, Fe
- rare earth metal salts of lanthanide and actinide series such as Eu, Ru, Gd, La, and so on.
- HOMO highest occupied molecular orbital
- the redox pair can be but is not limited to ⁇ 3 7 ⁇ , Br Br 2 , SCN7(SCN) 2 , SeCN7(SeCN) 2 or Co(ll)/Co(lll).
- ⁇ 3 7 ⁇ is preferred as a redox pair because the diffusion rate of iodine ion is higher.
- the electrolyte composition optionally includes nanostructures dispersed homogeneously within the semi-IPN polymer matrix. By adding a nanomaterial, the crystallinity of the polyethylene oxide can be significantly disturbed and thereby the non-crystalline regions can be increased to form an ion channel, thus increasing the conductivity the solid electrolyte.
- the hardness of the nanoparticles is helpful in increasing the mechanical strength and modulus of the solid electrolyte.
- the nanostructured materials can be selected from the group but not limited to, consisting of titanium dioxide (Ti0 2 ), zinc oxide (ZnO), silicon dioxide (Si0 2 ), tin oxide (SnO, Sn0 2 ), aluminium oxide (Al 2 0 3 ), zirconium oxide (Zr0 2 ), iron oxide (FeO, Fe 2 0 3 , Fe 3 0 4 , FeOOH), cerium oxide (Ce0 2 ), vanadium oxide (V 2 0 5 ), manganese oxide (Mn0 2 ), magnesium oxide (MgO), nickel oxide (NiO), niobium oxide (Nb 2 0 5 ), chromium oxide (Cr 2 0 3 ), lead oxide (PbO), calcium oxide (Ca
- titanium dioxide, zinc oxide or their mixtures are selected. More preferably, titanium dioxide is selected.
- the nanoparticles used in the present invention has been obtained by synthetic routes known to the persons having ordinary skill in the art, for example, by hydrolysis, sol-gel, hydrbthermal, solvothermal, co-precipitation, thermolysis, sonochemical, etc.
- the nanoparticles can be used in an amount of 0.01 parts by weight to 10 parts by weight, and preferably 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the total amount of (a) polyethylene oxide and (b) polyethylene oxide based network polymer of the electrolyte composition.
- the size of the nanoparticles is about 1 to 50 nm, more preferably in the range of 1-30 nm.
- Figure - 3 is a simplified schematic representation of the 3D-matrix of bi- or tri- component semi-interpenetrating polymer networks as illustrated in Figure-2 with interspersed nanostructured materials to obtain the polymer-nanocomposites 300 discussed in the embodiments of the present invention.
- the bi- or tri- component semi-interpenetrating polymer networks- nanocomposites 300 consists of a first monomeric unit 310, a second monomeric unit 320 and a third monomeric unit 330 covalently bonded together to form the component-l of the present invention.
- the first monomer 310 represents the multi-functional groups (hydroxy!-, amine- or carboxyl-terminated) carrying organic moieties used as the cross linker, the typical functionality depicted in the present illustration being 3.
- 320 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-l and 330 illustrates the di- isocyanate containing compound that covalently links the cross linker 310 to the polyether backbone 320.
- a second linear or branched oligomer / polymer or a combination of two linear oligomers/polymers or one linear and one branched oligomer/polymer or two branched oligomer/polymers 340 (Component-ll and/or Component-Ill) interpenetrated in juxtaposition of the host polymer networks (Component-I) and an intimate dispersion of nanostructured material of choice 350 yields a matrix of bi- or tri- component semi-interpenetrating polymer networks-nanocomposite 300.
- Figure - 4 is a simplified schematic view of another embodiment of the present invention depicting the 3D-matrix of bi- or tri- component semi-interpenetrating polymer networks as illustrated in Figure-2 with interspersed surface functionalized nanostructured materials to obtain the desired nanocomposites 400.
- the bi- or tri- component semi- interpenetrating polymer networks-nanocomposites 400 consists of a first monomeric unit 410, a second monomeric unit 420 and a third monomeric unit 430 covalently bonded together to form the component-l of the present invention.
- the first monomer 410 represents the multi-functional groups (hydroxyl-, amine- or carboxyl-terminated) carrying organic moieties used as the crosslinker, the typical functionality depicted in the present illustration being 3.
- 420 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-I and 430 illustrates the di- isocyanate containing compound that covalently links the crosslinker 410 to the polyether backbone 420.
- a second linear or branched oligomer / polymer or a combination of two linear oligomers / polymers or one linear and one branched oligomer / polymer or two branched oligomer/polymers 440 (Component-ll and/or Component-Ill) interpenetrated in juxtaposition of the host polymer networks (Component-I) and an intimate dispersion of nanostructured material of choice 450 suitably surface functionalized with small organic molecules 460 yields a matrix of bi- or tri- component semi-interpenetrating polymer networks-nanocomposite 400.
- the electrolyte composition of the present invention can optionally have an additive known in the art, such as an additive used for modifying the properties of the nanoparticles and/or improving the efficiency of the hybrid solar- cells.
- the additive when used either individually or in combinations, competitively adsorb on the semiconductor material of the photo-anode, such as titanium dioxide, leading to considerable improvement in of the charge (electron) transfer mechanism of the photo-anode, help in increasing the short-circuit current (J S c) and improving the open circuit voltage (V 0 c) of the cells.
- the additive can be selected from the group consisting of 4-tert-butylepyridine (TBP), N-methyl-benzimidazole (MBI), 1 ,2-dimethyl-3-propyimidazolium iodide (DMPII), lithium iodide (Lil), and sodium iodide (Nal).
- additives can be used in the semi-IPN and their nanocomposites as electrolytes described herein.
- additives that help with overcharge protection, provide stable SEI (solid electrolyte interface) layers, and/or improve electrochemical stability can be used.
- Such additives are well known to people with ordinary skill in the art.
- Additives that make polymers easier to process, such as plasticizers can also be used.
- Certain additives that can enhance the bulk conductivity levels, such as, low molecular weight conductive polymers, high dielectric constant platicizers, and room temperature ionic liquids, can also be optionally used if so desired.
- Additives that functions as anion receptors such as calixarenes, crown ethers, salen-type complexes can be optionally used to preferentially enhance cationic transport in the matrix.
- the process of preparing an electrolyte composition of the invention includes, for example, forming the isocyanate terminated pre-polymer by reacting the preferred molecular weight di- or multi-(hydroxyl, amine or carboxyl groups) terminated organic moiety with di- or multi-isocyanate compound as described above; mixing both the isocyanate terminated pre-polymer, a di- or multi- (hydroxyl, amine or carboxyl groups) terminated polyether and catalyst to initiate the formation of polymer networks (Component-I), incorporation of component-ll and/or component-Ill (for formation of binary or ternary semi-IPN system), i.e.
- Component-I polymer networks
- oligomeric / or low molecular weight linear, branched or hyperbranched polymer with preferably non-reactive end groups to intimately entangle within the growing polymer network, addition of desired electrolyte salt and/or redox couple system in required concentration of the electrolyte composition, optionally adding the nanostructured materials, mixing the additives, under continuous stirring (for 48 hrs at room temperature) in inert atmosphere, till a uniformly homogeneous viscous mix of an electrolyte composition is obtained.
- the viscous polymer / polymer-nanocomposite electrolyte compositions are thereafter casted onto a teflon petri-dish or directly deposited onto the desired substrate by spin coating, screen-printing or using doctor-blade technique, dried at room temperature followed by curing at higher temperature and inert atmosphere to ensure the completion of isocyanate reaction (at 80 °C for 48 hrs) thereby forming quasi-solid or solid semi-IPN / nanocomposite semi- IPN electrolyte paste or films prior to characterizations and use in battery, solar-cells, or similar device applications.
- the process of forming the quasi- solid/solid semi-IPN or nanocomposite semi-IPN electrolyte pastes or films of the desired electrolyte composition of the invention includes the following steps:
- the solvent of step (a) of the above process is not limited, and can be selected from the group consisting of tetrahydrofuran (THF), acetonitrile (CH 3 CN), chloroform (CHCI 3 ), dichioromethane (DCM), ethyl acetate (EtOAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diglyme, N-methyl pyrrolidone (NMP), mixtures thereof and so on.
- THF tetrahydrofuran
- CH 3 CN acetonitrile
- CHCI 3 chloroform
- DCM dichioromethane
- EtOAc ethyl acetate
- DMF dichioromethane
- EtOAc ethyl acetate
- DMF dichioromethane
- DME ethyl acetate
- DMF dichioromethane
- EtOAc ethyl acetate
- DMF dimethyl
- the solvent of step (c) of the above process is not limited, and can be selected from the group consisting of tetrahydrofuran (THF), acetonitrile (CH 3 CN), chloroform (CHCI 3 ), dichioromethane (DCM), ethyl acetate (EtOAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diglyme, N- methyl pyrrolidone (NMP) and so on.
- THF tetrahydrofuran
- CH 3 CN acetonitrile
- CHCI 3 chloroform
- DCM dichioromethane
- EtOAc ethyl acetate
- DMF dichioromethane
- EtOAc ethyl acetate
- the catalyst of step (c) of the above process is not limited, and can be selected from the group consisting of tertiary amines dimethyl aniline (DMA), diethyl aniline (DEA) and so on. Preference is DMA.
- DMA dimethyl aniline
- DEA diethyl aniline
- Preference is DMA.
- component-ll and/or component-Ill for formation of binary- or ternary- semi-IPN system
- oligomeric or low molecular weight linear, branched or hyperbranched polymer with preferably non-reactive end groups pre-dissolved in a solvent separately and in required weight percent of the total polymer content of the final product was charged into the reaction flask to intimately entangle within the growing polymer network and form the desired mix of semi-IPN matrix.
- the solvent of step (f) of the above process is not limited, and can be selected from the group consisting of tetrahydrofuran (THF), acetonitrile (CH 3 CN), chloroform (CHCI 3 ), dichloromethane (DCM), ethyl acetate (EtOAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diglyme, N- methyl pyrrolidone (NMP) and so on.
- THF tetrahydrofuran
- CH 3 CN acetonitrile
- DCM dichloromethane
- EtOAc ethyl acetate
- DMF dichloromethane
- EtOAc ethyl acetate
- DMF dimethylformamide
- DMSO dimethyl sulfoxide
- NMP N- methyl pyrrolidone
- Preference is THF, CH 3 CN or a 1 : 1 solvent mixture of THF/CH 3 CN,
- step (j) The mixing of nanostructured materials and other additives of choice in required amounts are optional and can be done along with step (f) to incorporate them in the final product i.e. the formation of nanocomposite semi-IPN electrolyte matrix.
- the viscous semi-IPN / nanocomposite semi-IPN electrolyte compositions are subsequently casted onto a teflon petri-dish or directly deposited onto the desired substrate by spin coating, screen-printing or using doctor-blade technique.
- the semi-IPN / nanocomposite semi-IPN electrolyte compositions were dried at room temperature followed by curing at higher temperature (at 60 -100 °C for 48-96 hrs) and inert atmosphere to ensure trapped solvent evaporation, the completion of isocyanate reaction thereby forming quasi-solid/solid semi-IPN / nanocomposite semi-IPN electrolyte paste or films.
- the curing temperature is preferably 80 °C and the curing time 48 hrs.
- the images reveal fairly homogeneous bulk and minimal phase separation except at the substrate interface, probably due to slightly preferential stratification of the polymer network component during the cure process.
- the SEM images 5(d) and 6(d), at magnification, X 3.
- both the compositions of the semi-IPN electrolytes reveal significant porosity in the semi-IPN films indicating possibility of co-continuous channels present throughout the matrices. Presence of high porosity or free volume while retaining the structural integrity of the polymer matrix can considerably impact the ion-transport in such systems leading to enhancement of ionic conductivity.
- Both the semi-IPN nanocomposite samples reveal good homogeneity in the bulk and almost no agglomeration of the dispersed nanomaterials, indicating reasonable nanoparticle-polymer interaction at the interfaces.
- the alternating current electrochemical impedance measurements were carried out on a Zahner® Zennium electrochemical workstation controlled by Thales Operational Software.
- the system was interfaced with a thermostated oven equipped with parallel test channels independently connected to spring loaded Swagelok cells to test the samples at identical conditions.
- the synthesized semi-IPN electrolyte samples were vacuum dried overnight before carrying out the electrical measurements. Punched circular disc shaped polymer films (thickness ⁇ 0.6mm) of surface area 0.8cm 2 were sandwiched between two 316 stainless steel blocking electrodes with a Teflon spacer of appropriate dimension and loaded in the Swagelok assembly.
- the spring and Teflon spacer ensured the application of same amount of spring pressure during the sample mounting and throughout the test.
- the sample holders were placed in the controlled heating chamber to carry out the variable temperature impedance measurements over a range of ⁇ 20°C to 90°C at an interval of ⁇ 5-7°C during heating.
- the temperature was measured with accuracy better than ⁇ 0.1 °C using a K-type thermocouple placed in close proximity with the sample.
- the samples were equilibrated at each temperature for 30 minutes prior to acquiring the frequency sweep impedance data. No corrections for thermal expansion of the cells were carried out.
- the real part of the impedance was appropriately normalized for the cell dimensions and ionic conductivity ( ⁇ (Scm " )) was determined. All the data point plotted represents an average of at least three different sets of measurements under similar conditions with appropriate standard deviation provided as Y-Error.
- the plot shows varying weight ratio in the intermediate range of Component-I (polyether networks) : Component-ll (polyethylene glycol dimethylether); 60:40; 50:50; 40;60 and 30:70 in the synthesized Semi-IPN polymer matrix, with the best relative conductivity observed for the 30:70 composition. Though the conductivity showed steady increase, structural integrity of the semi-IPN matrix was heavily compromised beyond 70wt% of the component-ll.
- Differential scanning calorimetry was performed on a DSC Q200 differential scanning calorimeter (TA Instruments) under dry nitrogen atmosphere.
- the synthesized semi-IPN electrolyte samples were vacuum dried overnight before carrying out the thermal studies.
- a sample (5- 10mg) of the semi-IPN electrolyte was loaded in an aluminum pan and hermetically sealed, rapidly cooled down to -150°C using liquid nitrogen, equilibrated for 5 minutes and then heated up to 150°C at scan rate of 10°C min.
- the power and temperature scales were calibrated using pure indium.
- the glass transition temperature (T g ) was determined from the inflection-point of the transitions.
- the glass transition temperature is well below the ambient ( ⁇ 40 °C) for all the samples.
- the semi-IPNs also exhibited a suppressed melting over a broader temperature range.
- the effect of cross-linking and networks formation is obvious with a very significant decrease in the degree of crystallinity and lowering of T m .
- the thermal stabilities of the synthesized semi-IPNs were assessed by a TA Q500 modulated thermo gravimetric analyzer. 10 to 20 mg of the samples were carefully weighed in an aluminum pan and TG scans- were recorded at -a rate of 10 °C/min under nitrogen ⁇ atmosphere _ in the temperature range 35 °C to 600°C.
- Figure - 19 is a representative dual Y-axis plot of a thermogravimetry scan and the corresponding differential plot for the synthesized bi-component Semi-IPN Polymer matrix.
- the thermogravimetry studies coupled wit differential analysis of the scans reveal that the degradation onset temperature of all the semi-IPN electrolyte compositions is > 50 °C.
- the first stage usually in the range of 180 - 250 °C corresponds to the scission of the transient crosslinks in the Polymer (M + ...0)
- the second stage in the range of 250 - 375 °C are the further scission of the polymer backbones at the urethane, urea, ether and amide linkages, finally beyond 400 °C the polymer undergoes advanced fragmentation, degradation and charring.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to high-ionic conductivity electrolyte compositions. The invention particularly relates to high-ionic conductivity electrolyte compositions of semi-interpenetrating polymer networks and their nanocomposites as quasi-solid/solid electrolyte matrix for energy generation, storage and delivery devices, in particular for hybrid solar cells, rechargeable batteries, capacitors, electrochemical systems and flexible devices. The binary or ternary component semi-interpenetrating polymer network electrolyte composition comprises: a) a polymer network with polyether backbone (component I); b) a low molecular weight linear, branched, hyper-branched polymer or any binary combination of such polymers with preferably non-reactive end groups (component-ll and/ or component-Ill, for formation of ternary semi-IPN system); c) an electrolyte salt and/or a redox pair, and optionally d) a bare or surface modified nanostructured material to form a nanocomposite.
Description
HIGH-IONIC CONDUCTIVITY ELECTROLYTE COMPOSITIONS COMPRISING SEMI-INTERPENETRATING POLYMER
NETWORKS AND THEIR COMPOSITES
FIELD OF THE INVENTION
The invention relates to high-ionic conductivity electrolyte compositions. The invention particularly relates to high-ionic conductivity electrolyte compositions of semi-interpenetrating polymer networks and their nanocomposites as quasi-solid/solid .electrolyte matrix for energy generation, storage and delivery devices, in particular for hybrid solar cells, rechargeable batteries, capacitors, electrochemical systems and flexible devices.
BACKGROUND OF THE INVENTION
In recent years, interest and demand for all solid devices that can be processed roll-to-roll or as thin films or sheets has increased considerably. Electrolytes remain an integral component of these next generation devices. Current rechargeable Li-ion batteries and third generation DSSCs/Q-DSSCs cell configurations have a liquid or gel electrolyte along with a separator between the anode and cathode. In such systems, apart from all the other parameters related to electrodes, dyes, catalysts, etc., the device performance and life-time is dominated by the functioning and stability of the electrolytes under operational conditions. Most of the present day devices use multiple layers of an inert porous polymeric (polyolefin) separator membrane with defined porosity as described in U.S. Pat. No. 4,650,730, 1987 impregnated with electrolytes dissolved in a wide variety of low molar mass solvents / mixed solvent systems, such as those disclosed in U.S. Pat. No. 5,643,695, 1997 and U.S. Pat. No. 5,456,000, 1995. The occasional problems encountered in such liquid/gel based systems are electrolyte loss or drying of the liquid component, unstable SEI layers, active layer dissolution, associated volume changes during cycling, corrosion, prone to fire and decreased performance over time. The highly reactive nature of such electrolytes also necessitates the use of protective enclosures with design limitations that add to the size and bulk of the battery or similar devices. A long-standing goal in polymer electrolyte research is the preparation of an ideal electrolyte that combines the processing characteristics of conventional thermoplastics and the ionic conductivity of low molar mass liquids. PEs contrast sharply compared to the usual electrolyte materials with respect to the mode of charge transport and the value of ionic conductivity; however, for electrochemical applications the flexibility offered by the polymer electrolyte is important. Unlike their conventional glass or ceramics counterparts, lightweight, shape-conforming, compliant, polymer electrolyte-based systems could find widespread application as energy generation and storage/delivery devices.
The use of polymeric matrix as an electrolyte medium was first conceived in 1973 with the complex forming capability of poly(ethylene oxide) (PEO) and alkali metal salts, (see Fenton et al., Polymer 1973, 14, 589; Wright PV, Br. Polym. J. 1975, 7, 319; J. Polym. Sci. polym. Phys. Ed.
1976, 14, 955.) the proof of concept in actual device was demonstrated in 1978 (see Armand et
al., Extended Abstracts, Second International Conference on Solid Electrolytes, St. Andrews, Scotland, 1978.)· Over four decades of research literature on polymer electrolytes and its related usage in a variety of device architectures are available in the public domain in form of several patents, papers, and reports. Ion transport in polymer electrolytes is considered to take place by a combination of ion motion coupled to the local motion of polymer segments and inter- and intrapolymer transitions between ion coordinating sites (see Gray, FM In Solid Polymer Electrolytes-Fundamentals and Technological Applications; VCH, Weinhem, Germany, 1991.). The polymer has to solvate inorganic salts, such as LiX and NaX (X = ClOy or CF3S03~, BF4 ", AsF6 ", SCN", Γ etc.), which will be thermodynamically favorable (AG0 < 0) only if the Gibbs energy of solvation of the salt by the polymer is large enough to overcome the lattice energy of the salt. Thus, to achieve the dissolution of electrolytes in a polymer, there by producing a homogeneous solution some form of interaction between the polymer chains and the electrolyte is necessary. Interaction is most easily obtained when there is an electron donor atom in the polymer chain that can coordinate with the cation of the salt through a Lewis acid-base reaction, thus providing a favorable Gibbs energy of polymer-salt interactions (see Gray, FM In Solid Polymer Electrolytes- Fundamentals and Technological Applications; VCH, Weinhem, Germany, 1991 ; Ratner et al., Chem. Rev. 1988, 88, 109; MacCallum et al., In Polymer Electrolyte Reviews-1; MacCallum, JR; Vincent, CA; Eds. Elsevier Applied Science: New York, 1987; Vol. 1.; Cowie et al., Annu. Rev. Phys. Chem. 1989, 40, 85). Movement of free ions, ion pairs, triple ions or even higher aggregates in the polymer matrix contributes to the overall conductivity of the polymer electrolytes. This type of ionic mobility stipulates that the polymer matrix should be soft and pliable, allowing the polymer segments to undergo fairly large amplitude motions (see Cowie, JMG. In Polymer Electrolyte Reviews-1; MacCallum, JR.; Vincent, CA; Eds. Elsevier Applied Science: New York, 1987; Vol. 1 ). Moreover, several studies have pointed out that the polymer motions relevant to ionic conductivity are not the gross backbone diffusion as in a solution or melt, but segmental plasticity (see Mertens et al., Macromolecules, 1999, 32, 3314; Allcock et al., Macromolecules, 1996, 29, 1951 ; Macromolecules 1998, 31, 8026; Jean-Franois et al., Macromolecules, 1988, 21, 1 1 17 ; Hawker et al., Macromolecules 1996, 29, 3831 ; Druger et al., J. Chem. Phys. 1983, 79, 3133; Shi et al., Solid State Ionics 1993, 60, 11 ; Andreev et al., Electrochim. Acta 2000, 45, 1417). Consequently a material with a low glass transition temperature (i.e. well below ambient) is more likely to produce a high conductivity at a specified temperature than a more rigid material (see Armand et al., Fast Ion Transport in Solids: Electrodes & Electrolytes, Proc. Int. Conf. Elsevier/North Holland, Amsterdam, 1979). In addition, for a particular cation-polymer coordination group, the distance between the coordinating groups and the polymers ability to adopt conformations that allow multiple inter- and intra- molecular coordination are important.
Hence an ideal polymer host must satisfy the criteria such as (i) a high concentration of sequential polar groups on the polymer chain with sufficient electron donor power to form coordinate bonds with cations thereby achieving effective salt salvation; (ii) preferably have a low glass transition temperature where in low barriers to bond rotation thermodynamically allows facile segmental reorientation of the polymer chain, and (iii) suitable distance between the coordination sites to allow flexibility to the polymer segment.
Following the direction proposed by Wright and Armand, several polymers such as poly(ethylene oxide) (see Fenton et al. , Polymer 1973, 14, 589; Wright PV, Br. Polym. J. 1975, 7, 319; J. Polym. Sci. Polym. Phys. Ed. 1976, 14, 955; Gauthier et al., D. J. Electrochem. Soc. 1985, 132, 1333; Abraham et al., J. Electrochem. Soc. 1988, 135, 535; Bonino et al., J. Power Sources 1986, 18, 75; Vallee et al., Electrochim. Acta 1992, 37, 1579; Sorensen et al., Electrochim. Acta 1982, 27, 1671 ), polypropylene oxide) (see Watanabe et al., Macromolecules 1985, 18, 1945; Watanabe et al., In Polymer Electrolyte Reviews; Elsiever, London, 1987; Cheradame et al. Mater. Res. Bull. 1980, 15, 1 173), poly (acrylonitrile) (see Abraham et al., J. Electrochem. Soc. 1990, 136, 1657; Perera et al., Electrochim. Acta 2000, 45, 1361 ; Munichandraiah et al. , J. Appl. Polym. Sci. 1997, 65, 2191 ), poly(methylmethacrylate) (see Appetecchi et al., Electrochim. Acta 1995, 40, 991 ; Kim et al., Electrochim. Acta 2001 , 46, 1323; Vondrak et al., Electrochim. Acta 2001 , 46, 2047), poly(phosphazene) (see Blonsky et al., J. Am. Chem. Soc. 1984, 106, 6854; Allcock et al., Macromolecules 1986, 19, 1508; Blonsky et al., Solid State Ionics 1989, 18-19, 258), poly(ethylene imine) (see Davis et al., Solid State Ionics, 1986, 18-19, 321 ; Chiang et al., Solid State Ionics, 1986, 18-19, 300), poly(siloxane) (see Fish et al., Br. Polym. J. 1988, 20, 281 ; Fish et al., Makromol. Chem. Rapid. Commun. 1986, 7, 115; Hall et al, Polym. Commun. 1986, 27, 98), etc. have been identified as suitable hosts for SPEs.
Among the broad spectrum of polymers which satisfy the essential criteria for being a host matrix for SPEs, poly(ethylene oxide) is the most widely studied one. The inorganic salt containing poly(ethylene oxide) is a representative starting system to design solid polymer electrolytes of high ionic conductivity. Poly (ethylene oxide) has attracted special attention owing to its low glass transition temperature (Tg < -60 °C) and its ability to solvate a wide range of salts. In spite of the advantages, PEO has two serious drawbacks: (1 ) its high degree of crystallinity, which renders a very low specific conductivity (σ ~ 10"8Scm"1) at ambient temperature and (2) its poor dimensional stability complicated by a low melting temperature (Tm ~ 50-60°C). The challenge in successfully using PEO as SPEs hence lies in achieving a low degree of crystallinity and good dimensional stability along with the requisite ionic conductivity. Several approaches have been adopted by various researchers to reduce the crystallinity and increase the dimensional stability of poly(ethylene oxide). Structural modifications by forming blends (see Munichandraiah et al., J. Appl. Polym. Sci. 1997, 65, 2191 ; Tsuchida et al., Solid State Ionics 1983, 11, 227; Li et al. , J. Polym. Sci. Polym. Chem. 1995, 33, 1657; Acosta et al., Appl. Polym. Sci. 1996, 60, 1 185),
copolymerization (see Xia et al., Solid State Ionics 1984, 14, 221 ; Banister et al., Polymer 1984, 25, 1600; Kobayashi et al., J. Phys. Chem. 1985, 89, 987; Robitaille et al., Macromolecules 1983, 16, 665 ; Watanabe et al., J. Appl. Phys. 1985, 57, 123), grafting (see Florjanczyk et al., J. Polym. Sci., Part B, Polym. Phys. Ed. 1995, 33, 629; Allcock et al., Macromolecules 1996, 29, 7544) and crosslinking (see Killis et al., J. Polym. Sci., Polym. Phys. Ed. 1981 , 19, 1073; Levesque et al., Makromol. Chem. Rapid Commun. 1983,' 4, 497; Killis et al., Solid State Ionics 1984, 14, 231 ; Zhang et al., J. Appl. Polym. Sci. 2000, 77, 2957; lchikawa et al., Polymer 1992, 33, 4699) have been tried. Blending of poly(ethylene oxide) with suitable polymers is the simplest of the alternatives to improve the dimensional stability and/or mechanical strength. Various polymers such as poly(2-vinylpyridine), poly(acrylonitrile), poly(vinlylacetate), poly(methylmethacrylate), nafion and polyurethanes have been used to prepare blends (see MacCallum et al., In Polymer Electrolyte Reviews-1; MacCallum, JR; Vincent, CA; Eds. Elsevier Applied Science: New York, 1987; Vol. 1 ; Gray, FM In Solid Polymer Electrolytes-Fundamentals and Technological Applications; VCH, Weinhem, Germany, 1991 ). Even though, these systems showed remarkable improvement in their dimensional stability and a reduction in the crystallinity, the considerable phase separation in such systems was undesired.
A number of oligo(oxyethylene)-based . amorphous polymers with low crystallinity has been achieved by chemical modification such as grafting and copolymerization. For example poly(siloxane)s with pendant oligo(oxyethylene) side chains and poly[bis((methoxyethoxy) ethoxy)phosphazene] complexed with lithium salts exhibit high ionic conductivity. However, a major drawback of such amorphous polymer/salt complexes is the lack of dimensional stability. This problem was addressed by synthesizing block copolymers where the low Tg ionic conductive block is reinforced by a high Tg non-conducting block. While these new polymer electrolytes are promising materials, the fact that their preparation requires nontrivial synthetic processes presents a drawback.
Amorphous linear polymers are inconvenient because they tend to flow at elevated temperatures, which is serious drawback with potential commercial applications where long term dimensional stability is required. Cheradame et. al. provided the solution to this problem by the synthesis of network polymers consisting of crosslinked poly(ether glycols) (see Killis et al., J. Polym. Sci., Polym. Phys. Ed. 1981 , 19, 1073; Levesque et al., Makromol. Chem. Rapid Commun. 1983, 4, 497; Killis et al., Solid State Ionics 1984, 14, 231 ). Polymer electrolytes with superior mechanical stability without sacrificing high ionic conductivity could possibly be achieved by controlling the degree of crosslinking of these network systems. Gray, however, pointed out that it is important to control the cross-linking in polymer electrolytes with network structures: at low level of cross-links the network is not stable and at high level of cross-links the material is very rigid, which adversely affects the ion mobility.
Among the various structural modifications, the formation of polymer networks is suggested to be the most effective strategy to achieve low degree of crystallinity as well as good dimensional stability. If the degree of crosslinking is kept low or if flexible crosslinks are employed, segmental chain motion is not significantly impaired and salt complexes of these network polymers have conductivities that are superior to those of the crystalline linear polymers.
In this perspective, interpenetrating polymer networks (IPNs) can be thought to be advantageous in several respects, especially where dimensional, thermal and mechanical stability along with homogeneity and lower degree of crystallinity of the polymer matrix are the pre-requisites.
The idea of using IPNs as polymer matrix for electrolytes is due to some of the exceptional properties expected of these composite materials. First, due to their three-dimensional crosslinked networks and inherent entanglements with each other, IPNs satisfy the primary requisite of dimensional stability. Second, the formation of IPNs reduces the presence of crystalline domains, which enhances the ionic mobility. Third, for most of the IPN compositions, the glass transition temperature is seen to be very broad and the range stretches between that of the two polymers leading to improved properties at the ambient temperatures. Finally, if the gelation and phase separation can be controlled at will, it is especially convenient to achieve homogeneous dispersion of nano- and micro-structured fillers/components to yield polymer- nanocomposites. Although, other multicomponent materials can be made to do the same thing, it seems especially convenient with the IPNs. The ease of preparation of IPNs either simultaneously or sequentially also offers excellent flexibility towards designing such matrices. The recent years have seen the efforts warming up towards exploring IPNs as potential candidates for electrochemical applications.
Frisch et al., reported synthesis of electrically conducting sequential s-IPNs from polycarbonate urethane) (PCU) and cross-linked poly(chloroprene); achieving electrical conductivity of the order of 10"4 Son"1 was exhibited by l2 doped linear PGU chains (see Frisch et al., J. Polym. Sci., Part A: Polym.Chem. , 1992, 30, 937; J. Polym. Sci., Part A: Polym. Chem., 1994, 32, 2395). A semi- IPN prepared from an insulating derivative of a natural polymer, cellulose acetobutyrate (CAB), an a conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) showed promise for application as polymeric actuators (see Randriamahazaska et al., Synthetic Metals 2002, 128 , 197). Feasibility of a similar conducting semi-IPNs based on a poly(ethylene oxide) network and poly(3,4-ethylenedioxythiophene) in actuator design was demonstrated by Vidal et al.( see Vidal et al., Journal of Applied Polymer Science, 2003, 90, 3569).
There have been other attempts to synthesize conducting semi-IPNs following modified techniques. In most of these reports a conducting polymer (polypyrrole (PPy) or polyaniline (PAn)) is synthesized chemically or electrochemically within a crosslinked network of a conventional polymer. A series of such IPNs in which crosslinked networks of SIS rubber (see Gan et al., Polym. Int., 1999, 48, 1 160; Gan et al., Polymer, 1999, 40, 4035), cellulose (see Henry
et al., Chem. Mater., 1999, 11, 1024; Yin et al., Polym. Int., 1997, 42, 276), PMMA (see Yin et al., J. Appl. Polym. Sci., 1997, 65, 1 ) and a few other polymers and copolymers (see Yin et al., J. Appl. Polym. Sci., 1997, 63, 13; Yin et al., J. Appl. Polym. Sci., 1997, 64, 2293) are used as the matrix for chemical or electrochemical polymerization of pyrrole and aniline have so far been reported. Mandal et al. have suggested that chemical oxidative polymerization of pyrrole or aniline within the films of different polymers viz. polyvinyl acetate) (PVAc), SBA etc. results in in situ crosslinking of the matrix (see Mandal et al., Synth. Met., 1996, 80, 83; Chakraborty et al., Synth. Met, 1999, 98, 193). Gangopadhyay et al. reported electrochemical synthesis of a semi- IPNs following electropolymerization of pyrrole from an aqueous medium within a crosslinked network of PVA (see Gangopadhyay et al., J. Mater. Chem., 2002, 72, 3591 ). Conductive electroactive polymers made of chitosan/polyaniline IPNs based hydrogels were reported by Shin ef al. (see Shin et al, Synthetic Metals, 2005, 154, 213) to demonstrate alteration of surrounding electrolyte composition such as pH, by electrochemical simulation.
In another interesting finding, the design of a single layer two-component system through the combination of p- and n- dopable polymers into a semi-interpenetrating polymers network architecture (semi-IPNs) for organic photovoltaic applications was demonstrated by Lav ef a/.(see Lav et al., J Solid State Electrochem.; 2007, 11, 859). A self-supported semi-interpenetrating polymer networks for new design of electrochromic devices was reported by Francois ef a/.(see Francois et al., Electrochimica Acta 2008, 53, 4336) The electro-copolymerization of alternate layer-by-layer (LbL) self-assembled polyelectrolytes with thiophene and carbazole pendant monomers was demonstrated facilitating nanostructured IPN formation of p-conjugated polymers or conjugated polymer network (CPN) films (see Waenkaew et al., Macromol. Chem. Phys. 2011 , 212, 1039). Nevertheless, most of these reports concentrated on the use of electronically conducting polymers, which are by very nature insoluble and infusible and therefore cannot be easily processes in solution or in melt form.
A full interpenetrating polymer network (IPN) of polyethylene oxide-polyurethane/poly (4- vinylpyridine) (PEO-PU/PVP), was synthesized as a host polymer and subsequently doped with UCIO4 to demonstrate the feasibility of using these matrices (see Basak et al., J. Macromol. Sci. - Pure and Appl. Chem. 2001 , A38 (4), 399). Though, the glass transition temperatures were encouragingly low (-50°C to -35°C), the maximum conductivity achieved for this system (~ 5 x 10" 8 Scm'1 at RT without any plasticization) was considerably low owing to the excessive crosslinking as a full-IPN. Another class of polyethylene oxide-polyurethane/poly (acrylonitrile) (PEO-PU/PAN) semi-IPNs and there nanocomposites with significantly improved properties were synthesized and reported (see Basak et al., Solid State Ionics 2004, 167(1-2), 113; Basak et al., Eur. Polym. J. 2004, 40(6), 1 155; Basak et al., J. Phys. Chem. B 2005, 109(3), 1174; Basak et al., J. Macromol. Sci. - Pure and Appl. Chem. 2006, A43 (2), 369; Selim et al., J. Phys. Chem. C 2010, 114, 14281 ; Ramanjaneyulu et al., Journal of Power Sources, 2012, 217, 29).
A Cross-linked methoxyoligo (oxyethylene) methacrylate (Cr-MOEnM)/PMMA interpenetrating polymer network (IPN) electrolyte was synthesized by Hou et al. (see Hou et al., Polymer 2001 , 42, 4181 ) and reported ionic conductivities of about 10"3 Scm"1 at room temperature with 1 :1 EC/PC incorporated as low molecular weight plasticizers. Gauthier ef al. reported on IPNs formed by combining poly(ethylene oxide)/polybutadiene (PEO/PB) prepared by free radical copolymerization of poly(ethylene glycol) dimethacrylate andmethacrylate, and polyaddition of hydroxy functionalized polybutadiene doped with Lithium perchlorate (see Gauthier et al., Polymer 2007, 48, 7476). A new solid polymer electrolyte based on semi-IPNs of crosslinked poly(glycidyl methacrylate-co-acrylonitrile)/poly(ethylene oxide) (P(GMA-co-AN)/PEO) was synthesized with diethylenetriamine (DETA) as the crosslinking agent and characterized (see Luo et al., J. Appl. Polym. Sci., 2008, 708, 2095). A new monomer and Poly(PEG200 maleate) was synthesized as a crosslinkable prepolymer and the semi-IPN gel electrolytes were prepared by means of thermal polymerization (see Li et al., J. Appl. Polym. Sci., 2008, 708, 39). Choi et al. synthesized a semi-IPN based on copolymer of vinylidene fluoride and hexafluoropropylene (PVdF-HFP) and curable crosslinking agent (1 ,6-hexanediol diacrylate) under UV incorporating 150 wt% EC/PC/1 M LiCI04 solution resulting gel polymer electrolyte (see Choi et al., Electrochimica Acta, 2008, 53, 6575). Hourston et a/.116 prepared polyetherurethane/ polyethylmethacrylate IPN by simultaneous polymerization of both poly(propylene glycol) based polyurethane and polyethylmethacrylate from respective monomers to demonstrate their feasibility as electrolytes (see Hourston et al., J. Polym. Adv. Technol. 1996, 7, 1). Shibata and co-workers (see Shibata et al., Eur. Polym. J. 2000, 36, 485) studied polymer electrolytes based on blends of polyurethane and two different types of modified polysiloxane, poly(dimethylsiloxane-co-methylphenylsiloxane)s and polyether-modified polysilxoane, prepared by solution casting.
Similarly, a semi-IPN polymer alloy electrolyte, composed of non-cross-linkable siloxane-based polymer and crosslinked 3D network polymer, was prepared by Noda et al. (see Noda et al., Electrochimica Acta , 2004, 50, 243). Such polymer alloy electrolyte showed quite high ionic conductivity with EC/PC plasticization (more than 0"4 S cm"1 at 25 °C and 10"5 S cm"1 at -10 °C) yet appreciable mechanical strength as a separator film and a wide electrochemical stability window. The crosslinkable compounds such as PEGDMA helped incorporation and entrapment of poly(siloxane-g-ethylene oxide)s are in the network using semi-IPN approach to improve the flexibility (see Oh et al., Electrochimica Acta , 2003, 48, 2215). A comblike poly(siloxane-g-allyl cyanide) as a base material for an IPN type polymer electrolyte was also reported with electrolyte ionic conductivity of 1.05x10"5 Scm"1 at 30 °C, which is appreciably higher than that of unplasticized PEO polymers doped with lithium salts (see Min et al., J. Appl. Polym. Sci. 2008, 707, 1609). An IPN solid polymer electrolyte with 60 wt % of comb-shaped siloxane showed an
ionic conductivity greater than 5x1 CT4 Scm"1 at 37°C, with a wide electrochemical stability window of up to 4.5 V vs. lithium (see Oh et al., Electrochem. Solid State Lett. 2002, 5, E59).
Proton conducting semi-IPNs based on Nafion and crosslinked poly(AMPS) for direct methanol fuel cell was reported by Cho et al. (see Cho et al., Electrochimica Acta 2004, 50, 589). Membranes that can reduce methanol crossover were synthesized by Matsuguchi and co- workers (see Matsuguchi et al., J. Membrane Sci. , 2006, 281, 707) to form semi-IPN membranes composed of Nafion® and cross-linked divinylbenzene (DVB). In these semi-IPNs, the linear Nafion® carries the ionic groups while the cross-linked DVB provides the other desirable properties, including good mechanical strength and low affinity to methanol and water. Cheng ef al. reported microporous PVdF-HFP based gel polymer electrolytes reinforced by PEGDMA network (see Cheng et al. , Electrochemistry Communications 2004, 6, 531). Semi-IPN membranes based on novel sulfonated polyimide (SPI) and poly (ethylene glycol) diacrylate (PEGDA) have been prepared and demonstrated by Lee ef al. for fuel cell applications (see Lee et al., J. Appl. Polym. Sci., 2007, 104, 2965). Hybrid inorganic/organic polymer electrolyte membranes for potential fuel cell applications were prepared by centrifugal casting from solutidhs of sulfonated polyetheretherketone (SPEEK) (DS 64%) and polyethoxysiloxane (PEOS) in dimethylacetamide, following the concept of a semi-interpenetrating network by Colicchio and coworkers (see Colicchio et al., Fuel Cells 06, 2006, 3-4, 225). Woo et al. and Chen et al. prepared a proton exchange membrane using polymer blends of polyvinyl alcohol) and poly(styrene sulfonic acid-co-maleic acid) (i.e. PVA/PSSA-MA) (see Woo et al, J. Membr. Sci. 2003, 220, 31 ; Chen et al., J. Membr. Sci. 2006, 269, 194). Novel epoxy-based semi-interpenetrating polymer networks (semi-IPNs) of aromatic polyimide, derived from 2,2-benzidinedisulfonic acid (BDSA), were prepared through a thermal imidization reaction for proton exchange membrane applications (see Lee et al., J. Polym. Sci.: Part A: Polym. Chem., 2008, 46, 2262).
Recent reports suggests that a two-polymer composite forms an IPN composed of proton- conducting 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS) and a second polymer, polyvinyl alcohol), serves as an effective methanol barrier (see Ehrenberg et al., U.S. Pat. 1997, 5, 679,482; Sone et al. , J. Electrochem. Soc.1996, 143, 1254; Fu et al., J. Power Sources, 2008, 179, 458). In another report, crosslinking polyvinyl alcohol) with sulfosuccinic acid (SSA) as a crosslinking agent and poly(styrene sulfonic acid-comaleic acid) (PSSA-MA) as a proton source, forms a semi-IPN PVA/SSA/PSSA-MA membrane (see Zhang et al., J. Solid State Chem. , 2005, 178, 2292; Komkova et al., J. Membr. Sci. 2004, 244, 25). Fu ef al. reported on a covalent organic/inorganic hybrid and semi-IPN technology, are combined together to develop a series of new proton-conductive membranes (see Fu et al., J. Power Sources, 2008, 179, 458). Very recently, a semi-IPN proton exchange membrane from the sulfonated poly(ether ether ketone) (sPEEK) and organosiloxane-based organic/inorganic hybrid network (organosiloxane network) where, the organosiloxane network is synthesized from 3-glycidyloxypropyltrimethoxysiane and 1-
hydroxyethane-1 , 1-diphosphonic acid was reported (see Luu et al., J. Power Sources 2011 , 196, 10584).
In an attempt to increase the conductivity of these materials, it has been recently proposed to introduce inorganic oxides into the polymer matrix to form nanocomposites (see Croce et al., Nature 1998, 394, 456; Jayathalaka et al., Electrochim. Acta 2002, 47, 3257; Best et al., Macromolecules 2001 , 34, 4549; Marcinek et al., Solid State Ionics 2000, 136-137, 1 175; Scrosati et al., J. Power Sources 2001 , 100, 93; Ana et al., J Mater. Chem. 2006, 16, 3107; Selim et al., J. Phys. Chem. C 2010, 114, 14281). In these materials the incorporated oxide particles create grain boundaries, which are responsible for the formation of highly conductive layers of polymer ceramic interfaces and prevent the polymeric chains from crystallizing.
An alternative route to create hybrid- / composite electrolytes for devices can be used and have been in practice. Herein, a porous inert separator material can be impregnated with an organic, long chained, uncured, polymerizable composition and subsequently taken through polymerization and curing stages to obtain a maultilayered gelled polymer system as described in U.S. Pat. No. 5,658,685, 1997; U.S. Pat. No. 5,681 ,357, 1997; U.S. Pat. No. 5,688,293, 1997; U.S. Pat. No. 5,716,421 , 1998; U.S. Pat. No. 5,837,015, 1998; U.S. Pat. No. 5,853,916, 1998, U.S. Pat. No. 5,952, 120, 1999 and U.S. Pat. No. 5,856,039, 1999.
Practical realization of functional devices and commercialization of the same using so.lid/quasi- solid polymer electrolytes have however remained elusive until very recently. Examples of the few important patents in the recent years, some of them which are licensed to start-ups or filed by corporate giants are U.S. Pat. No. 0263725 Al , 2009; U.S. Pat. No. 0075176 A1 , 2009; U.S. Pat. No. 0239918 A1 , 2010; U.S. Pat. No. 0269674 A1 , 2009; U.S. Pat. No. 0075232 A1 , 2010; U.S. Pat. No. 0255369 A1 , 2010; U.S. Pat. No. 0036060 A1 , 2010; U.S. Pat. No. 0081060 A1 , 2010; U.S. Pat. No. 0075195 A1 , 2010; U.S. Pat. No. 0092870 A1 , 2010; U.S. Pat. No. 0104947 A1 , 2010; U.S. Pat. No. 01 19950 A1 , 2010; U.S. Pat. No. 0255370 A1 , 2010 and U.S. Pat. No. 0255383 A1 , 2010. These polymer electrolyte compositions could however achieve significant ionic conductivity levels only when substantial plasticization with low molar mass organic liquids such as EC, PC, EMC, DEC, DMC, etc. were used for these matrices to enable faster ion transport. In alternate scenarios, appreciable conductivities could only be achieved by practicing very stringent control on the polymer matrix formation such as making well-defined block co- polymeric systems that require precise manipulation of the morphology to obtain the required architecture and oriented ion channels. Thus, the absence of liquid containment and leakage problems, possibility to operate with highly reactive electrodes over a wider temperature range and the prospects of miniaturization make these electrolyte systems stays very attractive. Though the polymer electrolytes are projected to address multiple issues related to device performance, unfortunately the factors such as relatively low ionic conductivity, the ability of polymer
electrolytes to operate with highly reactive electrodes such as lithium over a wider temperature range without deterioration in the charge capacity and electrolyte properties, the high interracial electrode-electrolyte impedances are still major technological challenges and roadblocks in practical realization. Thus, there is a need for a solid/quasi-solid electrolyte that exhibits high ion transport at room temperature compared to traditional solid polymer electrolytes.
OBJECTIVE OF THE INVENTION
The main objective of the present- invention is to create high-ionic conductivity electrolyte compositions.
Another objective of the present invention is to create high-ionic conductivity electrolyte compositions with semi-interpenetrating polymer networks (semi-IPN) and their nanocomposites as quasi-solid / solid electrolyte matrices suitable for use in next generation electrochemical devices.
Yet another objective of the present invention relates to electrolyte compositions comprised of polyether polymers, semi-interpenetrating polymer networks, surface-functionalized nanoparticles, salts / redox couples with enhanced ionic conductivity, low crystallinity, thermal stability, non-volatility to yield homogeneous semi-IPNs and their nanocomposites as electrolytes, and methods of making them.
SUMMARY OF THE INVENTION Accordingly, the present invention provides a high-ionic conductivity electrolyte composition comprising: a polymer network with polyether backbone,
a low molecular weight linear, branched, hyperbranched polymer or a binary combination of such polymers with non-reactive end groups, semi-IPN matrix.
an electrolyte salt, redox pair or a combination thereof;
d), a bare or surface modified nanostructured material to form a nanocomposite matrix.
In an embodiment of the present invention, the polymer networks forming component-l is selected from the group consisting of di- or multi-end functionalized hydroxyl, amine or carboxyl groups terminated polyether backbone, methylenediphenylene diisocyanate (MDI), polymeric methylenediphenylene diisocyanate (p-MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), dicyclohexanemethylene diisocyanate (H12MDI), isophoronediisocyanate (IPDI), xylene diisocyanate, hydrogenated xylene diisocyanate, Desmodur-N, glycerol, erythritol, pentaerythritol, xylitol, sorbitol, catechol, ascorbic acid,
catechol, dopamine, alizarin, gallic acid, dihydroxy benzoic acid, maltitol, triglycerides such as castor oil methylenediphenylene diisocyanate (MDI).
In another embodiment of the present invention, the polyether backbone is selected from the group consisting of di-hydroxyl, di-amine or di-carboxyl terminated compound of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG). In another embodiment of the present invention, the polyether backbone used as the building block have purity in the range of 80-90%.
In yet another embodiment of the present invention, the polyether backbone used has an average molecular weight in the range of 4,000 - 10,000 Daltons.
In still another embodiment of the present invention, the . second and/or third component of the semi-IPN matrix is selected from the group consisting of polyethylene glycol dimethylether, polypropylene glycol dimethylether, polytetramethylene glycol dimethylether, polyethelene glycol diacrylate, polyethelene glycol dimethacrylate, polystyrene, polymethylmethacrylate, polyvinylpyridine, polyvinylcyclohexane, polyamide, polyimide, polyethylene, polypropylene, polyolefins, polyacrylonitrile, polybutadine, polypyrrole, polysiloxanes, polyvinylidene fluoride, poly(t-butylvinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), Poly(t-butyl vinyl eher), polyphosphazene, copolymers containing ethylene oxide, styrene, methyacrylate, vinylpyridine.
In still another embodiment of the present invention the electrolyte salts is selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bistrifluorosulfonimide (LiN(CF3S02)2), lithium trifluorosulfonate (LiCF3S03), lithium perchlorate (LiCI04), lithium iodide (Lil), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), Li(CF3S02)3C, LiN(S02CF2CF3)2, LiB(C204)2, sodium perchlorate (NaCI04), sodium iodide (Nal), sodium thiocyanate (NaSCN), sodium tetrafluoroborate (NaBF4), potassium perchlorate (KCI04), . potassium iodide (Kl), potassium thiocyanate (KSCN). In still yet another embodiment of the present invention wherein the redox pair is selected from the group consisting of l37l", Br Br2, SCN7(SCN)2, SeCN7(SeCN)2 or Co(ll)/Co(lll).
In still another embodiment of the present invention the nanostructured materials is selected from the group consisting of titanium dioxide (Ti02), zinc oxide (ZnO), silicon dioxide (Si02), tin oxide (SnO, Sn02), aluminium oxide (Al203), zirconium oxide (Zr02), iron oxide (FeO, Fe203, Fe30 , FeOOH), cerium oxide (Ce02), vanadium oxide (V205), manganese oxide
(Mn02), magnesium oxide (MgO), nickel oxide (NiO), niobium oxide (Nb205), chromium oxide (Cr203), lead oxide (PbO), calcium oxide (CaO), calcium phosphate (CaP04), cadmium
sulfide (CdS), blends or core-shell morphologies of metal oxides such as Si02/Al203,
ZnO/Ti02; various phases of ceramic metal oxides, such as anatase-Ti02, rutile-Ti02, brookite-Ti02, alpha-AI203, beta- Al203, gamma-AI203 and mixed metal oxides such as ferrites, titanates, zirconates, zeolites, layered double hydroxides, fumed silica, organosilicates, clay, fly-ash.
BRIEF DESCRIPTION OF THE DRAWINGS & FIGURES
Figure - 1 is a simplified schematic illustration of the 3D-crosslinked polymer networks that forms the component-l of the present invention.
Figure - 2 is a simplified schematic illustration of the 3D-crosslinked polymer networks that constitutes the component-l interpenetrated in juxtaposition with a linear or branched oligomer / polymer that forms component-ll and/or component-Ill to yield a matrix of bi- or tri- component semi-interpenetrating polymer networks discussed in the embodiments of the present invention.
Figure - 3 is a simplified schematic representation of the 3D-matrix of bi- or tri- component semi- interpenetrating polymer networks as illustrated in Figure-2 with interspersed nanostructured materials to obtain the nanocomposites discussed in the embodiments of the present invention.
Figure - 4 is a simplified schematic view of another embodiment of the present invention depicting the 3D-matrix of bi- or tri- component semi-interpenetrating polymer networks as illustrated in Figure-2 with interspersed surface functionalized nanostructured materials to obtain the desired nanocomposites.
Figure - 5 (a)-(d) are a series of scanning electron microscopy images at increasingly higher magnifications showing the cross-sectional morphology of the synthesized semi-IPN Polymer with compositional ratio of Component-l : Component-ll = 50 : 50; LiCI04 salt as the electrolyte and EO/Li = 20 in accordance with the present invention.
Figure - 6 (a)-(d) are a series of scanning electron microscopy images at increasingly higher magnifications showing the cross-sectional morphology of the synthesized semi-IPN Polymer for a different compositional ratio of Component-l : Component-ll = 30 : 70; LiCI04 salt as the electrolyte and EO/Li = 20 in accordance with the present invention.
Figure - 7 BT and CT are the representative scanning electron microscopy images depicting the cross-sectional morphology of the synthesized semi-IPN Polymer-Nanocomposites with bare titania nanoparticles and surface modified catechol functionalized titania nanoparticles at 2wt% loading in a semi-compositional ratio of Component-l : Component-ll = 30 : 70; LiCI04 salt as the electrolyte and EO/Li = 30 in accordance with the present invention.
Figure - 8 is a graph illustrating the dependence of ionic conductivity as a function of temperature and with variation of reactant ratios forming the 3D-networks of component-l in the
synthesized semi-IPN Polymer matrix; the compositional ratio of Component-I : Component-ll was maintained at 30 : 70; LiCI04 salt as the electrolyte and EO/Li = 30 in accordance with the present invention.
Figure - 9 is a graph illustrating the dependence of ionic conductivity as a function of temperature and with variation of electrolyte concentration (salt content) in the synthesized semi- IPN Polymer matrix; the compositional ratio of Component-I : Component-ll was maintained at 30 : 70; LiCI04 salt as the electrolyte and the reactant ratio of Component-I = 1.2 in accordance with the present invention.
Figure - 10 is another graph illustrating the dependence of ionic conductivity as a function of temperature and with variation of compositional weight ratio of Component-I : Component-ll in the synthesized semi-IPN Polymer matrix; LiCI04 salt is used as the electrolyte with EO/Li = 30 and the reactant ratio of Component-I = 1.2 are maintained in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the application of binary or ternary component semi- interpenetrating polymer networks and their nanocomposites to create a homogeneous polymer / polymer-nanocomposite matrix that serves as a non-volatile quasi-solid/solid electrolyte with enhanced ionic conductivity, low crystallinity, thermal stability, and film forming capability. The binary- or ternary- component semi-interpenetrating polymer networks electrolyte composition according to the invention comprises of: a) a polymer networks with polyether backbone (Component-I); b) a low molecular weight linear, branched, hyper branched polymer or any binary combination of such polymers with preferably non-reactive end groups, Component-ll and/or component-Ill (for formation of ternary semi-IPN system); c) an electrolyte salt and/or a redox pair; and d) optionally, a bare or surface modified nanostructured material to form a nanocomposite matrix.-Polyethylene glycol (MW > 1000) is a linear crystalline polymer, including a high electronegative element such as oxygen on the main chain to produce polar bonding and help dissociation of salts. Ions bond with the polymers by forming transient crosslinks, which is reversible in nature. Therefore, ions transfer can occur either by ionic hopping from occupied to vacant site under an external field or percolate with the segmental movement of the polymer chain. However, since in the later case, the ions can transfer on the more flexible ether (— O— ) chain (non-crystalline regions) and are restricted in the crystalline domains, the ion diffusion rate will be low for polymers with higher degree of crystallinity (leading to low conductivity), if polyethylene glycol or polyethylene oxide is the only base material for electrolyte and hence the need of the industry cannot be satisfied. Thus, the present invention utilizes select chemistry to modify the polymeric architectures, forming nanocomposites, tailor morphology, reduce crystallinity, thermal and dimensional stability, enhance film forming capability, reduce/limit the
use of plasticizers prone to leakage and evaporation, and promote the ionic charge transport capability of polyether systems to address the gaps and bottlenecks. -Polyether backbone applied in the present invention should have a purity of more than 90%, and an average molecular weight in the range of 200 - 35,000 Daltons, preferably in the range of 400 - 15,000 Daltons, and more preferably in the range of 4,000 - 10,000 Daltons. The oligomers, macromonomers or polymers in the networks of component-l can be selected from end functionalized di- or multi-(hydroxyl, amine or carboxyl groups) terminated polyether backbone The hydroxyl, amine or carboxyl containing organic compound mentioned above can contain one or more hydroxyl, amine or carboxyl groups or can be a mixture of the compounds with different amounts of hydroxyl, amine or carboxyl groups. For example, the hydroxyl, amine or carboxyl terminated compound can be selected but is not limited to from the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), their block copolymers or branched/graft copolymers or combinations thereof. Preference for the polymer used in the formation of the semi-IPN polymer network and their nanocomposite is polyethylene glycol (PEG). In another embodiment, the cross linker in the networks of component-l can be selected from the range of organic molecules that contains multi-(hydroxyl, amine, carboxyl groups or any combination thereof). For example, the cross linker can be selected from but is not limited to from a group of organic molecules containing polyols, polyacids, polyamines or combination of one or more functional groups such glycerol, erythritol, pentaerythritol, xylitol, sorbitol, catechol, ascorbic acid, catechol, dopamine, alizarin, gallic acid, dihydroxy benzoic acid, maltitol, triglycerides such as castor oil, etc. combinations of these and so on. The polyether-urethane linkages, polyether- urea linkages or polyether-carboxyl linkages of the semi-IPN network in the present invention can be obtained by any methods known to the persons having ordinary skill in the art, for example, by polymerizing a hydroxyl, amine or carboxyl containing compound with an isocyanate containing compound. The mole ratio of the hydroxyl, amine and/or carboxyl containing compounds to that of the isocyanate containing compound is 1.0 : 0.6 to 1.0 : 5.0, preferably 1.0 : 1.0 to 1.0 : 3.0, and more preferably 1.0 : 1.1 to 1.0 : 2.5 According to the invention, the isocyanate containing compound can contain two or more isocyanate groups or a mixture of compounds with different amounts of isocyanate groups. For example, the isocyanate containing compound can be selected but is not limited to from the group consisting of methylenediphenylene diisocyanate (MDI), polymeric methylenediphenylene diisocyanate (p-MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), dicyclohexanemethylene diisocyanate (H12MDI), isophoronediisocyanate (IPDI), xylene diisocyanate, hydrogenated xylene diisocyanate, Desmodur-N, and so on. Preference for the polymer/polymer-nanocomposite-polymer network formation is MDI or HMDI. As described in detail above, a 3D-crosslinked polymer network preferably consisting of polyether segments is used in the embodiments of the invention as the component-l of the semi-IPN electrolyte compositions. Figure - 1 is a simplified schematic
illustration of an exemplary 3D-crosslinked polymer networks 100 that consists of an arrangement showing a first monomeric unit 110, a second monomeric unit 120 and a third monomeric unit 130 covalently bonded together to form the component-l of the present invention. The first monomer 110 represents the multi-functional groups (hydroxyl-, amine- or carboxyl-terminated) carrying organic moieties used as the crosslinker, the typical functionality depicted in the present illustration being 3. In the present arrangement, 120 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-l and 130 illustrates the di- isocyanate containing compound that covalently links the crosslinker 110 to the polyether backbone 120. The arrangements shown is merely representative and alternate arrangements, random repeats of the building blocks and combinations to achieve the polymer networks of component-l 100 are possible. In addition, the electrolyte composition of the present invention have a linear, branched or hyperbranched component or any combination thereof entangled within the polymer network (Component-l) to create a binary or ternary semi-interpenetrating polymer (semi-IPNs) matrix. According to the invention, Figure - 2 is a simplified schematic illustration of the 3D-crosslinked polymer networks that constitutes the component-l interpenetrated in juxtaposition with a linear or branched oligomer / polymer that forms component-ll and/or component-Ill to yield a matrix of bi- or tri- component semi-interpenetrating polymer networks 200 discussed in the embodiments of the present invention. In one exemplary arrangement the bi- or tri- component semi-interpenetrating polymer networks 200 consists of a first monomeric unit 210, a second monomeric unit 220 and a third monomeric unit 230 covalently bonded together to form the component-l of the present invention. The first monomer 210 represents the multi-functional groups (hydroxyl-, amine- or carboxyl-terminated) carrying organic moieties used as the crosslinker, the typical functionality depicted in the present illustration being 3. In the present arrangement, 220 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-l and 230 illustrates the di- isocyanate containing compound that covalently links the cross linker 210 to the polyether backbone 220. A second linear or branched oligomer / polymer or a combination of two linear oligomers/polymers or one linear and one branched oligomer/polymer or two branched oligomer/polymers 240 (Component-ll and/or Component-Ill) interpenetrate in juxtaposition of the host polymer networks (Component-l) to yield a matrix of bi- or tri- component semi-interpenetrating polymer networks 200. The arrangements shown is merely representative and several other alternate arrangements, random repeats of the building blocks and combinations thereof to achieve the semi-IPN polymer networks 200 are possible^ The second and/or third component of semi-IPN matrix in the present invention is a oligomeric or low molecular weight linear, branched or hyper branched polymer with preferably non-reactive end groups (Component-ll and/or Component-Ill). The oligomeric or low molecular weight linear, branched or hyper branched polymer of the present invention can be
selected from a group but is not limited to, such as polyethylene glycol dimethylether, polypropylene glycol dimethylether, polytetramethylene glycol dimethylether, polyethelene glycol diacrylate, polyethelene glycol dimethacrylate, polystyrene, polymethylmethacrylate, polyvinylpyridine, polyvinylcyclohexane, polyamide, polyimide, polyethylene, polypropylene, polyolefins, polyacrylonitrile, polybutadine, polypyrrole, polysiloxanes, polyvinylidene fluoride, poly(t-butylvinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), Poly(t-butyl vinyl eher), polyphosphazene, copolymers containing ethylene oxide, styrene, methacrylate, vinylpyridine, combinations of these and so on. The oligomer or low molecular weight polymer, however, should also preferentially possess low glass transition temperature, significant chemical and electrochemical stability; possibly also have the salt-solvation capability and considerable miscibility with the parent polymer network (Component-I) matrix. The purity of the oligomer or low molecular weight linear branched or hyper branched polymer should be preferably more than 90%, and an average molecular weight in the range of 200 - 5,000 Daltons, preferably in the range of 200 - 2,000 Daltons, and more preferably in the range of 4,00 - 1 ,000 Daltons. Preference for the polymeric Component-I I used to form the semi-IPN is polyethylene glycol dimethylether (PEGDME). There are no restrictions on the electrolyte salt that can be used in the semi-IPN electrolyte matrix. Any electrolyte salt that includes the ion identified as the desirable charge carrier for the applications envisaged can be used. As a thumb rule, it is especially convenient to choose electrolyte salts that have a higher dissociation constant, low lattice energy, and ease of solvation with the semi-IPN matrix. Suitable examples of electrolyte salts that can be selected from the group but are not , limited to includes alkali metal salts, such as, Li, Na, K cations with preferential larger anions. Examples of useful lithium salts include, but are not limited to, lithium hexafluorophosphate (LiPF6), lithium bistrifluorosulfonimide (LiN(CF3S02)2), lithium trifluorosulfonate (LiCF3S03), lithium perchlorate (LiCI04), lithium iodide (Lil), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF„), Li(CF3S02)3C, LiN(S02CF2CF3)2, LiB(C204)2, and mixtures thereof. Examples of useful sodium salts include, but are not limited to, sodium perchlorate (NaCI04), sodium iodide (Nal), sodium thiocyanate (NaSCN), sodium tetrafluoroborate (NaBF4), and so on. Examples of useful potassium salts include, but are not limited to, potassium perchlorate (KCI04), potassium iodide (Kl), potassium thiocyanate (KSCN), and so on. Electrolyte salts are not limited to alkali metal cation and can also include other cations with multiple valancy if desired, such as, transition metal cations of Mg, Cu, Co, Ni, Fe, rare earth metal salts of lanthanide and actinide series, such as Eu, Ru, Gd, La, and so on. There is no limitations as to the redox pair used in a dye sensitized solar cell as long as the energy level of the redox pair can match the highest occupied molecular orbital (HOMO) of the dye. For example, the redox pair can be but is not limited to Ι37Γ, Br Br2, SCN7(SCN)2, SeCN7(SeCN)2 or Co(ll)/Co(lll). Among them Ι37Γ is preferred as a redox pair because the diffusion rate of iodine ion is higher. The electrolyte composition optionally includes
nanostructures dispersed homogeneously within the semi-IPN polymer matrix. By adding a nanomaterial, the crystallinity of the polyethylene oxide can be significantly disturbed and thereby the non-crystalline regions can be increased to form an ion channel, thus increasing the conductivity the solid electrolyte. On the other hand, the hardness of the nanoparticles is helpful in increasing the mechanical strength and modulus of the solid electrolyte. There is no limitation to the species of the nanomaterials, their phase and morphology used in the invention. For example, the nanostructured materials can be selected from the group but not limited to, consisting of titanium dioxide (Ti02), zinc oxide (ZnO), silicon dioxide (Si02), tin oxide (SnO, Sn02), aluminium oxide (Al203), zirconium oxide (Zr02), iron oxide (FeO, Fe203, Fe304, FeOOH), cerium oxide (Ce02), vanadium oxide (V205), manganese oxide (Mn02), magnesium oxide (MgO), nickel oxide (NiO), niobium oxide (Nb205), chromium oxide (Cr203), lead oxide (PbO), calcium oxide (CaO), calcium phosphate (CaP04), cadmium sulfide (CdS), blends or core-shell morphologies of metal oxides such as Si02/Al203, ZnO/Ti02; various phases of ceramic metal oxides, such as anatase-Ti02, rutile-Ti02, brookite-Ti02, alpha-AI203, beta- Al203, gamma-AI203 and mixed metal oxides such as ferrites, titanates, zirconates, zeolites, layered double hydroxides, fumed silica, organosilicates, clay, fly-ash, etc. Preferably, titanium dioxide, zinc oxide or their mixtures are selected. More preferably, titanium dioxide is selected. The nanoparticles used in the present invention has been obtained by synthetic routes known to the persons having ordinary skill in the art, for example, by hydrolysis, sol-gel, hydrbthermal, solvothermal, co-precipitation, thermolysis, sonochemical, etc. The nanoparticles can be used in an amount of 0.01 parts by weight to 10 parts by weight, and preferably 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the total amount of (a) polyethylene oxide and (b) polyethylene oxide based network polymer of the electrolyte composition. In general, the size of the nanoparticles is about 1 to 50 nm, more preferably in the range of 1-30 nm. Figure - 3 is a simplified schematic representation of the 3D-matrix of bi- or tri- component semi-interpenetrating polymer networks as illustrated in Figure-2 with interspersed nanostructured materials to obtain the polymer-nanocomposites 300 discussed in the embodiments of the present invention. In one exemplary arrangement the bi- or tri- component semi-interpenetrating polymer networks- nanocomposites 300 consists of a first monomeric unit 310, a second monomeric unit 320 and a third monomeric unit 330 covalently bonded together to form the component-l of the present invention. The first monomer 310 represents the multi-functional groups (hydroxy!-, amine- or carboxyl-terminated) carrying organic moieties used as the cross linker, the typical functionality depicted in the present illustration being 3. In the present arrangement, 320 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-l and 330 illustrates the di- isocyanate containing compound that covalently links the cross linker 310 to the polyether backbone 320. A second linear or branched oligomer / polymer or a combination of two linear oligomers/polymers or one linear and one
branched oligomer/polymer or two branched oligomer/polymers 340 (Component-ll and/or Component-Ill) interpenetrated in juxtaposition of the host polymer networks (Component-I) and an intimate dispersion of nanostructured material of choice 350 yields a matrix of bi- or tri- component semi-interpenetrating polymer networks-nanocomposite 300. The arrangements shown is merely representative and several other alternate arrangements, random repeats of the building blocks, choice of nanomaterials, their morphology and combinations thereof to achieve the semi-IPN polymer-nanocomposites 300 are possible. Surface capping or functionalization of nanoparticles is a prior art and an effective technique to reduce coalescence, agglomeration and arrest particle growth, enhance dispersion / colloidal suspension in a variety of organic solvents, homogeneous distribution in polymer matrix and create possibility for active participation in the polymer network formation through other free reactive functional groups of the capping agent used. Several procedures for post-synthesis and in-situ functionalization of transition metal oxide nanoparticles via covalent linkages using a variety of ene-diol ligands such as ascorbic acid, catechol, dopamine, alizarin, etc. has been previously reported. The nanomaterials used in the present study were optionally functionalized post-synthesis or in-situ using routes known to the persons having ordinary skill in the art, for example, soaking, refluxing in high boiling solvent, sonochemistry, etc. The small organic molecules used for surface-functionalization of the nanoparticle surface were selected but is not limited to from the group, ascorbic acid, catechol, dopamine, alizarin, gallic acid, dihydroxy benzoic acid, glycerol, and so on.
[0077] Figure - 4 is a simplified schematic view of another embodiment of the present invention depicting the 3D-matrix of bi- or tri- component semi-interpenetrating polymer networks as illustrated in Figure-2 with interspersed surface functionalized nanostructured materials to obtain the desired nanocomposites 400. In one exemplary arrangement the bi- or tri- component semi- interpenetrating polymer networks-nanocomposites 400 consists of a first monomeric unit 410, a second monomeric unit 420 and a third monomeric unit 430 covalently bonded together to form the component-l of the present invention. The first monomer 410 represents the multi-functional groups (hydroxyl-, amine- or carboxyl-terminated) carrying organic moieties used as the crosslinker, the typical functionality depicted in the present illustration being 3. In the present arrangement, 420 is representative of di-functional-(hydroxyl, amine or carboxyl groups) terminated polyether backbone that forms the soft segment of the Component-I and 430 illustrates the di- isocyanate containing compound that covalently links the crosslinker 410 to the polyether backbone 420. A second linear or branched oligomer / polymer or a combination of two linear oligomers / polymers or one linear and one branched oligomer / polymer or two branched oligomer/polymers 440 (Component-ll and/or Component-Ill) interpenetrated in juxtaposition of the host polymer networks (Component-I) and an intimate dispersion of nanostructured material of choice 450 suitably surface functionalized with small organic molecules 460 yields a matrix of bi- or tri- component semi-interpenetrating polymer networks-nanocomposite 400. The
arrangements shown is merely representative and several other alternate arrangements, random repeats of the building blocks, choice of nanostructured materials, morphology of the nanomaterials, surface functionality and combinations thereof can be used to achieve the semi- IPN polymer-nanocomposites 400 are possible. In addition, the electrolyte composition of the present invention can optionally have an additive known in the art, such as an additive used for modifying the properties of the nanoparticles and/or improving the efficiency of the hybrid solar- cells. Such additives when used either individually or in combinations, competitively adsorb on the semiconductor material of the photo-anode, such as titanium dioxide, leading to considerable improvement in of the charge (electron) transfer mechanism of the photo-anode, help in increasing the short-circuit current (JSc) and improving the open circuit voltage (V0c) of the cells. In general, the additive can be selected from the group consisting of 4-tert-butylepyridine (TBP), N-methyl-benzimidazole (MBI), 1 ,2-dimethyl-3-propyimidazolium iodide (DMPII), lithium iodide (Lil), and sodium iodide (Nal). Other additives can be used in the semi-IPN and their nanocomposites as electrolytes described herein. For example, additives that help with overcharge protection, provide stable SEI (solid electrolyte interface) layers, and/or improve electrochemical stability can be used. Such additives are well known to people with ordinary skill in the art. Additives that make polymers easier to process, such as plasticizers, can also be used. Certain additives that can enhance the bulk conductivity levels, such as, low molecular weight conductive polymers, high dielectric constant platicizers, and room temperature ionic liquids, can also be optionally used if so desired. Additives that functions as anion receptors such as calixarenes, crown ethers, salen-type complexes can be optionally used to preferentially enhance cationic transport in the matrix.
Synthesis of semi-IPN matrix and electrolyte preparation
The process of preparing an electrolyte composition of the invention includes, for example, forming the isocyanate terminated pre-polymer by reacting the preferred molecular weight di- or multi-(hydroxyl, amine or carboxyl groups) terminated organic moiety with di- or multi-isocyanate compound as described above; mixing both the isocyanate terminated pre-polymer, a di- or multi- (hydroxyl, amine or carboxyl groups) terminated polyether and catalyst to initiate the formation of polymer networks (Component-I), incorporation of component-ll and/or component-Ill (for formation of binary or ternary semi-IPN system), i.e. oligomeric / or low molecular weight linear, branched or hyperbranched polymer with preferably non-reactive end groups, to intimately entangle within the growing polymer network, addition of desired electrolyte salt and/or redox couple system in required concentration of the electrolyte composition, optionally adding the nanostructured materials, mixing the additives, under continuous stirring (for 48 hrs at room temperature) in inert atmosphere, till a uniformly homogeneous viscous mix of an electrolyte composition is obtained. The viscous polymer / polymer-nanocomposite electrolyte compositions
are thereafter casted onto a teflon petri-dish or directly deposited onto the desired substrate by spin coating, screen-printing or using doctor-blade technique, dried at room temperature followed by curing at higher temperature and inert atmosphere to ensure the completion of isocyanate reaction (at 80 °C for 48 hrs) thereby forming quasi-solid or solid semi-IPN / nanocomposite semi- IPN electrolyte paste or films prior to characterizations and use in battery, solar-cells, or similar device applications.
According to the preferred embodiment of the invention, the process of forming the quasi- solid/solid semi-IPN or nanocomposite semi-IPN electrolyte pastes or films of the desired electrolyte composition of the invention includes the following steps:
(a) Dissolving, mixing, distributing and reacting the prefered molecular weight di- or multi- (hydroxyl, amine or carboxyl groups) terminated organic moieties (network crosslinkers) with di- or multi-isocyanate compound as described above in the pre-determined mole ratio and in a solvent under continuous stirring and inert atmosphere for 1 -2 hrs to form a viscous isocyanate- terminated pre-polymer solution.
(b) The solvent of step (a) of the above process is not limited, and can be selected from the group consisting of tetrahydrofuran (THF), acetonitrile (CH3CN), chloroform (CHCI3), dichioromethane (DCM), ethyl acetate (EtOAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diglyme, N-methyl pyrrolidone (NMP), mixtures thereof and so on. Preference is THF. The solvent volume was kept to minimal requirement.
(c) Dispersing, distributing and chemically reacting the a di- or multi-(hydroxyl, amine or carboxyl groups) terminated polyethers possessing free amine, hydroxyl or carboxyl groups with di- or multi-isocyanate terminated prepolymer compound in presence of a catalyst as described above in the pre-determined mole ratio and in a solvent under continuous stirring and inert atmosphere for 0.5 - 1.0 hr to initiate the formation of a viscous solution of slowly growing polymer networks which forms Component-I of the semi-IPN electrolyte composition. (d) The solvent of step (c) of the above process is not limited, and can be selected from the group consisting of tetrahydrofuran (THF), acetonitrile (CH3CN), chloroform (CHCI3), dichioromethane (DCM), ethyl acetate (EtOAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diglyme, N- methyl pyrrolidone (NMP) and so on. Preference is THF. The solvent volume was kept to minimal requirement. (e) The catalyst of step (c) of the above process is not limited, and can be selected from the group consisting of tertiary amines dimethyl aniline (DMA), diethyl aniline (DEA) and so on. Preference is DMA.
(f) At this stage of vigorous mixing at step (c); the component-ll and/or component-Ill (for formation of binary- or ternary- semi-IPN system), i.e. oligomeric or low molecular weight linear, branched or hyperbranched polymer with preferably non-reactive end groups pre-dissolved in a solvent separately and in required weight percent of the total polymer content of the final product was charged into the reaction flask to intimately entangle within the growing polymer network and form the desired mix of semi-IPN matrix.
(g) The solvent of step (f) of the above process is not limited, and can be selected from the group consisting of tetrahydrofuran (THF), acetonitrile (CH3CN), chloroform (CHCI3), dichloromethane (DCM), ethyl acetate (EtOAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), diglyme, N- methyl pyrrolidone (NMP) and so on. Preference is THF, CH3CN or a 1 : 1 solvent mixture of THF/CH3CN, more preferably solvent mixture of (1 :1 ) THF/CH3CN. The solvent volume was kept to minimal requirement.
(i) The addition of desired electrolyte salt and/or redox couple system in required concentration for the preferred electrolyte composition of the nanocomposite-polymer semi-IPN matrix is also done at this stage. This can be either added separately upon prior dissolution of the electrolyte salt and/or redox couple system in the preferred solvent mixture of (1 : 1 ) THF/CH3CN or pre- solvated along with the component-ll and/or component-Ill, step (g); in the preferred solvent mixture of (1 : 1 ) THF/CH3CN to hold the solvent volume to minimal requirement.
(j) The mixing of nanostructured materials and other additives of choice in required amounts are optional and can be done along with step (f) to incorporate them in the final product i.e. the formation of nanocomposite semi-IPN electrolyte matrix.
(k) The desired electrolyte composition mix is thereafter left under continuous stirring for 12 - 48 hrs at room temperature in inert atmosphere, till a uniformly homogeneous viscous and stable suspension of the semi-IPN / nanocomposite semi-IPN is obtained. Preferred time of mixing at this stage is 24 hrs. Preparation of semi-IPN matrix electrolyte films
(I) The viscous semi-IPN / nanocomposite semi-IPN electrolyte compositions are subsequently casted onto a teflon petri-dish or directly deposited onto the desired substrate by spin coating, screen-printing or using doctor-blade technique.
(m) Finally, the semi-IPN / nanocomposite semi-IPN electrolyte compositions were dried at room temperature followed by curing at higher temperature (at 60 -100 °C for 48-96 hrs) and inert atmosphere to ensure trapped solvent evaporation, the completion of isocyanate reaction thereby
forming quasi-solid/solid semi-IPN / nanocomposite semi-IPN electrolyte paste or films. The curing temperature is preferably 80 °C and the curing time 48 hrs.
(n) The quasi-solid/solid semi-IPN / nanocomposite semi-IPN electrolyte paste or films so formed were then taken up further for the required characterizations and evaluations of their physico- chemical properties as well as assessment of test-cell performance. EXAMPLES The following examples, which include preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of examples and for purpose of illustrative discussion of preferred embodiments of the invention only and are not limiting the scope of the invention
Morphology evaluation of semi-IPN electrolytes.
The morphology of the semi-IPN electrolytes were analysed with scanning electron microscopy on a JEOL JSM-5600N. The cross-sections of the matrix were sputtered with gold and SEM images were acquired at different magnifications to ascertain the sample homogeneity, extent of phase separation and porosity. Figure - 5 (a)-(d) depicts a exemplary series of scanning electron microscopy images at increasingly higher magnifications showing the cross-sectional morphology of the synthesized Semi-IPN Polymer with compositional ratio of Component-I (polyether networks) : Component-ll (polyethylene glycol dimethylether) = 50 : 50; LiCI0 salt as the electrolyte and EO/Li - 20. In another example, Figure - 6 (a)-(d) shows a series of scanning electron microscopy images at increasingly higher magnifications showing the cross-sectiorjal morphology of the synthesized Semi-IPN Polymer for a different compositional ratio of Component-I (polyether networks) : Component-ll (polyethylene glycol dimethylether) = 30 : 70; UCIO4 salt as the electrolyte and EO/Li = 20. The images reveal fairly homogeneous bulk and minimal phase separation except at the substrate interface, probably due to slightly preferential stratification of the polymer network component during the cure process. The SEM images 5(d) and 6(d), at magnification, X = 3. OK, both the compositions of the semi-IPN electrolytes reveal significant porosity in the semi-IPN films indicating possibility of co-continuous channels present throughout the matrices. Presence of high porosity or free volume while retaining the structural integrity of the polymer matrix can considerably impact the ion-transport in such systems leading to enhancement of ionic conductivity. Figure - 7 BT and CT are the representative scanning electron microscopy images depicting the cross-sectional morphology of the synthesized semi- IPN polymer-nanocomposites with bare titania nanoparticles and surface modified catechol functionalized titania nanoparticles at 2wt% loading in a semi-compositional ratio of Component-I : Component-ll = 30 : 70; L1CIO4 salt as the electrolyte and EO/Li = 30 in accordance with the present invention. Both the semi-IPN nanocomposite samples reveal good homogeneity in the
bulk and almost no agglomeration of the dispersed nanomaterials, indicating reasonable nanoparticle-polymer interaction at the interfaces.
Evaluation of ionic conductivity as a function of temperature for the semi-IPN electrolyte compositions.
The alternating current electrochemical impedance measurements were carried out on a Zahner® Zennium electrochemical workstation controlled by Thales Operational Software. The system was interfaced with a thermostated oven equipped with parallel test channels independently connected to spring loaded Swagelok cells to test the samples at identical conditions. The synthesized semi-IPN electrolyte samples were vacuum dried overnight before carrying out the electrical measurements. Punched circular disc shaped polymer films (thickness ~ 0.6mm) of surface area 0.8cm2 were sandwiched between two 316 stainless steel blocking electrodes with a Teflon spacer of appropriate dimension and loaded in the Swagelok assembly. The spring and Teflon spacer ensured the application of same amount of spring pressure during the sample mounting and throughout the test. The sample holders were placed in the controlled heating chamber to carry out the variable temperature impedance measurements over a range of ~20°C to 90°C at an interval of ~5-7°C during heating. The temperature was measured with accuracy better than ±0.1 °C using a K-type thermocouple placed in close proximity with the sample. The samples were equilibrated at each temperature for 30 minutes prior to acquiring the frequency sweep impedance data. No corrections for thermal expansion of the cells were carried out. The real part of the impedance was appropriately normalized for the cell dimensions and ionic conductivity (□ (Scm" )) was determined. All the data point plotted represents an average of at least three different sets of measurements under similar conditions with appropriate standard deviation provided as Y-Error. Analysis of the temperature dependence of the ionic conductivity data was done by non-linear least square fits (NLSF) using Microcal OriginPro 8.5 software. The maximum error associated with the simulated fits for the Arrhenius and/or Vogel-Tammann- Fulcher (VTF) equation is within ± 3%. The obtained ionic conductivity for all the semi-IPN compositions were > 10"5 Scm"1 at ambient temperatures (25-30 °C) as would be evident from the following examples.
As an example, the effect of reactant ratio variation 230 : (210+220) with reference to the Figure - 2 as described in detail above, forming the 3D-networks of component-l in the synthesized Semi- IPN Polymer matrix; Figure - 8 illustrates the dependence of ionic conductivity as a function of temperature. The compositional ratio in accordance with the present invention, Component-l (polyether networks): Component-ll (polyethylene glycol dimethylether) = 30 : 70; LiCI04 salt as the electrolyte and EO/Li = 30 was maintained. Lower crosslink density as provided by the - NCO/-OH ratio 1 : 1 yielded the best ionic conductivity behavior while maintaining reasonable structural integrity of the semi-IPN films.
In another example, the effect of total electrolyte concentration (salt content) in the synthesized semi-IPN Polymer matrix 200; Figure - 9 illustrates the dependence of ionic conductivity as a function of temperature and EO/Li mole ratio variation. The compositional ratio in accordance with the present invention, Component-I (polyether networks) : Component-ll (polyethylene glycol dimethylether) = 30 : 70; LiCI04 salt as the electrolyte and the reactant ratio of Component-I = 1.2 was maintained. As can be observed from the data, EO/Li mole ratio = 30 yielded the best ionic conductivity through-out the temperature window of the study.
In yet another example, Figure - 10 illustrates the dependence of ionic conductivity as a function of temperature with variation of semi-IPN composition 200 while LiCI04 salt is used as the electrolyte with EO/Li = 30 and the reactant ratio of Component-I = 1.2 are maintained in accordance with the present invention. The plot shows varying weight ratio in the intermediate range of Component-I (polyether networks) : Component-ll (polyethylene glycol dimethylether); 60:40; 50:50; 40;60 and 30:70 in the synthesized Semi-IPN polymer matrix, with the best relative conductivity observed for the 30:70 composition. Though the conductivity showed steady increase, structural integrity of the semi-IPN matrix was heavily compromised beyond 70wt% of the component-ll.
Evaluation of thermal properties for the semi-IPN electrolyte compositions.
Differential scanning calorimetry was performed on a DSC Q200 differential scanning calorimeter (TA Instruments) under dry nitrogen atmosphere. The synthesized semi-IPN electrolyte samples were vacuum dried overnight before carrying out the thermal studies. Typically a sample (5- 10mg) of the semi-IPN electrolyte was loaded in an aluminum pan and hermetically sealed, rapidly cooled down to -150°C using liquid nitrogen, equilibrated for 5 minutes and then heated up to 150°C at scan rate of 10°C min. The power and temperature scales were calibrated using pure indium. The glass transition temperature (Tg) was determined from the inflection-point of the transitions. Melting and crystallization temperatures, when they occurred, were defined as the maxima of the melting endotherms™ and crystallization exotherms (Tc), respectively. Heat of fusion (AHm) was measured by the area under the melting endotherms. Percentage crystallinity (%χ) was determined from the ratio of the experimentally measured enthalpy to the value of 205J/g reported for the enthalpy of melting of 100% crystalline PEO.
Figure - 18 (a)-(f) are the representative thermograms obtained by differential scanning calorimetry for the synthesized bi-component Semi-IPN Polymer matrix with variation in the electrolyte concentration (salt content); the compositional ratio of Component-I : Component-ll used is 30 : 70 with LiCI04 as the electrolyte salt and the reactant ratio of Component-I = 1.2 maintained along with other parameters in accordance with the present invention. The thermograms provided are for (a) EO/Li = 100, (b) EO/Li = 80, (c) EO/Li = 60, (d) EO/Li = 30, (e) EO/Li = 20 and (f) EO/Li = 10. As can be observed, the glass transition temperature is well below
the ambient (< 40 °C) for all the samples. The semi-IPNs also exhibited a suppressed melting over a broader temperature range. The effect of cross-linking and networks formation is obvious with a very significant decrease in the degree of crystallinity and lowering of Tm.
The thermal stabilities of the synthesized semi-IPNs were assessed by a TA Q500 modulated thermo gravimetric analyzer. 10 to 20 mg of the samples were carefully weighed in an aluminum pan and TG scans- were recorded at -a rate of 10 °C/min under nitrogen~atmosphere_ in the temperature range 35 °C to 600°C.
Figure - 19 is a representative dual Y-axis plot of a thermogravimetry scan and the corresponding differential plot for the synthesized bi-component Semi-IPN Polymer matrix. The compositional ratio in accordance with the present invention of Component-I : Component-ll used is 30 : 70 with LiCI04 as the electrolyte salt; EO/Li = 30 and the reactant ratio of Component-I = 1.2. The thermogravimetry studies coupled wit differential analysis of the scans reveal that the degradation onset temperature of all the semi-IPN electrolyte compositions is > 50 °C. An initial weight loss of 1-2 wt % observed for all the samples in the temperature range 50-150 °C is presumably due to the evaporation of low molecular weight species such as absorbed moisture, unreacted monomer (acrylonitrile), and residual solvents like THF, acetonitrile, or DMA which were used during synthesis. Three stages of degradation beyond 150 °C typical of all the semi- IPN electrolyte compositions are evident from the differential analysis. The first stage usually in the range of 180 - 250 °C corresponds to the scission of the transient crosslinks in the Polymer (M+...0), the second stage in the range of 250 - 375 °C are the further scission of the polymer backbones at the urethane, urea, ether and amide linkages, finally beyond 400 °C the polymer undergoes advanced fragmentation, degradation and charring.
Claims
A ionic conductivity electrolyte composition comprising: a) a polymer network with polyether backbone,
b) a low molecular weight linear, branched, hyperbranched polymer or a binary combination of such polymers with non-reactive end groups, semi-IPN matrix.
c) an electrolyte salt, redox pair or a combination thereof; and
d) , a bare or surface modified nanostructured material to form a nanocomposite matrix.
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the polymer networks forming component-l is selected from the group consisting of di- or multi-end functionalized hydroxyl, amine or carboxyl groups terminated polyether backbone, methylenediphenylene diisocyanate (MDI), polymeric methylenediphenylene diisocyanate (p-MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), dicyclohexanemethylene diisocyanate (H 2MDI), isophoronediisocyanate (IPDI), xylene diisocyanate, hydrogenated xylene, diisocyanate, Desmodur-N, glycerol, erythritol, pentaerythritol, xylitol, sorbitol, catechol, ascorbic acid, catechol, dopamine, alizarin, gallic acid, dihydroxy benzoic acid, maltitol, triglycerides such as castor oil methylenediphenylene diisocyanate (MDI).
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the polyether backbone is selected from the group consisting of di-hydroxyl, di-amine or di- carboxyl terminated compound of polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol (PTMG).
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the polyether backbone used as the building block have purity in the range of 80-90%.
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the polyether backbone used has an average molecular weight in the range of 4,000 - 10,000 Daltons.
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the second and/or third component of the semi-IPN matrix is selected from the group consisting of polyethylene glycol dimethylether, polypropylene glycol dimethylether, polytetramethylene glycol dimethylether, polyethelene glycol diacrylate, polyethelene glycol dimethacrylate, polystyrene, polymethylmethacrylate, polyvinylpyridine, polyvinylcyclohexane, polyamide, polyimide, polyethylene, polypropylene, polyolefins,
polyacrylonitrile, polybutadine, polypyrrole, polysiloxanes, polyvinylidene fluoride, poly(t- butylvinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), Poly(t-butyl vinyl eher), polyphosphazene, copolymers containing ethylene oxide, styrene, methyacrylate, and vinylpyridine.
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the electrolyte salts is selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bistrifluorosulfonimide (LiN(CF3S02)2), lithium trifluorosulfonate (UCF3SO3), lithium perchlorate (LiCI04), lithium iodide (Lil), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), Li(CF3S02)3C, LiN(S02CF2CF3)2, LiB(C204)2, sodium perchlorate (NaCI04), sodium iodide (Nal), sodium thiocyanate (NaSCN), sodium tetrafluoroborate (NaBF4), potassium perchlorate (KCI04), potassium iodide (Kl), and potassium thiocyanate (KSCN).
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the redox pair is selected from the group consisting of l37l", Br Br2, SCN7(SCN)2, SeCN7(SeCN)2 or Co(ll)/Co(lll).
The ionic conductivity electrolyte composition as claimed in claim 1 , wherein the nanostructured materials is selected from the group consisting of titanium dioxide (Ti02), zinc oxide (ZnO), silicon dioxide (Si02), tin oxide (SnO, Sn02), aluminium oxide (Al203), zirconium oxide (Zr02), iron oxide (FeO, Fe203, Fe30 , FeOOH), cerium oxide (Ce02), vanadium oxide (V205), manganese oxide (Mn02), magnesium oxide (MgO), nickel oxide (NiO), niobium oxide (Nb205), chromium oxide (Cr203), lead oxide (PbO), calcium oxide (CaO), calcium phosphate (CaP04), cadmium sulfide (CdS), blends or core-shell morphologies of metal oxides such as Si02/Al203, ZnO/Ti02; various phases of ceramic metal oxides, such as anatase-Ti02l rutile-Ti02, brookite-Ti02, alpha-AI203, beta- Al203, gamma-AI203 and mixed metal oxides such as ferrites, titanates, zirconates, zeolites, layered double hydroxides, fumed silica, organosilicates, clay and fly-ash.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/778,688 US20160049690A1 (en) | 2013-03-19 | 2014-03-19 | High-ionic conductivity electrolyte compositions comprising semi-interpenetrating polymer networks and their composites |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IN808DE2013 | 2013-03-19 | ||
IN808/DEL/2013 | 2013-03-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014147648A1 true WO2014147648A1 (en) | 2014-09-25 |
Family
ID=50732232
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IN2014/000174 WO2014147648A1 (en) | 2013-03-19 | 2014-03-19 | High-ionic conductivity electrolyte compositions comprising semi-interpenetrating polymer networks and their composites |
Country Status (2)
Country | Link |
---|---|
US (1) | US20160049690A1 (en) |
WO (1) | WO2014147648A1 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106268958A (en) * | 2016-07-18 | 2017-01-04 | 浙江大学 | The preparation of a kind of nanometer silver magnetic polystyrene microsphere and application thereof |
CN107658495A (en) * | 2017-09-27 | 2018-02-02 | 天津力神电池股份有限公司 | The solid lithium ion battery of composite polymer electrolyte |
CN107863553A (en) * | 2017-09-27 | 2018-03-30 | 天津力神电池股份有限公司 | Solid lithium ion battery based on inierpeneirating network structure polymer dielectric |
CN108906003A (en) * | 2018-08-02 | 2018-11-30 | 南通大学 | A kind of preparation method of the polypropylene-base adsorbent material based on poly-dopamine modified lithium |
CN109473715A (en) * | 2017-09-08 | 2019-03-15 | 松下知识产权经营株式会社 | Sulfide solid electrolyte material and the battery for using the material |
CN111335038A (en) * | 2020-04-13 | 2020-06-26 | 安徽省农业科学院棉花研究所 | Washable photocatalytic super-hydrophobic cotton fabric and preparation and application thereof |
CN111816925A (en) * | 2020-08-14 | 2020-10-23 | 中南大学 | Solid-state battery and preparation method thereof |
CN111916818A (en) * | 2020-07-08 | 2020-11-10 | 成都新柯力化工科技有限公司 | Solid lithium battery silicon dioxide aerogel frame electrolyte and preparation method thereof |
CN112812372A (en) * | 2021-01-05 | 2021-05-18 | 湘潭大学 | Tannin-phosphazene network functionalized hydrotalcite-based flame retardant and preparation method thereof |
DE102019132370A1 (en) * | 2019-11-28 | 2021-06-02 | Forschungszentrum Jülich GmbH | Semi-interpenetrating polymer networks based on polycarbonates as separators for use in alkali metal batteries |
CN113209981A (en) * | 2021-04-02 | 2021-08-06 | 华南理工大学 | FeOOH/Fe3O4/WO3/TiO2photo-Fenton catalytic membrane and preparation method and application thereof |
US20210265661A1 (en) * | 2018-09-28 | 2021-08-26 | Lg Chem, Ltd. | Solid electrolyte and method for manufacturing same |
EP3766103A4 (en) * | 2018-03-12 | 2021-12-29 | Omega Energy Systems, LLC | Solid-state energy harvester of transition metal suboxides |
US11476487B2 (en) | 2019-11-13 | 2022-10-18 | Omega Energy Systems, Llc | Three-electrode solid-state energy harvester of transition metal suboxides |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105070847B (en) * | 2015-09-10 | 2017-10-17 | 京东方科技集团股份有限公司 | A kind of composite bed, its preparation method and OLED |
US9972838B2 (en) | 2016-07-29 | 2018-05-15 | Blue Current, Inc. | Solid-state ionically conductive composite electrodes |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
KR102093965B1 (en) * | 2016-11-21 | 2020-03-26 | 주식회사 엘지화학 | Lithium-sulfur battery |
US9926411B1 (en) * | 2017-03-03 | 2018-03-27 | Blue Current, Inc. | Polymerized in-situ hybrid solid ion-conductive compositions |
US10457781B2 (en) | 2017-03-03 | 2019-10-29 | Blue Current, Inc. | Polymerized in-situ hybrid solid ion-conductive compositions |
DE112018003878T5 (en) * | 2017-07-31 | 2020-04-23 | Robert Bosch Gmbh | ACCUMULATORS WITH POLYMER ELECTROLYTE COMPOSITES BASED ON TETRAEDRIC ARYLBORATE NODES |
CN109400786B (en) * | 2017-08-16 | 2020-12-29 | 东莞东阳光科研发有限公司 | High-molecular polymer, preparation method thereof and electrolyte containing high-molecular polymer |
CN109837559B (en) * | 2017-11-28 | 2021-08-06 | 中国科学院大连化学物理研究所 | Hydrothermal-assisted preparation method of hydroxyl iron oxide-nickel iron hydrotalcite integrated electrode |
KR102255536B1 (en) * | 2017-11-30 | 2021-05-25 | 주식회사 엘지에너지솔루션 | Composition for gel polymer electrolyte, gel polymer electrolyte and lithium secondary battery comprising the same |
KR102617867B1 (en) * | 2018-07-09 | 2023-12-22 | 주식회사 엘지에너지솔루션 | Solid electrolytes for all solid state battery, methods for manufacturing the same, and all solid state battery including the same |
US11581570B2 (en) | 2019-01-07 | 2023-02-14 | Blue Current, Inc. | Polyurethane hybrid solid ion-conductive compositions |
CN110078957B (en) * | 2019-04-18 | 2021-07-02 | 厦门理工学院 | Preparation method of polypyrrole-polycaprolactone antibacterial nano composite film |
CN110224171B (en) * | 2019-05-10 | 2022-03-04 | 招远市国有资产经营有限公司 | Preparation method of solid polymer electrolyte |
CN112909328A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Ultrathin sulfide solid electrolyte layer and preparation method and application thereof |
JP2023507733A (en) | 2019-12-20 | 2023-02-27 | ブルー カレント、インコーポレイテッド | Composite electrolyte with binder |
US11394054B2 (en) | 2019-12-20 | 2022-07-19 | Blue Current, Inc. | Polymer microspheres as binders for composite electrolytes |
CN111430790A (en) * | 2020-03-03 | 2020-07-17 | 蜂巢能源科技有限公司 | Semi-solid electrolyte and preparation method and application thereof |
CN111793235A (en) * | 2020-06-08 | 2020-10-20 | 金华市金秋环保水处理有限公司 | Preparation method of cation exchange membrane with IPN structure |
US11855258B2 (en) | 2020-06-08 | 2023-12-26 | Cmc Materials, Inc. | Secondary battery cell with solid polymer electrolyte |
CN111653824A (en) * | 2020-06-22 | 2020-09-11 | 武汉瑞科美新能源有限责任公司 | Gel polymer electrolyte, rapid preparation method thereof and battery |
CN112635840B (en) * | 2020-12-21 | 2021-12-14 | 中南大学 | Preparation method of HNTs plasticized PAN/P (LLA-EG-MA) biogel polymer electrolyte and product thereof |
KR102583474B1 (en) * | 2020-12-30 | 2023-09-27 | 연세대학교 산학협력단 | Polymer-clay nanocomposite electrolyte for secondary battery and method for preparing the same |
CN113178614B (en) * | 2021-04-21 | 2022-11-04 | 深圳市合壹新能技术有限公司 | Composite solid electrolyte, solid lithium battery and preparation method |
EP4106073A1 (en) | 2021-06-16 | 2022-12-21 | VARTA Microbattery GmbH | Electrolyte hydrogel and its use in an electrochemical cell |
CN113832467B (en) * | 2021-09-26 | 2024-02-13 | 江西理工大学 | Polymer modified dopamine corrosion inhibitor, preparation method and application thereof |
WO2023069243A2 (en) * | 2021-09-29 | 2023-04-27 | Hyzon Motors Inc. | Fuel cells with improved membrane life |
CN114142081B (en) * | 2021-11-30 | 2022-11-29 | 南京信息工程大学 | Ion-selective gel-state electrolyte, preparation method and lithium-sulfur battery |
CN114361572A (en) * | 2021-12-08 | 2022-04-15 | 电子科技大学长三角研究院(湖州) | Modified ceramic material, and preparation method and application of composite electrolyte prepared from same |
CN114907529B (en) * | 2022-06-07 | 2023-03-10 | 华中科技大学 | Flexible gel polymer electrolyte based on in-situ polymerization and preparation method thereof |
Citations (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4650730A (en) | 1985-05-16 | 1987-03-17 | W. R. Grace & Co. | Battery separator |
US5456000A (en) | 1993-03-05 | 1995-10-10 | Bell Communications Research, Inc. | Method of making an electrolyte activatable lithium-ion rechargeable battery cell |
US5571392A (en) * | 1994-11-22 | 1996-11-05 | Nisshinbo Industries, Inc. | Solid ion conductive polymer electrolyte and composition and production method therefor |
US5643695A (en) | 1995-09-26 | 1997-07-01 | Valence Technology, Inc. | Carbonaceous electrode and compatible electrolyte |
US5658685A (en) | 1995-08-24 | 1997-08-19 | Motorola, Inc. | Blended polymer gel electrolytes |
US5679482A (en) | 1994-05-23 | 1997-10-21 | Dais Corporation | Fuel cell incorporating novel ion-conducting membrane |
US5681357A (en) | 1996-09-23 | 1997-10-28 | Motorola, Inc. | Gel electrolyte bonded rechargeable electrochemical cell and method of making same |
US5688293A (en) | 1996-05-15 | 1997-11-18 | Motorola, Inc. | Method of making a gel electrolyte bonded rechargeable electrochemical cell |
US5716421A (en) | 1997-04-14 | 1998-02-10 | Motorola, Inc. | Multilayered gel electrolyte bonded rechargeable electrochemical cell and method of making same |
US5837015A (en) | 1997-09-26 | 1998-11-17 | Motorola, Inc. | Method of making a multilayered gel electrolyte bonded rechargeable electrochemical cell |
US5853916A (en) | 1996-10-28 | 1998-12-29 | Motorola, Inc. | Multi-layered polymeric gel electrolyte and electrochemical cell using same |
US5856039A (en) | 1996-03-27 | 1999-01-05 | Sanyo Electric Company, Ltd. | Non-aqueous electrolyte secondary cell |
US5952120A (en) | 1997-04-15 | 1999-09-14 | Celgard Llc | Method of making a trilayer battery separator |
US20030054257A1 (en) * | 1998-09-07 | 2003-03-20 | Kazuhiro Noda | Electrolyte compound, and electrolyte, process for producing the same and battery using the same |
US20050072462A1 (en) * | 2003-10-01 | 2005-04-07 | Kang Moon Sung | Solid state dye-sensitized solar cell employing composite polymer electrolyte |
US20090075176A1 (en) | 2006-04-04 | 2009-03-19 | Seeo, Inc. | Solid Electrolyte Material Manufacturable by Polymer Processing Methods |
US20090263725A1 (en) | 2006-04-04 | 2009-10-22 | The Regents Of The University Of California | High Elastic Modulus Polymer Electrolytes |
US20090269674A1 (en) | 2002-04-03 | 2009-10-29 | Samsung Sdi Co., Ltd. | Electrolyte for lithium battery and lithium battery comprising same |
US20100036060A1 (en) | 2002-07-30 | 2010-02-11 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Electrolyte compositions |
US20100075195A1 (en) | 2006-03-14 | 2010-03-25 | Tda Research, Inc. | Nanoporous Polymer Electrolyte |
US20100075232A1 (en) | 1998-04-20 | 2010-03-25 | Electrovaya Inc. | Composite polymer electrolytes for a rechargeable lithium battery |
US20100081060A1 (en) | 2008-09-26 | 2010-04-01 | Shin-Kobe Electric Machinery Co., Ltd. | Electrolyte and lithium secondary battery using the same |
US20100092870A1 (en) | 2008-09-12 | 2010-04-15 | Enerize Corporation | Solid polymer electrolyte for solar cells and lithium batteries |
US20100104947A1 (en) | 2008-10-29 | 2010-04-29 | Samsung Electronics Co., Ltd. | Electrolyte composition and catalyst ink and solid electrolyte membrane formed by using the same |
US20100119950A1 (en) | 2008-11-10 | 2010-05-13 | Samsung Electronics Co., Ltd. | Polymer electrolyte, lithium battery comprising the polymer electrolyte, method of preparing the polymer electrolyte, and method of preparing the lithium battery |
US20100239918A1 (en) | 2009-03-17 | 2010-09-23 | Seeo, Inc | Nanoparticle-block copolymer composites for solid ionic electrolytes |
US20100255370A1 (en) | 2009-04-01 | 2010-10-07 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
US20100255369A1 (en) | 2009-04-01 | 2010-10-07 | Hwang Duck-Chul | Electrolyte for Rechargeable Lithium Battery Including Additives, and Rechargeable Lithium Battery Including the Same |
US20100255383A1 (en) | 2009-02-27 | 2010-10-07 | University Of Maryland, College Park | Polymer Solid Electrolyte for Flexible Batteries |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL105341A (en) * | 1993-04-08 | 1996-12-05 | Univ Ramot | Composite solid electrolyte and alkali metal batteries using this electrolyte |
-
2014
- 2014-03-19 WO PCT/IN2014/000174 patent/WO2014147648A1/en active Application Filing
- 2014-03-19 US US14/778,688 patent/US20160049690A1/en not_active Abandoned
Patent Citations (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4650730A (en) | 1985-05-16 | 1987-03-17 | W. R. Grace & Co. | Battery separator |
US5456000A (en) | 1993-03-05 | 1995-10-10 | Bell Communications Research, Inc. | Method of making an electrolyte activatable lithium-ion rechargeable battery cell |
US5679482A (en) | 1994-05-23 | 1997-10-21 | Dais Corporation | Fuel cell incorporating novel ion-conducting membrane |
US5571392A (en) * | 1994-11-22 | 1996-11-05 | Nisshinbo Industries, Inc. | Solid ion conductive polymer electrolyte and composition and production method therefor |
US5658685A (en) | 1995-08-24 | 1997-08-19 | Motorola, Inc. | Blended polymer gel electrolytes |
US5643695A (en) | 1995-09-26 | 1997-07-01 | Valence Technology, Inc. | Carbonaceous electrode and compatible electrolyte |
US5856039A (en) | 1996-03-27 | 1999-01-05 | Sanyo Electric Company, Ltd. | Non-aqueous electrolyte secondary cell |
US5688293A (en) | 1996-05-15 | 1997-11-18 | Motorola, Inc. | Method of making a gel electrolyte bonded rechargeable electrochemical cell |
US5681357A (en) | 1996-09-23 | 1997-10-28 | Motorola, Inc. | Gel electrolyte bonded rechargeable electrochemical cell and method of making same |
US5853916A (en) | 1996-10-28 | 1998-12-29 | Motorola, Inc. | Multi-layered polymeric gel electrolyte and electrochemical cell using same |
US5716421A (en) | 1997-04-14 | 1998-02-10 | Motorola, Inc. | Multilayered gel electrolyte bonded rechargeable electrochemical cell and method of making same |
US5952120A (en) | 1997-04-15 | 1999-09-14 | Celgard Llc | Method of making a trilayer battery separator |
US5837015A (en) | 1997-09-26 | 1998-11-17 | Motorola, Inc. | Method of making a multilayered gel electrolyte bonded rechargeable electrochemical cell |
US20100075232A1 (en) | 1998-04-20 | 2010-03-25 | Electrovaya Inc. | Composite polymer electrolytes for a rechargeable lithium battery |
US20030054257A1 (en) * | 1998-09-07 | 2003-03-20 | Kazuhiro Noda | Electrolyte compound, and electrolyte, process for producing the same and battery using the same |
US20090269674A1 (en) | 2002-04-03 | 2009-10-29 | Samsung Sdi Co., Ltd. | Electrolyte for lithium battery and lithium battery comprising same |
US20100036060A1 (en) | 2002-07-30 | 2010-02-11 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Electrolyte compositions |
US20050072462A1 (en) * | 2003-10-01 | 2005-04-07 | Kang Moon Sung | Solid state dye-sensitized solar cell employing composite polymer electrolyte |
US20100075195A1 (en) | 2006-03-14 | 2010-03-25 | Tda Research, Inc. | Nanoporous Polymer Electrolyte |
US20090263725A1 (en) | 2006-04-04 | 2009-10-22 | The Regents Of The University Of California | High Elastic Modulus Polymer Electrolytes |
US20090075176A1 (en) | 2006-04-04 | 2009-03-19 | Seeo, Inc. | Solid Electrolyte Material Manufacturable by Polymer Processing Methods |
US20100092870A1 (en) | 2008-09-12 | 2010-04-15 | Enerize Corporation | Solid polymer electrolyte for solar cells and lithium batteries |
US20100081060A1 (en) | 2008-09-26 | 2010-04-01 | Shin-Kobe Electric Machinery Co., Ltd. | Electrolyte and lithium secondary battery using the same |
US20100104947A1 (en) | 2008-10-29 | 2010-04-29 | Samsung Electronics Co., Ltd. | Electrolyte composition and catalyst ink and solid electrolyte membrane formed by using the same |
US20100119950A1 (en) | 2008-11-10 | 2010-05-13 | Samsung Electronics Co., Ltd. | Polymer electrolyte, lithium battery comprising the polymer electrolyte, method of preparing the polymer electrolyte, and method of preparing the lithium battery |
US20100255383A1 (en) | 2009-02-27 | 2010-10-07 | University Of Maryland, College Park | Polymer Solid Electrolyte for Flexible Batteries |
US20100239918A1 (en) | 2009-03-17 | 2010-09-23 | Seeo, Inc | Nanoparticle-block copolymer composites for solid ionic electrolytes |
US20100255370A1 (en) | 2009-04-01 | 2010-10-07 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
US20100255369A1 (en) | 2009-04-01 | 2010-10-07 | Hwang Duck-Chul | Electrolyte for Rechargeable Lithium Battery Including Additives, and Rechargeable Lithium Battery Including the Same |
Non-Patent Citations (114)
Title |
---|
ABRAHAM ET AL., J. ELECTROCHEM. SOC., vol. 135, 1988, pages 535 |
ABRAHAM ET AL., J. ELECTROCHEM. SOC., vol. 136, 1990, pages 1657 |
ACOSTA ET AL., APPL. POLYM. SCI., vol. 60, 1996, pages 1185 |
ALLCOCK ET AL., MACROMOLECULES, vol. 19, 1986, pages 1508 |
ALLCOCK ET AL., MACROMOLECULES, vol. 29, 1996, pages 1951 |
ALLCOCK ET AL., MACROMOLECULES, vol. 29, 1996, pages 7544 |
ANA ET AL., J. MATER. CHEM., vol. 16, 2006, pages 3107 |
ANDREEV ET AL., ELECTROCHIM. ACTA, vol. 45, 2000, pages 1417 |
APPETECCHI ET AL., ELECTROCHIM. ACTA, vol. 40, 1995, pages 991 |
ARMAND ET AL., EXTENDED ABSTRACTS, SECOND INTERNATIONAL CONFERENCE ON SOLID ELECTROLYTES, 1978 |
ARMAND ET AL.: "Proc. Int. Conf.", 1979, ELSEVIER, article "Fast Ion Transport in Solids: Electrodes & Electrolytes" |
BANISTER ET AL., POLYMER, vol. 25, 1984, pages 1600 |
BASAK ET AL., EUR POLYM. J., vol. 40, no. 6, 2004, pages 1155 |
BASAK ET AL., J. MACROMOL. SCI. - PURE AND APPL. CHEM., vol. A38, no. 4, 2001, pages 399 |
BASAK ET AL., J. MACROMOL. SCI. - PURE AND APPL. CHEM., vol. A43, no. 2, 2006, pages 369 |
BASAK ET AL., J. PHYS. CHEM. B, vol. 109, no. 3, 2005, pages 1174 |
BASAK ET AL., SOLID STATE LONICS, vol. 167, no. 1-2, 2004, pages 113 |
BEST ET AL., MACROMOLECULES, vol. 34, 2001, pages 4549 |
BLONSKY ET AL., J. AM. CHEM. SOC., vol. 106, 1984, pages 6854 |
BLONSKY ET AL., SOLID STATE LONICS, vol. 18-19, 1989, pages 258 |
BONINO ET AL., J. POWER SOURCES, vol. 18, 1986, pages 75 |
CHAKRABORTY ET AL., SYNTH. MET., vol. 98, 1999, pages 193 |
CHEN ET AL., J. MEMBR SCI., vol. 269, 2006, pages 194 |
CHENG ET AL., ELECTROCHEMISTRY COMMUNICATIONS, vol. 6, 2004, pages 531 |
CHERADAME ET AL., MATER. RES. BULL., vol. 15, 1980, pages 1173 |
CHIANG ET AL., SOLID STATE LONICS, vol. 18-19, 1986, pages 300 |
CHO ET AL., ELECTROCHIMICA ACTA, vol. 50, 2004, pages 589 |
CHOI ET AL., ELECTROCHIMICA ACTA, vol. 53, 2008, pages 6575 |
COLICCHIO ET AL., FUEL CELLS, vol. 06, no. 3-4, 2006, pages 225 |
COWIE ET AL., ANNU. REV. PHYS. CHEM., vol. 40, 1989, pages 85 |
COWIE, JMG: "Polymer Electrolyte Reviews-1", vol. 1, 1987, ELSEVIER APPLIED SCIENCE |
CROCE ET AL., NATURE, vol. 394, 1998, pages 456 |
DAVIS ET AL., SOLID STATE LONICS, vol. 18-19, 1986, pages 321 |
DRUGER ET AL., J. CHEM. PHYS., vol. 79, 1983, pages 3133 |
FENTON ET AL., POLYMER, vol. 14, 1973, pages 589 |
FISH ET AL., BR. POLYM. J., vol. 20, 1988, pages 281 |
FISH ET AL., MAKROMOL. CHEM. RAPID. COMMUN., vol. 7, 1986, pages 115 |
FLORJANCZYK ET AL., J. POLYM. SCI., PART B, POLYM. PHYS. ED., vol. 33, 1995, pages 629 |
FRANCOIS ET AL., ELECTROCHIMICA ACTA, vol. 53, 2008, pages 4336 |
FRISCH ET AL., J. POLYM. SCI., PART A: POLYM.CHEM., vol. 30, 1992, pages 937 |
FU ET AL., J. POWER SOURCES, vol. 179, 2008, pages 458 |
FU ET AL., POWER SOURCES, vol. 179, 2008, pages 458 |
GAN ET AL., POLYM. INT., vol. 48, 1999, pages 1160 |
GAN ET AL., POLYMER, vol. 40, 1999, pages 4035 |
GANGOPADHYAY ET AL., J. MATER. CHEM., vol. 12, 2002, pages 3591 |
GAUTHIER ET AL., D. J. ELECTROCHEM. SOC., vol. 132, 1985, pages 1333 |
GAUTHIER ET AL., POLYMER, vol. 48, 2007, pages 7476 |
GRAY, FM: "Solid Polymer Electrolytes-Fundamentals and Technological Applications", 1991, VCH |
HALL ET AL., POLYM. COMMUN., vol. 27, 1986, pages 98 |
HAWKER ET AL., MACROMOLECULES, vol. 29, 1996, pages 3831 |
HENRY ET AL., CHEM. MATER., vol. 11, 1999, pages 1024 |
HOU ET AL., POLYMER, vol. 42, 2001, pages 4181 |
HOURSTON ET AL., J. POLYM. ADV. TECHNOL., vol. 7, 1996, pages 1 |
ICHIKAWA ET AL., POLYMER, vol. 33, 1992, pages 4699 |
J. POLYM. SCI. POLYM. PHYS. ED., vol. 14, 1976, pages 955 |
J. POLYM. SCI., PART A: POLYM. CHEM., vol. 32, 1994, pages 2395 |
JAYATHALAKA ET AL., ELECTROCHIM. ACTA, vol. 47, 2002, pages 3257 |
JEAN-FRANOIS ET AL., MACROMOLECULES, vol. 21, 1988, pages 1117 |
KILLIS ET AL., J. POLYM. SCI., POLYM. PHYS. ED., vol. 19, 1981, pages 1073 |
KILLIS ET AL., SOLID STATE LONICS, vol. 14, 1984, pages 231 |
KIM ET AL., ELECTROCHIM. ACTA, vol. 46, 2001, pages 1323 |
KOBAYASHI ET AL., J. PHYS. CHEM., vol. 89, 1985, pages 987 |
KOMKOVA ET AL., J. MEMBR. SCI., vol. 244, 2004, pages 25 |
KOTA RAMANJANEYULU ET AL: "Semi-interpenetrating polymer networks as solid polymer electrolytes: Effects of ion-dissociation, crosslink density and oligomeric entanglements on the conductivity behavior in poly(ethylene oxide)-polyurethane/poly(acrylonitrile) matrix", JOURNAL OF POWER SOURCES, vol. 217, 1 November 2012 (2012-11-01), pages 29 - 36, XP055127966, ISSN: 0378-7753, DOI: 10.1016/j.jpowsour.2012.05.075 * |
LAV ET AL., J SOLID STATE ELECTROCHEM., vol. 11, 2007, pages 859 |
LEE ET AL., J. APPL. POLYM. SCI., vol. 104, 2007, pages 2965 |
LEE ET AL., J. POLYM. SCI.: PART A: POLYM. CHEM., vol. 46, 2008, pages 2262 |
LEVESQUE ET AL., MAKROMOL. CHEM. RAPID COMMUN., vol. 4, 1983, pages 497 |
LI ET AL., J. APPL. POLYM. SCI., vol. 108, 2008, pages 39 |
LI ET AL., J. POLYM. SCI. POLYM. CHEM., vol. 33, 1995, pages 1657 |
LUO ET AL., J. APPL. POLYM. SCI., vol. 108, 2008, pages 2095 |
LUU ET AL., J. POWER SOURCES, vol. 196, 2011, pages 10584 |
MACCALLUM ET AL.: "Polymer Electrolyte Reviews-1", vol. 1, 1987, ELSEVIER APPLIED SCIENCE |
MACROMOLECULES, vol. 31, 1998, pages 8026 |
MANDAL ET AL., SYNTH. MET., vol. 80, 1996, pages 83 |
MARCINEK ET AL., SOLID STATE LONICS, vol. 136-137, 2000, pages 1175 |
MATSUGUCHI ET AL., J. MEMBRANE SCI., vol. 281, 2006, pages 707 |
MD. SELIM ARIF SHER SHAH ET AL: "Polymer Nanocomposites as Solid Electrolytes: Evaluating Ion-Polymer and Polymer-Nanoparticle Interactions in PEG-PU/PAN Semi-IPNs and Titania Systems", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 114, no. 33, 26 August 2010 (2010-08-26), pages 14281 - 14289, XP055127969, ISSN: 1932-7447, DOI: 10.1021/jp105450q * |
MERTENS ET AL., MACROMOLECULES, vol. 32, 1999, pages 3314 |
MUNICHANDRAIAH ET AL., J. APPL. POLYM. SCI., vol. 65, 1997, pages 2191 |
MUNICHANDRAIAH, J. APPL. POLYM. SCI., vol. 65, 1997, pages 2191 |
NARESH CHILAKA ET AL: "Solid-state poly(ethylene glycol)-polyurethane/polymethylmethacrylate/rutile TiO2 nanofiber composite electrolyte-correlation between morphology and conducting properties", ELECTROCHIMICA ACTA, vol. 62, 1 February 2012 (2012-02-01), pages 362 - 371, XP055127951, ISSN: 0013-4686, DOI: 10.1016/j.electacta.2011.12.052 * |
OH ET AL., ELECTROCHEM. SOLID STATE LETT., vol. 5, 2002, pages E59 |
PERERA ET AL., ELECTROCHIM. ACTA, vol. 45, 2000, pages 1361 |
PRATYAY BASAKA ET AL: "Thermomechanical Properties of PEO-PU/PAN Semi-Interpenetrating Polymer Networks and their LiClO4 Salt-Complexes", JOURNAL OF MACROMOLECULAR SCIENCE : PART A - CHEMISTRY, MARCEL DEKKER, NEW YORK, NY, US, vol. 43, no. 2, 1 January 2006 (2006-01-01), pages 369 - 382, XP008170488, ISSN: 0022-233X, [retrieved on 20070207], DOI: 10.1080/10601320500437292 * |
RAMANJANEYULU ET AL., JOURNAL OF POWER SOURCES, vol. 217, 2012, pages 29 |
RANDRIAMAHAZASKA ET AL., SYNTHETIC METALS, vol. 128, 2002, pages 197 |
RATNER ET AL., CHEM. REV., vol. 88, 1988, pages 109 |
ROBITAILLE ET AL., MACROMOLECULES, vol. 16, 1983, pages 665 |
SCROSATI B ET AL: "IMPEDANCE SPECTROSCOPY STUDY OF PEO-BASED NANOCOMPOSITE POLYMER ELECTROLYTES", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, ELECTROCHEMICAL SOCIETY, MANCHESTER, NEW HAMPSHIRE; US, vol. 147, no. 5, 1 May 2000 (2000-05-01), pages 1718 - 1721, XP001051666, ISSN: 0013-4651, DOI: 10.1149/1.1393423 * |
SCROSATI ET AL., J. POWER SOURCES, vol. 100, 2001, pages 93 |
SELIM ET AL., J. PHYS. CHEM. C, vol. 114, 2010, pages 14281 |
SHI ET AL., SOLID STATE LONICS, vol. 60, 1993, pages 11 |
SHIBATA ET AL., EUR. POLYM. J., vol. 36, 2000, pages 485 |
SHIN ET AL., SYNTHETIC METALS, vol. 154, 2005, pages 213 |
SONE ET AL., J. ELECTROCHEM. SOC., vol. 143, 1996, pages 1254 |
SORENSEN ET AL., ELECTROCHIM. ACTA, vol. 27, 1982, pages 1671 |
TSUCHIDA ET AL., SOLID STATE LONICS, vol. 11, 1983, pages 227 |
VALLEE ET AL., ELECTROCHIM. ACTA, vol. 37, 1992, pages 1579 |
VIDAL ET AL., JOURNAL OF APPLIED POLYMER SCIENCE, vol. 90, 2003, pages 3569 |
VONDRAK ET AL., ELECTROCHIM. ACTA, vol. 46, 2001, pages 2047 |
WAENKAEW ET AL., MACROMOL. CHEM. PHYS., vol. 212, 2011, pages 1039 |
WATANABE ET AL., J. APPL. PHYS., vol. 57, 1985, pages 123 |
WATANABE ET AL., MACROMOLECULES, vol. 18, 1985, pages 1945 |
WATANABE ET AL.: "Polymer Electrolyte Reviews", 1987, ELSIEVER |
WOO ET AL., J. MEMBR. SCI., vol. 220, 2003, pages 31 |
WRIGHT PV, BR. POLYM. J., vol. 7, 1975, pages 319 |
XIA ET AL., SOLID STATE LONICS, vol. 14, 1984, pages 221 |
YIN ET AL., J. APPL. POLYM. SCI., vol. 63, 1997, pages 13 |
YIN ET AL., J. APPL. POLYM. SCI., vol. 64, 1997, pages 2293 |
YIN ET AL., J. APPL. POLYM. SCI., vol. 65, 1997, pages 1 |
YIN ET AL., POLYM. INT., vol. 2, 1997, pages 276 |
ZHANG ET AL., J. APPL. POLYM. SCI., vol. 77, 2000, pages 2957 |
ZHANG ET AL., J. SOLID STATE CHEM., vol. 178, 2005, pages 2292 |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106268958A (en) * | 2016-07-18 | 2017-01-04 | 浙江大学 | The preparation of a kind of nanometer silver magnetic polystyrene microsphere and application thereof |
CN109473715A (en) * | 2017-09-08 | 2019-03-15 | 松下知识产权经营株式会社 | Sulfide solid electrolyte material and the battery for using the material |
CN109473715B (en) * | 2017-09-08 | 2023-11-03 | 松下知识产权经营株式会社 | Sulfide solid electrolyte material and battery using the same |
CN107658495A (en) * | 2017-09-27 | 2018-02-02 | 天津力神电池股份有限公司 | The solid lithium ion battery of composite polymer electrolyte |
CN107863553A (en) * | 2017-09-27 | 2018-03-30 | 天津力神电池股份有限公司 | Solid lithium ion battery based on inierpeneirating network structure polymer dielectric |
CN107863553B (en) * | 2017-09-27 | 2024-02-23 | 天津力神电池股份有限公司 | Solid lithium ion battery based on interpenetrating network structure polymer electrolyte |
EP3766103A4 (en) * | 2018-03-12 | 2021-12-29 | Omega Energy Systems, LLC | Solid-state energy harvester of transition metal suboxides |
CN108906003A (en) * | 2018-08-02 | 2018-11-30 | 南通大学 | A kind of preparation method of the polypropylene-base adsorbent material based on poly-dopamine modified lithium |
US20210265661A1 (en) * | 2018-09-28 | 2021-08-26 | Lg Chem, Ltd. | Solid electrolyte and method for manufacturing same |
US11901507B2 (en) * | 2018-09-28 | 2024-02-13 | Lg Energy Solution, Ltd. | Solid electrolyte and method for manufacturing same |
US11476487B2 (en) | 2019-11-13 | 2022-10-18 | Omega Energy Systems, Llc | Three-electrode solid-state energy harvester of transition metal suboxides |
WO2021105023A1 (en) | 2019-11-28 | 2021-06-03 | Forschungszentrum Jülich GmbH | Semi-interpenetrating polymer networks based on polycarbonates as separators for use in alkali-metal batteries |
DE102019132370B4 (en) | 2019-11-28 | 2021-11-11 | Forschungszentrum Jülich GmbH | Semi-interpenetrating polymer networks based on polycarbonates as separators for use in alkali-metal batteries and alkali-metal batteries manufactured with them |
DE102019132370A1 (en) * | 2019-11-28 | 2021-06-02 | Forschungszentrum Jülich GmbH | Semi-interpenetrating polymer networks based on polycarbonates as separators for use in alkali metal batteries |
CN111335038A (en) * | 2020-04-13 | 2020-06-26 | 安徽省农业科学院棉花研究所 | Washable photocatalytic super-hydrophobic cotton fabric and preparation and application thereof |
CN111916818B (en) * | 2020-07-08 | 2021-10-29 | 成都新柯力化工科技有限公司 | Solid lithium battery silicon dioxide aerogel frame electrolyte and preparation method thereof |
CN111916818A (en) * | 2020-07-08 | 2020-11-10 | 成都新柯力化工科技有限公司 | Solid lithium battery silicon dioxide aerogel frame electrolyte and preparation method thereof |
CN111816925B (en) * | 2020-08-14 | 2022-11-29 | 中南大学 | Solid-state battery and preparation method thereof |
CN111816925A (en) * | 2020-08-14 | 2020-10-23 | 中南大学 | Solid-state battery and preparation method thereof |
CN112812372A (en) * | 2021-01-05 | 2021-05-18 | 湘潭大学 | Tannin-phosphazene network functionalized hydrotalcite-based flame retardant and preparation method thereof |
CN113209981A (en) * | 2021-04-02 | 2021-08-06 | 华南理工大学 | FeOOH/Fe3O4/WO3/TiO2photo-Fenton catalytic membrane and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
US20160049690A1 (en) | 2016-02-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20160049690A1 (en) | High-ionic conductivity electrolyte compositions comprising semi-interpenetrating polymer networks and their composites | |
Wang et al. | Siloxane-based polymer electrolytes for solid-state lithium batteries | |
Xi et al. | Polymer‐based solid electrolytes: material selection, design, and application | |
Saal et al. | Polymers for battery applications—active materials, membranes, and binders | |
Yang et al. | Review of ionic liquids containing, polymer/inorganic hybrid electrolytes for lithium metal batteries | |
Li et al. | Polymers in lithium‐ion and lithium metal batteries | |
Wu et al. | Polymer electrolytes and interfaces toward solid-state batteries: Recent advances and prospects | |
Ding et al. | Polyethylene oxide-based solid-state composite polymer electrolytes for rechargeable lithium batteries | |
Reinoso et al. | Strategies for rational design of polymer-based solid electrolytes for advanced lithium energy storage applications | |
Barbosa et al. | Toward sustainable solid polymer electrolytes for lithium-ion batteries | |
CN107039680A (en) | Solid electrolyte and the lithium battery for including the solid electrolyte | |
US20180226679A1 (en) | Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries | |
Ulaganathan et al. | Surface analysis studies on polymer electrolyte membranes using scanning electron microscope and atomic force microscope | |
Hu et al. | Recent progress of polymer electrolytes for solid-state lithium batteries | |
Liu et al. | Recent development in topological polymer electrolytes for rechargeable lithium batteries | |
Zuo et al. | Fabrication of elastic cyclodextrin-based triblock polymer electrolytes for all-solid-state lithium metal batteries | |
Wang et al. | Solid polymer electrolytes based on cross-linked polybenzoxazine possessing poly (ethylene oxide) segments enhancing cycling performance of lithium metal batteries | |
Szczęsna-Chrzan et al. | Lithium polymer electrolytes for novel batteries application: the review perspective | |
Andersson et al. | Designing polyurethane solid polymer electrolytes for high-temperature lithium metal batteries | |
Wang et al. | High-Capacity, Sustainable Lithium–Sulfur Batteries Based on Multifunctional Polymer Binders | |
Lee et al. | Tough polymer electrolyte with an intrinsically stabilized interface with Li metal for all-solid-state lithium-ion batteries | |
He et al. | Hybrid Dynamic Covalent Network as a Protective Layer and Solid-State Electrolyte for Stable Lithium-Metal Batteries | |
Ye et al. | Polymer electrolytes as solid solvents and their applications | |
Saminathan et al. | Enhanced electrochemical performance of a silica bead-embedded porous fluoropolymer composite matrix for Li-ion batteries | |
Bristi et al. | Ionic Conductivity, Na Plating–Stripping, and Battery Performance of Solid Polymer Na Ion Electrolyte Based on Poly (vinylidene fluoride) and Poly (vinyl pyrrolidone) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14724518 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14778688 Country of ref document: US |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14724518 Country of ref document: EP Kind code of ref document: A1 |