CN110997684A - Polar polysiloxane electrolyte for lithium batteries - Google Patents
Polar polysiloxane electrolyte for lithium batteries Download PDFInfo
- Publication number
- CN110997684A CN110997684A CN201780089708.0A CN201780089708A CN110997684A CN 110997684 A CN110997684 A CN 110997684A CN 201780089708 A CN201780089708 A CN 201780089708A CN 110997684 A CN110997684 A CN 110997684A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrolyte
- group
- polymer
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 polysiloxane Polymers 0.000 title claims abstract description 119
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 239000003792 electrolyte Substances 0.000 title claims description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 39
- 229920001296 polysiloxane Polymers 0.000 title abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 26
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical group C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 25
- 229920001400 block copolymer Polymers 0.000 claims description 21
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 19
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- 125000005504 styryl group Chemical group 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 125000001624 naphthyl group Chemical group 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 14
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 14
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 14
- 150000003462 sulfoxides Chemical class 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical group CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 12
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 12
- 229920001519 homopolymer Polymers 0.000 claims description 12
- 229920002554 vinyl polymer Chemical group 0.000 claims description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 11
- 150000004678 hydrides Chemical class 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 11
- PFXVKGGZWQQTSE-UHFFFAOYSA-N sulfuryl dicyanide Chemical compound N#CS(=O)(=O)C#N PFXVKGGZWQQTSE-UHFFFAOYSA-N 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012965 benzophenone Substances 0.000 claims description 10
- 239000006182 cathode active material Substances 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 10
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical group 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 claims description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical group ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- NOXDLRAACCQLQR-UHFFFAOYSA-N 2-methyl-N-(2-methyl-1-phenylpropoxy)-N-(1-phenylethoxy)propan-2-amine Chemical compound C(C)(C)(C)N(OC(C)C1=CC=CC=C1)OC(C(C)C)C1=CC=CC=C1 NOXDLRAACCQLQR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- 239000002482 conductive additive Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000001989 lithium alloy Substances 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 150000003457 sulfones Chemical class 0.000 claims description 5
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 claims description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 4
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920002776 polycyclohexyl methacrylate Polymers 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 claims description 3
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 3
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 3
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 abstract description 11
- 239000010406 cathode material Substances 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 abstract description 3
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 1
- 239000003999 initiator Substances 0.000 description 7
- 229920005604 random copolymer Polymers 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 6
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 5
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 5
- 239000002001 electrolyte material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 150000002825 nitriles Chemical group 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 101100136728 Cricetulus griseus Pisd gene Proteins 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
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- 125000001174 sulfone group Chemical group 0.000 description 3
- 125000003375 sulfoxide group Chemical group 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910013884 LiPF3 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000001566 impedance spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 2
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- FPFRTDOMIFBPBZ-UHFFFAOYSA-N n-tert-butyl-2-methyl-1-phenyl-n-(1-phenylethoxy)propan-1-amine Chemical compound C=1C=CC=CC=1C(C(C)C)N(C(C)(C)C)OC(C)C1=CC=CC=C1 FPFRTDOMIFBPBZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
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- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 description 1
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- 229910008367 Li-Pb Inorganic materials 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
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- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
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- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 208000020960 lithium transport Diseases 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
The synthesis and electrochemical performance of novel polymer electrolytes based on polar polysiloxane polymers are described. Unlike ethylene oxide based polymers, these materials have oxidative stability up to a voltage of at least 4.2V, a voltage of 4.2V being the operating voltage of high energy batteries using cathode materials such as lithium nickel cobalt aluminum oxide (NCA) and lithium nickel cobalt manganese oxide (NCM). The invention also describes the use of these polymer electrolytes in solid state lithium batteries to replace PEO.
Description
The inventor: khaladilol swainson, Hani balsam Eatoni
[ technical field ] A method for producing a semiconductor device
The present invention relates generally to electrolytes for lithium battery cells, and more particularly to electrolytes particularly suitable for use in high voltage cells.
[ background of the invention ]
More and more lithium battery manufacturers are using next generation cathode materials, such as NCA (lithium nickel cobalt aluminum oxide) and NCM (lithium nickel cobalt manganese oxide), to take advantage of their potentially high gravimetric energy density (up to 300-. Cells made with such oxide materials typically operate at higher voltages (e.g., up to 4.5V) than cells with olivine cathode materials such as LFP (lithium iron phosphate) (e.g., 3.6-3.8V). Electrolytes that are stable at the lower voltages of LFP cells may be difficult to operate at higher voltages. Polyethylene oxide (PEO) type electrolytes commonly used in conventional solid state lithium batteries are known to be stable only at lower voltages (e.g., below 4.0V) and may be difficult to operate at these new higher voltages, especially in the cathode. Oxidative form Degradation (Degradation) may lead to capacity fade early in the life of the cell.
Therefore, there is a need to develop non-PEO based polymer electrolytes that are well suited for operation under the High Voltage (HV) conditions of next generation cathode materials.
[ summary of the invention ]
In one embodiment of the present invention, the polymer composition comprises a homopolymer having the structure:
wherein each X is independently selected from the group consisting of sulfone, cyanomethyl ester, sulfoxide, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl; each R is independently selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, t-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, nitroxide, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-t-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine (hudroxylamine), hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthyl, anthracenyl, styryl, acylate, norbornene, epoxy groups, and substituted portions of phenyl, benzyl, naphthyl, anthracenyl, styryl, acylate, norbornene, epoxy groups, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl; z is an integer from 2 to 1000.
In another embodiment of the present invention, the polymer composition comprises a copolymer having the structure:
wherein each X is independently selected from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl; each R is independently selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, t-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, nitroxide, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-t-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine, hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene, epoxy groups, and substituted portions of phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene and epoxy groups, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl; m and n are integers, and the sum of m and n is from 2 to 1000.
An electrolyte salt may be added to the polymer or copolymer shown above so that it can be used as an electrolyte material. Examples of useful salts are set forth below. In one arrangement, the electrolyte salt is a lithium salt.
In another embodiment of the present invention, the block copolymer composition comprises ordered nanostructures comprising a matrix (matrix) of first regions formed by association of first polymers and second regions formed by association of second polymers. The first polymer and the second polymer form a first copolymer. The first copolymer is a block copolymer in which the first polymer forms a first block and the second polymer forms a second block. The first block comprises one or more of a homopolymer and a copolymer having the following structure:
wherein each X is independently selected from the group consisting of cyano, sulfone, cyanomethyl ester, sulfoxide, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl. Each R is independently selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, t-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, nitroxide, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-t-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine (hudroxylamine), hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthyl, anthracenyl, styryl, acylate, norbornene, epoxy groups, and substituted portions of phenyl, benzyl, naphthyl, anthracenyl, styryl, acylate, norbornene, epoxy groups, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl; z is an integer from 2 to 1000; m and n are integers, and the sum of m and n is from 2 to 1000.
The second block can include one or more polymers such as polystyrene, hydrogenated polystyrene, polymethacrylate, poly (methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefin, poly (t-butyl vinyl ether), poly (cyclohexyl methacrylate), poly (cyclohexyl vinyl ether), poly (t-butyl vinyl ether), polyethylene, polyphenylene oxide, poly (2, 6-dimethyl-1, 4-phenylene ether) (PXE), poly (phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide amide, polysulfone, polyvinylidene fluoride, and copolymers containing styrene, methacrylate, or vinylpyridine.
In another embodiment of the present invention, the electrolyte material includes an electrolyte salt and a homopolymer having the structure:
wherein each X is independently selected from the group consisting of cyano, sulfone, cyanomethyl ester, sulfoxide, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl. Each R is independently selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, t-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, nitroxide, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-t-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine, hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene, epoxy groups, and substituted portions of phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene and epoxy groups, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl; and z is an integer from 2 to 1000.
In another embodiment of the invention, an electrolyte includes ordered nanostructures comprising a matrix (matrix) of first regions formed by association of first polymers and second regions formed by association of second polymers. The first polymer and the second polymer form a first copolymer, which may be a block copolymer, wherein the first polymer forms a first block and the second polymer forms a second block. The first block may comprise a polymer selected from the group consisting of:
a homopolymer having the structure:
and a copolymer having the structure:
wherein each X is independently selected from the group consisting of cyano, sulfone, cyanomethyl ester, sulfoxide, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl. Each R is independently selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, t-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, nitroxide, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-t-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine, hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene, epoxy groups, and substituted portions of phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene, epoxy groups, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl; z is an integer from 2 to 1000; and m and n are integers and the sum of m and n is from 2 to 1000.
The second block may comprise one or more polymers selected from the group consisting of polystyrene, hydrogenated polystyrene, polymethacrylate, poly (methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefin, poly (t-butyl vinyl ether), poly (cyclohexyl methacrylate), poly (cyclohexyl vinyl ether), poly (t-butyl vinyl ether), polyethylene, polyphenylene oxide, poly (2, 6-dimethyl-1, 4-phenylene ether) (PXE), poly (phenylene sulfide sulfone), poly (phenylene sulfide ketone), poly (phenylene sulfide amide), polysulfone, polyvinylidene fluoride, and copolymers containing styrene, methacrylate, or vinylpyridine.
In one arrangement, the block copolymer composition has a first block comprising the copolymer, and each X is independently selected from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl.
In one arrangement, the first block further comprises an electrolyte salt, and the block copolymer composition is an electrolyte. Each X is independently selected from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl. The electrolyte salt may be a lithium salt.
In another embodiment of the invention, an electrochemical cell has an anode configured to absorb and release lithium ions; a cathode comprising cathode active material particles, a conductive additive, a catholyte, and optionally a binder material; a current collector adjacent to an outer surface of the cathode; and a separator region located between the anode and the cathode, the separator region comprising a separator electrolyte configured to facilitate movement of lithium ions back and forth between the anode and the cathode. At least one of the separator electrolyte and the catholyte comprises any of the electrolytes described herein. In one arrangement, the separator electrolyte and the catholyte are the same.
In some arrangements, the electrochemical cell further comprises a cover layer positioned between the cathode and the separator region, the cover layer comprising a cover layer electrolyte. The blanket electrolyte may comprise any of the electrolytes described herein. In one arrangement, the blanket electrolyte and the catholyte are the same.
The anode may include lithium metal, lithium alloys, graphite, and/or silicon. The cathode active material particles may include one or more of the group consisting of lithium iron phosphate, nickel cobalt aluminum oxide, nickel cobalt manganese oxide, lithium manganese phosphate, lithium cobalt phosphate, lithium nickel phosphate, and lithium manganese spinel. The binder material may include polyvinylidene fluoride, poly (ethylene fluoride-co-hexafluoropropylene), polyacrylonitrile, polyacrylic acid, polyethylene oxide, carboxymethyl cellulose, styrene-butadiene rubber, or a combination thereof.
[ description of the drawings ]
The foregoing aspects and others will become apparent to those skilled in the art from the following description of the illustrative embodiments, when read in light of the accompanying drawings.
Fig. 1 is a schematic diagram of one configuration of a lithium battery cell including a catholyte in accordance with an embodiment of the present invention.
Fig. 2 is a schematic view of another configuration of a lithium battery cell including a catholyte and a cathode capping layer according to an embodiment of the present invention.
Fig. 3 is a schematic view of another configuration of a lithium battery cell including a catholyte in accordance with an embodiment of the present invention.
[ detailed description ] embodiments
The preferred embodiments are described in the context of silicone polymers that can be combined with salts (e.g., lithium or other alkali metal salts) to produce ion conducting materials for use in lithium battery cells and the like. However, one skilled in the art will readily appreciate that the materials and methods disclosed herein will be useful in many other applications where high voltage electrolytes are required, particularly where long term stability is important.
These and other objects and advantages of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings.
All publications mentioned herein are incorporated by reference in their entirety for all purposes as if fully set forth herein. All ranges described herein are intended to include all ranges subsumed therein.
In the present disclosure, the terms "negative electrode" and "anode" are both used to describe a negative electrode. Likewise, the terms "positive electrode" and "cathode" are both used to describe a positive electrode.
It is to be understood that the term "lithium metal" or "lithium foil" as used herein with respect to the negative electrode describes pure lithium metal and lithium-rich metal alloys known in the art. Examples of lithium-rich metal alloys suitable for use as the anode include Li-Al, Li-Si, Li-Sn, Li-Hg, Li-Zn, Li-Pb, Li-C, or any other Li-metal alloy suitable for use in a lithium metal battery. Other negative electrode materials that may be used in embodiments of the present invention include materials into which lithium may be intercalated, such as graphite, and other materials that may absorb and release lithium ions, such as silicon, germanium, tin, and alloys thereof. Many of the embodiments described herein relate to batteries that include a solid polymer electrolyte that functions as both an electrolyte and a separator. As is well known in the art, batteries utilizing liquid electrolytes also use inactive separator materials other than liquid electrolytes. Such batteries are also included in embodiments of the present invention.
It is well known that functional groups such as ethers and esters are unstable at 4V or higher, while functional groups such as carbonates and nitriles are stable at 4.2V or higher. Thus, for non-PEO based polymer electrolytes, inclusion of only HV stable functional groups, such as carbonates and nitriles, may be useful when used in high voltage batteries. However, such stable functional groups are highly polar (or have a high dipole moment) and, when incorporated into polymers, may cause polymer chain rigidification, which may result in an increase in glass transition temperature (Tg) and a decrease in ionic conductivity.
Flexible, low Tg polymers such as polysiloxane, polyethylene, polybutadiene, and polycarbosilanes are ideal platforms for incorporating HV stable functional groups such as carbonates and nitriles, as the flexibility of such polymers can balance any rigidity caused by the interaction between these functional groups. Of these low Tg polymers, polysiloxanes are the best choice in terms of ability to synthesize modifications, high thermal stability and high oxidative stability (stable above 4.2V).
In various embodiments of the present invention, the electrochemical properties of a number of low glass transition temperature (low Tg) polysiloxane polymers with polar substituents are described. This Polar Polysiloxane (PPS) polymer also has oxidative stability above 4.2V, making it well suited for use as an electrolyte and/or cathode electrolyte in next generation high energy lithium battery cells using cathode materials such as lithium nickel cobalt aluminum oxide (NCA) and lithium nickel cobalt manganese oxide (NCM).
Homopolymer and copolymer polar polysiloxanes:
in one embodiment of the invention, the use of a polar polysiloxane homopolymer (PPSH) material as a High Voltage (HV) stable electrolyte for lithium battery cells is disclosed. In another embodiment, novel polymeric materials based on polar polysiloxane copolymer (PPSC) materials may also be used as HV stable electrolytes. The general structures of PPSH and PPSC are shown below. Note that the PPSC may be a random copolymer or a block copolymer.
In the homopolymer, z is an integer from 2 to 1000, m and n are integers, and the sum of m and n is from 2 to 1000. X is a polar group. Examples of X include, but are not limited to, cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl (structures shown below). In some embodiments of the invention, each X in the homopolymer is independently selected from the group shown below, and each X in the copolymer is independently selected from the group shown below.
Wherein i is the graft length and is an integer in the range of 1 to 8.
Properties such as solubility, polarity, mechanical strength and conductivity in PPSH and PPSC can be adjusted by varying the graft length i. A larger value of i corresponds to a lower concentration of polar groups X in the polymer. Similarly, a smaller value of i corresponds to a higher concentration of polar groups X in the polymer. The concentration of the polar group X determines the dipole moment, the dielectric constant, the ability to dissolve salts, the ionic conductivity and the mechanical strength of the polymer. Higher concentrations of X increase dipole moment, dielectric constant and the ability to dissolve salts. The conductivity and mechanical properties may reach a maximum at an intermediate value of the X concentration.
Polymer properties such as polarity, ionic conductivity and mechanical strength in PPSH and PPSC can also be adjusted by careful selection of the X group. For example, a sulfone group has a higher dipole moment than a sulfoxide group, and thus a polymer containing a sulfone group has a stronger polarity than a polymer containing a sulfoxide group. Indeed, polymers containing sulfone groups have a higher Tg and higher mechanical strength than polymers containing sulfoxide groups.
There are many possible groups for R. Each R in the homopolymers and copolymers may be independently selected from the groups shown below. In various embodiments of the present invention, R may be any one of:
saturated hydrocarbons, examples of which include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-hexyl, 2-ethylhexyl, and cyclohexyl;
-CH3(methyl group)
-CH2-CH3(Ethyl group)
-CH2-CH2-CH3(n-propyl group)
-CH(CH3)2(isopropyl group)
-C(CH3)3(tert-butyl)
-CH2-(CH2)4-CH3(n-butyl)
-CH2-CH(CH2CH3)-(CH2)3CH3(2-ethylhexyl)
Unsaturated hydrocarbons, examples of which include, but are not limited to, vinyl, allyl, propargyl, norbornene, and cyclopentadienyl;
-CH＝CH2(vinyl)
-CH2-CH＝CH2(allyl)
Aromatic hydrocarbons, examples of which include, but are not limited to, substituted and unsubstituted moieties of phenyl, benzyl, naphthyl, and anthracenyl,
wherein Y can be methyl, ethyl, propyl, n-butyl or tert-butyl;
polymerizable groups, examples of which include, but are not limited to, styrene, acylate (acrylate), norbornene, and epoxy groups;
polymerization initiators, examples of which include, but are not limited to, nitroxide initiators such as 2,2,6, 6-tetramethyl-1-piperidinyloxy and N-tert-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine and atom transfer radical polymerization initiators such as bromoisobutyryl bromide;
examples of crosslinkable groups include, but are not limited to, hydride, vinyl, azidopropyl, aminopropyl, mercaptopropyl, and benzophenone groups.
-H (hydride)
-CH＝CH2(vinyl)
-(CH2)3-N3(azidopropyl)
-(CH2)3-NH2(aminopropyl)
-(CH2)3-SH (mercaptopropyl)
In one embodiment of the invention, R may be any one of methyl, ethyl, N-propyl, isopropyl, tert-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-tert-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine, hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthalene, anthryl, styryl, acylate, norbornene or epoxy groups, or a substituted portion of a phenyl, benzyl, naphthalene, anthryl, styryl, acylate, norbornene or epoxy group, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl.
Properties such as solubility, ionic conductivity and lithium transport number can be adjusted by careful selection of the R group. Polymers containing bulky R groups with hydrophobicity have increased hydrophobicity and decreased polarity, which decreases their ability to dissolve lithium salts, resulting in lower ionic conductivity. For example, cyclohexyl groups are more bulky and more hydrophobic than methyl groups, and thus polymers containing cyclohexyl groups are less polar than polymers containing methyl groups. This weaker polarity reduces the ability to dissolve the lithium salt, which reduces the ionic conductivity of the polymer.
Any of the PPSH and PPSC polymers disclosed herein may be used as an electrolyte when combined with a suitable electrolyte salt.
Polar polysiloxane structures
In one embodiment of the invention, the polar polysiloxane (random or block) copolymer PPSC has two different X groups, X1And X2As followsThe structure is shown.
The sum of m and n is an integer from 2 to 1000. X1And X2Different, and each independently selected from the examples of X listed above. Each R is independently selected from the examples of R listed above.
In another embodiment of the invention, the polar polysiloxane (random or block) copolymer PPSC is a copolymer having two different R groups1And R2And only one X group (polymer with three different repeat units), as shown in the following structure.
The sum of m and n is 2 to 1000, and m and n are integers. R1And R2Different, and each is selected from the examples of R listed above. Each X is independently selected from the examples of X listed above.
In another embodiment of the invention, the polar polysiloxane (random or block) copolymer PPSC is a copolymer with two different R groups R1And R2And two different X groups X1And X2The terpolymer of (4) is represented by the following structure.
The sum of m and n is 2 to 1000, and m and n are integers. R1And R2Different, and each selected from the examples of R listed above. X1And X2Different, and each selected from the examples of X listed above.
In one embodiment of the invention, the copolymer may be formed from two different polar polysiloxane homopolymers and have two different R groups R1And R2And only one X group, as shown in the structure below.
The sum of m and n is 2 to 1000, and m and n are integers. R1And R2Different, and each selected from the examples of R listed above. Each X is independently selected from the examples of X listed above.
In one embodiment of the invention, PPSH has two different X groups, X1And X2And only one R group, as shown in the following structure.
The sum of m and n is 2 to 1000, and m and n are integers. X1And X2Different, and each selected from the examples of X listed above. Each R is independently selected from the examples of R listed above.
In one embodiment of the invention, PPSH may be a block or random copolymer having two or more X and R groups.
In one embodiment of the invention, PPSC and PPSH are terminated on both terminal chain ends by R groups, which are the same as the pendant R groups used elsewhere in the structure shown below.
The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000. The R groups are all the same and are selected from the examples of R listed above. The X groups may or may not be the same, and each X is independently selected from the examples of X listed above.
In one embodiment of the invention, the PPSC and PPSH are R-terminated at both terminal chain ends1End-capped with the group R1The groups are different from the pendant R groups.
The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000. R and R1Different, and each selected from the examples of R listed above. The R groups themselves may be the same or different. The X groups may be the same or different, and each X is independently selected from the examples of X listed above.
In one embodiment of the invention, PPSC and PPSH are capped at each end with two different R groups R, as shown below1And R2And (4) end capping.
The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000. R, R1And R2Different, and each selected from the examples of R listed above. These X groups may be the same or different, and each X is independently selected from the examples of X listed above.
In one embodiment of the invention, the PPSH and PPSC have any of the structures shown below, wherein the pendant R group is methyl (-CH)3) And X is cyanopropyl (-CH)2CH2CH2-CN). The PPSC may be a random or block copolymer. Such PPSH and PPSC polymer materials may be used as electrolytes when electrolyte salts are added. The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000.
In one arrangement, a triblock copolymer based on PPSC and PPSH has endcaps at both chain ends with an initiator group, such as bromoisobutyryl bromide, as shown in the structure below. Such initiator groups may be used to grow mechanically strong polymers from the end groups of PPSC and PPSH, such as polymethyl acrylate (PMA), polybutyl acrylate (PBA), polymethyl methacrylate (PMMA), Polystyrene (PS), polyvinylpyridine (PVP), poly-t-butylstyrene (PtBS), to form tri-or multi-block copolymers. The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000.
In one arrangement, the below shown diblock copolymers based on PPSC and PPSH have endcaps with an initiator group such as bromoisobutyryl bromide on only one of the chain ends. Such initiator groups are useful for growing mechanically robust polymers from PPSC and PPSH, such as polymethyl acrylate (PMA), polybutyl acrylate (PBA), polymethyl methacrylate (PMMA), Polystyrene (PS), polyvinylpyridine (PVP), poly-t-butylstyrene (PtBS). The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000.
In one arrangement, brush or comb copolymers based on PPSC and PPSH may be synthesized using two or more pendant initiator groups, such as bromoisobutyryl bromide, as shown below. Such initiator groups are useful for growing mechanically robust polymers from PPSC and PPSH, such as polymethyl acrylate (PMA), polybutyl acrylate (PBA), polymethyl methacrylate (PMMA), Polystyrene (PS), polyvinylpyridine (PVP), poly-t-butylstyrene (PtBS). In one arrangement, a brush polymer may be obtained by having two or more initiating groups as pendant groups in the PPSC and PPSH molecules. The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000.
PPSH and PPSC may also form random, alternating, block, or graft copolymers with non-silicone based polymers such as Polybutadiene (PBD), Polyethylene (PE), polyphenylene ether (PPE), and/or Polyimide (PI), ionically conductive polymers such as polyethylene oxide (PEO), polyphosphonate (PPN), Polycarbonate (PC), Polydimethylsiloxane (PDMS), and Polyacrylonitrile (PAN) (when R is an atom transfer radical polymerization initiator).
In one arrangement, as shown below, the PPSC and PPSH polymers form a crosslinkable network when R (pendant or end-capped) is a crosslinkable group such as benzophenone. The benzophenone group can be activated by ultraviolet light to generate a carbonyl radical that can recombine to promote cross-linking of the polymer chains. The X groups may be the same or different and are each independently selected from the above examples. The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000.
In another arrangement, as shown below, the PPSC and PPSH polymers form a crosslinkable network when the chain ends are terminated with a crosslinkable group such as benzophenone. R and X are each independently selected from the above examples. The sum of m and n is from 2 to 1000, m and n are integers, and z is in the range from 2 to 1000.
In one arrangement, one or more PPSH or PPCS polymers form a block copolymer with a second polymer, and together they form an ordered nanostructure. The second polymer is not a PPH or PPCS polymer. The ordered nanostructure may comprise a matrix (matrix) formed of a first region composed of a PPCS or PPSH polymer block and a second region composed of a second polymer block. The PPCS/PPSH block may also contain an electrolyte salt.
Conductivity of PPSH:
impedance spectroscopy was used to measure the conductivity of PPSH, where the pendant and capped R groups were methyl, X was cyanopropyl, and z ranged from 10 to 500. PPSH was mixed with various concentrations of LiTFSI and placed as an electrolyte in aluminum symmetrical cells. These measurements were carried out at 80 ℃. The data in Table I show that PPSH is present at 80 deg.CHas a lithium ion conductivity (between 10 wt% (10 wt%) and 30 wt% of LiTFSI of 10) sufficient for use in lithium battery cells-4Of the order of S/cm).
Table I: conductivity of PPSH at 80 ℃
Conductivity of PPSC:
impedance spectroscopy was used to measure the conductivity of PSSC, where the pendant group R was methyl, X was cyanopropyl, and the m: n ratio was 7: 3. PSSC was mixed with various concentrations of LiTFSI and placed as electrolyte in an aluminum symmetrical cell. These measurements were carried out at 80 ℃. The data in table II show that PSSC has sufficient lithium ion conductivity at 80 ℃ for use in lithium battery cells (between 10 and 30 wt% LiTFSI of 10-4Of the order of S/cm).
Table II: conductivity of PPSC at 80 ℃
Voltage stability of PPSH and PPSC electrolyte materials:
the PPSH and PPSC electrolyte materials having conductivities shown in tables I and II were tested for voltage stability using cyclic voltammetry. The device consists of an aluminum working electrode, a lithium reference electrode and a lithium counter electrode. Preparation of PPSH with LiBF4(10 wt% relative to PPSH) of a solution (10 wt%) of propylene carbonate and PPSC in a solution with LiBF4(10 wt% relative to PPSC) solution in propylene carbonate (10 wt%). At room temperature, these solutions were swept from a voltage of 1.38V (open circuit voltage) to 5V and monitored for current response. The occurrence of a surge current at a particular voltage is considered to be the voltage at which PPSH or PPSC undergoes oxidation. Both PPSH and PPSC electrolyte materials have been found to be stable at least up to 4.2V (standard lithium cell operating voltage).
Polar polysiloxane electrolytes
PPS polymer materials can be used as electrolytes when combined with appropriate electrolyte salts. There is no particular limitation on the electrolyte salt that can be used in such a PPS electrolyte. Any electrolyte salt containing an ion determined to be the most ideal charge carrier for the application may be used. It is particularly useful to use an electrolyte salt having a large dissociation constant within the polymer electrolyte. When the electrolyte is used in a cathode, it may be referred to as a catholyte.
Examples of salts suitable for use in any of the electrolytes disclosed herein include, but are not limited to, metal salts selected from the group consisting of chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, sulfonamides, triflates, thiocyanates, perchlorates, borates, or selenides of alkali metals (e.g., lithium, sodium, potassium, and cesium), or of silver, barium, lead, calcium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten, or vanadium. Examples of specific lithium salts include LiSCN, LiN (CN)2、LiClO4、LiBF4、LiAsF6、LiPF6、LiCF3SO3、Li(CF3SO2)2N、Li(CF3SO2)3C、LiN(SO2C2F5)2、LiN(SO2CF3)2、LiN(SO2CF2CF3)2Lithium alkyl fluorophosphates (LiFAP), lithium oxalato borate and other lithium bis (chelated) borates with 5 to 7 membered rings, lithium bis (trifluoromethylsulfonimide) (LiTFSI), LiPF3(C2F5)3、LiPF3(CF3)3、LiB(C2O4)2、LiOTf,LiC(Tf)3Lithium bis- (oxalate) borate (LiBOB), lithium difluoro (oxalate) borate (lidpob), lithium bis- (perfluoroethylsulfonyl) imide (LiBETI), lithium difluoro (oxalate) borate (lidpob), lithium tetracyanoborate (LiTCB), and mixtures thereof.
In other arrangements, for other electrochemical compositions, i.e., for electrochemical compositions in which non-lithium metals are the basis of the battery, electrolytes are prepared by combining the polymers disclosed herein with various non-lithium salts. For example, non-lithium salts, such as aluminum, sodium, potassium, calcium, silver, barium, lead, andsalts of magnesium may be used with their corresponding metals. Specific examples of such salts include, but are not limited to, AgSO3CF3、NaSCN、NaSO3CF3、KTFSI、NaTFSI、Ba(TFSI)2、Pb(TFSI)2And Ca (TFSI)2. The concentration of the metal salt in the electrolyte disclosed herein is 5 wt% to 50 wt%, 5 wt% to 30 wt%, 10 wt% to 20 wt%, or any range contained therein.
In one embodiment of the invention, the PPS electrolyte disclosed herein is used as a catholyte in a lithium battery cell. Referring to fig. 1, a lithium battery cell 100 has an anode 120 configured to absorb and release lithium ions. Anode 120 may be a lithium or lithium alloy foil or may be made of a material capable of absorbing lithium ions therein, such as graphite or silicon. The lithium battery cell 100 also has a cathode 140, which cathode 140 includes cathode active material particles 142, a conductive additive (not shown), a current collector 144, a catholyte 146, and an optional binder (not shown). Catholyte 146 may be any PPS polymer electrolyte disclosed herein. A separator region 160 is present between the anode 120 and the cathode 140. Separator region 160 contains an electrolyte that facilitates lithium ions (or other metal ions that form the basis of a single cell) to move back and forth between anode 120 and cathode 140 as cell 100 is cycled. The separator region 160 may include any electrolyte suitable for such use in a lithium battery cell. In one arrangement, the separator region 160 comprises a porous plastic material saturated with a liquid electrolyte. In another arrangement, the separator region 160 contains a viscous liquid electrolyte or a gel electrolyte. In another arrangement, the separator region 160 comprises a solid polymer electrolyte.
The solid polymer electrolyte used in the separator region 160 can be any such electrolyte suitable for use in a lithium battery. Of course, many such electrolytes also include electrolyte salts that help provide ionic conductivity. Examples of such electrolytes include, but are not limited to, block copolymers comprising ion-conductive blocks and structural blocks constituting an ion-conductive phase and a structural phase, respectively. In one arrangement, the ionically conductive phase comprises one or more PPS, as disclosed herein. The ionically conductive phase may also comprise PPS, for example in a copolymer, in combination with one or more other ionically conductive polymers, such as polyethers, polyamines, polyimides, polyamides, polyalkyl carbonates, polynitriles, perfluoropolyethers, fluorocarbons substituted with high dielectric constant groups (e.g., nitriles, carbonates, and sulfones), and combinations thereof.
The above structural phase may be formed of, for example, polystyrene, hydrogenated polystyrene, polymethacrylate, poly (methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefin, poly (t-butyl vinyl ether), poly (cyclohexyl methacrylate), poly (cyclohexyl vinyl ether), poly (t-butyl vinyl ether), polyethylene, poly (phenylene ether), poly (2, 6-dimethyl-1, 4-phenylene ether) (pxe), poly (phenylene sulfide sulfone), poly (phenylene sulfide ketone), poly (phenylene sulfide amide), polysulfone, fluorocarbon (e.g., polyvinylidene fluoride), or copolymers containing styrene, methacrylate, or vinylpyridine. It is particularly useful if the structural phase is rigid and is in a glassy or crystalline state. More information on such block copolymer electrolytes may be found in U.S. patent 9136562 granted on 9/15/2015, U.S. patent 8889301 granted on 11/18/2014, U.S. patent 8563168 granted on 10/22/2013, and U.S. patent 8268197 granted on 9/18/2012, the entire contents of which are incorporated herein by reference.
In another embodiment of the present invention, a battery cell having a second configuration is described. Referring to fig. 2, the lithium battery cell 200 has an anode 220 configured to absorb and discharge lithium ions. Anode 220 may be a lithium or lithium alloy foil or may be made of a material that can absorb lithium ions into it, such as graphite or silicon. The lithium battery cell 200 also has a cathode 250, which cathode 250 includes cathode active material particles 252, a conductive additive (not shown), a current collector 254, a catholyte 256, an optional binder (not shown), and a capping layer 258. Both the electrolyte in overlayer 258 and catholyte 256 comprise any of the PPS polymer electrolytes disclosed herein. In one arrangement, the electrolyte in the capping layer 258 is the same as the catholyte 256. In another arrangement, the electrolytes in the capping layer 258 and catholyte 256 are different. A separator region 260 is present between the anode 220 and the cathode 250. Separator region 260 contains an electrolyte that facilitates lithium ion movement back and forth between anode 220 and cathode 250 as cell 200 is cycled. As noted above, the separator region may include any electrolyte suitable for use in a lithium battery cell.
In another embodiment of the present invention, a battery cell having a third configuration is described. Referring to fig. 3, the lithium battery cell 300 has an anode 320 configured to absorb and discharge lithium ions. Anode 320 may be a lithium or lithium alloy foil or may be made of a material capable of absorbing lithium ions therein, such as graphite or silicon. The lithium battery cell 300 also has a cathode 340, the cathode 340 including cathode active material particles 342, a conductive additive (not shown), a current collector 344, a cathode electrolyte 346, and an optional binder (not shown). Catholyte 346 may be any of the PPS polymer electrolytes disclosed herein. Between the anode 320 and the cathode 340 there is a separator region 360. Catholyte 346 extends into separator region 360 and facilitates movement of lithium ions back and forth between anode 320 and cathode 340 as cell 300 cycles.
With respect to the embodiments discussed in fig. 1, 2, and 3, suitable cathode active materials include, but are not limited to, LFP (lithium iron phosphate), LMP (lithium metal phosphate, where the metal can be Mn, Co, or Ni), NCA, NCM, high energy NCM, lithium manganese spinel, and combinations thereof. The cathode active material particles may be one or more materials selected from the group consisting of: lithium iron phosphate, nickel cobalt aluminum oxide, nickel cobalt manganese oxide, lithium manganese phosphate, lithium cobalt phosphate, lithium nickel phosphate, and spinel lithium manganese. Suitable conductive additives include, but are not limited to, carbon black, graphite, vapor grown carbon fibers, graphene, carbon nanotubes, and combinations thereof. A binder may be used to hold the cathode active material particles and the conductive additive together. Suitable binders include, but are not limited to, PVDF (polyvinylidene fluoride), PVDF-HFP (polyvinylidene fluoride-co-hexafluoropropylene), PAN (polyacrylonitrile), PAA (polyacrylic acid), PEO (polyethylene oxide), CMC (carboxymethylcellulose), and SBR (styrene-butadiene rubber).
Examples of the invention
The following examples provide details relating to the synthesis of PPSH electrolytes according to the present invention. It should be understood that the following is representative only, and that the invention is not limited to the details set forth in this example.
Poly (cyanopropyl) methylsiloxane was synthesized according to the following scheme:
a solution of polymethylhydrosiloxane (2.2g, 37.2mmol), allyl cyanide (10.0g, 148.8mmol) in dry toluene (12mL) was prepared and maintained at 0 ℃. To this solution was added 0.5mL of 2% platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane catalyst complex (in xylene). The solution was gradually heated to 120 ℃ and IR spectroscopy (from 1270 cm) was used-1The disappearance of the Si — H stretching frequency) to monitor the progress of the reaction. Additional platinum catalyst (0.2mL) was added to the reaction mixture every 12 hours until the reaction was complete. After completion of the reaction, the solution was passed through a plug of celite, and excess allylnitrile and toluene were removed by vacuum distillation. The polymer was dissolved in dichloromethane to prepare a concentrated solution, which was then added to vigorously stirred 2-propanol to precipitate the polymer. The polymer was then obtained by carefully decanting the 2-propanol. The polymer was dried under high vacuum at 50 ℃ overnight.
The present invention has been described herein in considerable detail in order to provide those skilled in the art with information relevant to the application of the novel principles and the construction and use of such specialized components. However, it is to be understood that the invention can be carried out by different equipment, materials and devices, and that various modifications can be made without departing from the scope of the invention itself.
Claims (15)
1. A block copolymer composition comprising:
an ordered nanostructure comprising a matrix of first and second regions:
the first region is formed by association of a first polymer; and
the second region is formed by association of a second polymer;
wherein the first polymer and the second polymer form a first copolymer, wherein the first copolymer is a block copolymer, and wherein the first polymer forms a first block and the second polymer forms a second block; and is
Wherein the first block comprises:
one or more polymers selected from the group consisting of:
a homopolymer having the structure:
and a copolymer having the structure:
wherein each X is independently selected from the group consisting of sulfone, cyanomethyl ester, sulfoxide, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl;
each R is independently selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, t-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, nitroxide, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-t-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine, hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene, epoxy groups, and substituted portions of phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene, epoxy groups, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl;
z is an integer from 2 to 1000; and is
m and n are integers, and the sum of m and n is 2 to 1000; and is
The second block comprises one or more polymers selected from the group consisting of polystyrene, hydrogenated polystyrene, polymethacrylate, poly (methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefin, poly (t-butyl vinyl ether), poly (cyclohexyl methacrylate), poly (cyclohexyl vinyl ether), poly (t-butyl vinyl ether), polyethylene, polyphenylene oxide, poly (2, 6-dimethyl-1, 4-phenylene ether) (PXE), poly (phenylene sulfide sulfone), poly (phenylene sulfide ketone), poly (phenylene sulfide amide), polysulfone, polyvinylidene fluoride, and copolymers containing styrene, methacrylate, or vinylpyridine.
2. The block copolymer composition of claim 1, wherein the first block comprises the copolymer and each X is independently selected from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl.
3. The block copolymer composition of claim 1, wherein the first block further comprises an electrolyte salt, wherein each X is independently selected from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl; and wherein the block copolymer composition is an electrolyte.
4. The polymer composition of claim 3, wherein the electrolyte salt is a lithium salt.
5. An electrochemical cell, comprising:
an anode configured to absorb and release lithium ions;
a cathode comprising cathode active material particles, a conductive additive, a catholyte, and optionally a binder material;
a current collector adjacent to an outer surface of the cathode; and
a separator region between the anode and the cathode, the separator region comprising a separator electrolyte configured to facilitate lithium ion movement back and forth between the anode and the cathode;
wherein at least one of the separator electrolyte and the catholyte comprises the electrolyte of claim 4.
6. The electrochemical cell of claim 5, wherein the separator electrolyte and the catholyte are the same.
7. The electrochemical cell of claim 5, further comprising a cover layer positioned between the cathode and the separator region, the cover layer comprising a cover layer electrolyte comprising the electrolyte of claim 4.
8. The electrochemical cell of claim 7, wherein the cover electrolyte and the catholyte are the same.
9. The electrochemical cell of claim 5, wherein the anode comprises a material selected from the group consisting of lithium metal, lithium alloys, graphite, and silicon.
10. The electrochemical cell of claim 5, wherein the cathode active material particles comprise one or more materials selected from the group consisting of lithium iron phosphate, nickel cobalt aluminum oxide, nickel cobalt manganese oxide, lithium manganese phosphate, lithium cobalt phosphate, lithium nickel phosphate, and lithium manganese spinel.
11. The electrochemical cell of claim 5, wherein the binder material is selected from the group consisting of polyvinylidene fluoride, poly (ethylene fluoride-co-hexafluoropropylene), polyacrylonitrile, polyacrylic acid, polyethylene oxide, carboxymethyl cellulose, styrene-butadiene rubber, and combinations thereof.
12. A polymer composition comprising:
a polymer selected from the group consisting of:
a homopolymer having the structure:
and a copolymer having the structure:
wherein each X is independently selected from the group consisting of sulfone, cyanomethyl ester, sulfoxide, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl;
each R is independently selected from the group consisting of methyl, ethyl, N-propyl, isopropyl, t-butyl, N-hexyl, 2-ethylhexyl, cyclohexyl, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, nitroxide, bromoisobutyryl bromide, 2,6, 6-tetramethyl-1-piperidinyloxy, N-t-butyl-N- (2-methyl-1-phenylpropyl) -O- (1-phenylethyl) hydroxylamine, hydride, azidopropyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene, epoxy groups, and substituted portions of phenyl, benzyl, naphthyl, anthryl, styryl, acylate, norbornene and epoxy groups, wherein the substituent of the substituted moiety is methyl, ethyl, propyl, n-butyl or tert-butyl;
z is an integer from 2 to 1000; and is
m and n are integers, and the sum of m and n is from 2 to 1000.
13. The polymer composition of claim 12, wherein the polymer is a copolymer and each X is independently selected from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl.
14. The polymer composition of claim 12, further comprising an electrolyte salt, wherein each X is independently selected from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate, and perfluoroalkyl, and wherein the polymer is an electrolyte.
15. The polymer composition of claim 14, wherein the electrolyte salt is a lithium salt.
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| US20100239918A1 (en) * | 2009-03-17 | 2010-09-23 | Seeo, Inc | Nanoparticle-block copolymer composites for solid ionic electrolytes |
| CN102272990A (en) * | 2008-11-07 | 2011-12-07 | 西奥公司 | multiple electrolyte electrochemical cells |
| US20110318648A1 (en) * | 2009-03-06 | 2011-12-29 | Seeo, Inc | High ionic conductivity electrolytes from block copolymers of grafted poly(siloxanes-co-ethylene oxide) |
| US20140322614A1 (en) * | 2013-04-29 | 2014-10-30 | Seeo, Inc | Long cycle life lithium sulfur electrochemical cells |
| US20160028114A1 (en) * | 2008-02-13 | 2016-01-28 | Seeo, Inc. | Multi-phase electrolyte lithium batteries |
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| JP2000154254A (en) * | 1998-11-20 | 2000-06-06 | Mitsubishi Paper Mills Ltd | Gel electrolyte for lithium secondary battery |
| US9160003B2 (en) * | 2010-12-21 | 2015-10-13 | Uchicago Argonne, Llc | Polysiloxane binder for lithium ion battery electrodes |
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| US20160028114A1 (en) * | 2008-02-13 | 2016-01-28 | Seeo, Inc. | Multi-phase electrolyte lithium batteries |
| CN102272990A (en) * | 2008-11-07 | 2011-12-07 | 西奥公司 | multiple electrolyte electrochemical cells |
| US20110318648A1 (en) * | 2009-03-06 | 2011-12-29 | Seeo, Inc | High ionic conductivity electrolytes from block copolymers of grafted poly(siloxanes-co-ethylene oxide) |
| US20100239918A1 (en) * | 2009-03-17 | 2010-09-23 | Seeo, Inc | Nanoparticle-block copolymer composites for solid ionic electrolytes |
| US20140322614A1 (en) * | 2013-04-29 | 2014-10-30 | Seeo, Inc | Long cycle life lithium sulfur electrochemical cells |
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