EP3601299A1 - Polar polysiloxane electrolytes for lithium batteries - Google Patents
Polar polysiloxane electrolytes for lithium batteriesInfo
- Publication number
- EP3601299A1 EP3601299A1 EP17902302.3A EP17902302A EP3601299A1 EP 3601299 A1 EP3601299 A1 EP 3601299A1 EP 17902302 A EP17902302 A EP 17902302A EP 3601299 A1 EP3601299 A1 EP 3601299A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- groups
- lithium
- electrolyte
- poly
- group
- 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.)
- Pending
Links
- -1 polysiloxane Polymers 0.000 title claims abstract description 178
- 239000003792 electrolyte Substances 0.000 title claims abstract description 73
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 39
- 229920001296 polysiloxane Polymers 0.000 title abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 22
- 229920001400 block copolymer Polymers 0.000 claims description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 19
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 19
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 19
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 18
- 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-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
- 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 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
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 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
- 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 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
- 239000012965 benzophenone Substances 0.000 claims description 11
- 229920001519 homopolymer Polymers 0.000 claims description 11
- 150000004678 hydrides Chemical class 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
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000006182 cathode active material Substances 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 9
- 125000005577 anthracene group Chemical group 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
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical group 0.000 claims description 9
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- MQMJQPYOEGFMAZ-UHFFFAOYSA-N anthracene;styrene Chemical compound C=CC1=CC=CC=C1.C1=CC=CC2=CC3=CC=CC=C3C=C21 MQMJQPYOEGFMAZ-UHFFFAOYSA-N 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 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
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- 229920000069 polyphenylene sulfide 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
- 239000002033 PVDF binder Substances 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 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
- 239000011159 matrix material 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
- 239000004926 polymethyl methacrylate Substances 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
- 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
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims 4
- 239000005518 polymer electrolyte Substances 0.000 abstract description 10
- 239000010406 cathode material Substances 0.000 abstract description 5
- 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
- 150000002118 epoxides Chemical group 0.000 description 14
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 239000003999 initiator Substances 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
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- 239000002001 electrolyte material Substances 0.000 description 5
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-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
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001566 impedance spectroscopy Methods 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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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 239000002861 polymer material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910001560 Li(CF3SO2)2N Inorganic materials 0.000 description 1
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- 229910008367 Li-Pb Inorganic materials 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 208000020960 lithium transport Diseases 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
- 229910052749 magnesium Chemical class 0.000 description 1
- 239000011777 magnesium Chemical class 0.000 description 1
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- 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
- 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
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 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
- 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
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 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
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003346 selenoethers Chemical class 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
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 238000012360 testing method Methods 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
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 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
Classifications
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
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- 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
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- H01M10/052—Li-accumulators
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
- H01M2300/0022—Room temperature molten salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- 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
Definitions
- This invention relates generally to electrolytes for lithium battery cells, and, more specifically, to electrolytes that are especially suited for use in high voltages cells.
- next-generation cathode materials such as NCA (lithium nickel cobalt aluminum oxide) and NCM (lithium nickel cobalt manganese oxide) in order to exploit their potentially high gravimetric energy densities (as high as 300-500 Wh/kg), their good rate capabilities and their long-term stability.
- Cells made with such oxidic materials often operate at higher voltages (e.g. , as high as 4.5V) than do cells (e.g., 3.6-3.8V) with olivine cathode materials such as LFP (lithium iron phosphate). Electrolytes that have been stable at the lower voltages of LFP cells may have difficulty operating at the higher voltages.
- Polyethyleneoxide (PEO) based electrolytes that are commonly used in conventional solid-state lithium batteries are known to be stable only at the lower voltages (e.g., lower than 4.0V) and may have difficulty operating at these new higher voltages, especially in the cathode. Degradation, in the form of oxidation, may lead to capacity fade early in the life of a cell.
- lower voltages e.g., lower than 4.0V
- Figure 1 is a schematic illustration of one configuration of a lithium battery cell that contains a catholyte, according to an embodiment of the invention.
- FIG. 2 is a schematic illustration of another configuration of a lithium battery cell that contains a catholyte and a cathode overlay er, according to an embodiment of the invention.
- FIG. 3 is a schematic illustration of another configuration of a lithium battery cell that contains a catholyte, according to an embodiment of the invention.
- a polymer composition includes a homo polymer with the structure:
- a polymer composition includes a copolymer with the structure:
- An electrolyte salt may be added to either the polymer or the copolymer shown above to make them useful as electrolyte materials. Examples of useful salts are listed below.
- the electrolyte salt is a lithium salt.
- a block copolymer composition in another embodiment, includes an ordered nanostructure that includes a matrix of first domains formed by an association of first polymers and second domains formed by an association of second polymers.
- the first polymers and the second polymers form first copolymers.
- the first copolymers are block copolymers in which the first polymers form first blocks and the second polymers form second blocks.
- the first blocks include one or more of a homopolymer and a copolymer with the following structure
- the second blocks may include one or more polymers such as polystyrene, hydrogenated polystyrene, polymethacrylate, poly(methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefins, poly(t-butyl vinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), poly(t-butyl vinyl ether), polyethylene, poly(phenylene oxide), poly(2,6-dimethyl-l,4-phenylene oxide) (PXE), poly(phenylene sulfide), poly(phenylene sulfide sulfone), poly(phenylene sulfide ketone), poly(phenylene sulfide amide), polysulfone, polyvinylidene fluoride, and copolymers that contain styrene, methacrylate, or vinylpyridine, poly
- an electrolyte material includes an electrolyte salt and a homo polymer with the structure:
- an electrolyte includes an ordered
- nanostructure comprising a matrix of first domains formed by an association of first polymers and second domains formed by an association of second polymers.
- the first polymers and the second polymers form first copolymers that may be block copolymers in which the first polymers form first blocks and the second polymers form second blocks.
- the first blocks may include polymer selected from the group consisting of: and a copolymer with the structure: wherein each X is selected independently from the group consisting of cyano, sulfone, cyanomethyl ester, sulfoxide, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate and perfluoroalkyl groups; each R is selected independently from the group consisting of methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, n-hexyl, 2-ethylhexyl, cyclohexy, vinyl, allyl, propargyl, norbomene, cyclopentadienyl, nitroxide, bromo-isobutry bromide, 2,2,6,6- tetramethy 1- 1 - piperidiny loxy , n-tertpbuty l-n-(
- the second blocks may include one or more polymers selected from the group consisting of polystyrene, hydrogenated polystyrene, polymethacrylate, poly(methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefins, poly(t-butyl vinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), poly(t- butyl vinyl ether), polyethylene, poly(phenylene oxide), poly(2,6-dimethyl-l ,4-phenylene oxide) (PXE), poly(phenylene sulfide), poly(phenylene sulfide sulfone), poly(phenylene sulfide ketone), poly(phenylene sulfide amide), polysulfone, polyvinylidene fluoride, and copolymers that contain styrene, methacrylate,
- the block copolymer composition has first blocks that comprise the copolymer and each X is selected independently from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate and perfluoroalkyl groups.
- the first blocks also include an electrolyte salt
- the block copolymer composition is an electrolyte.
- Each X is selected independently from the group consisting of cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate and perfluoroalkyl groups.
- the electrolyte salt may be a lithium salt.
- an electrochemical cell has an anode configured to absorb and release lithium ions; a cathode comprising cathode active material particles, an electronically-conductive additive, a catholyte, and an optional binder material; a current collector adjacent to an outside surface of the cathode; and a separator region 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 includes any of the electrolytes described herein. In one arrangement, the separator electrolyte and the catholyte are the same.
- the electrochemical cell also has an overlayer between the cathode and the separator region, the overlayer comprising an overlayer electrolyte.
- the overlayer electrolyte may include any of the electrolytes described herein.
- the overlayer electrolyte and the catholyte are the same.
- the anode may include lithium metal, lithium alloy, graphite and/or silicon.
- the cathode active material particles may include one or more 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 difluoride, poly(vinylidene fluoride-co-hexafluoropropylene, polyacrylonitrile, polyacrylic acid, polyethylene oxide, carboxymethyl cellulose, styrene- butadiene rubber, or combinations thereof.
- organosilicon polymers that can be combined with salts (e.g. , lithium or other alkali metal salts) to create ionically conductive materials for use in lithium battery cells and the like.
- salts e.g. , lithium or other alkali metal salts
- the skilled artisan will readily appreciate, however, that the materials and methods disclosed herein will have application in a number of other contexts where high-voltage electrolytes are desirable, particularly where long- term stability is important.
- negative electrode and “anode” are both used to describe a negative electrode.
- positive electrode and “cathode” are both used to describe a positive electrode.
- lithium metal or “lithium foil,” as used herein with respect to negative electrodes, describe both pure lithium metal and lithium-rich metal alloys as are known in the art.
- lithium rich metal alloys suitable for use as anodes 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 lithium metal batteries.
- Other negative electrode materials that can be used in the embodiments of the invention include materials in which lithium can intercalate, such as graphite, and other materials that can absorb and release lithium ions, such as silicon, germanium, tin, and alloys thereof.
- batteries with solid polymer electrolytes which serve the functions of both electrolyte and separator.
- batteries with liquid electrolytes use an inactive separator material that is distinct from the liquid electrolyte.
- Such batteries are also included in the embodiments of the invention.
- Flexible, low Tg polymers such as polysiloxane, polyethylene, polybutadiene, and polycarbosilane are ideal platforms for incorporating HV-stable functional groups such as carbonates and nitriles because the flexibility of such polymers may balance any rigidity caused by interaction among such functional groups.
- polysiloxane is the best candidate in terms of the ability for synthetic modification, high thermal stability and high oxidative stability (stable above 4.2 V).
- electrochemical properties for a number of low- glass-transition-temperature (low Tg) polysiloxane polymers with polar substituents are described.
- Such polar polysiloxane (PPS) polymers are oxidatively stable above 4.2 V, making them ideal for use as electrolytes and/or catholytes in next-generation high energy lithium battery cells that use cathode materials such as lithium nickel cobalt aluminum oxide (NCA) and lithium nickel cobalt manganese oxide (NCM).
- polar polysiloxane homopolymer (PPSH) materials as high voltage (HV) stable electrolytes for lithium battery cells
- novel polymeric materials based on polar polysiloxane copolymer (PPSC) materials can also be used as HV stable electrolytes.
- Generalized structures for PPSH and PPSC are shown below. Note that the PPSC may be either a random copolymer or a block copolymer.
- z is an integer that ranges from 2 to 1000
- m and n are integers
- the sum of m and n ranges from 2 to 1000
- X is a polar group. Examples for X include but are not limited to cyano, sulfone, sulfoxide, cyanomethyl ester, pyrrolidone, cyclic carbamate, phosphonate, phosphate, carbonate and perfluoroalkyl groups (structures shown below).
- each X in the homopolymer is chosen independently from the groups shown below, and each X in the copolymer is chosen independently from the groups shown below.
- i is the graft length and is an integer with a range of 1 to 8.
- Properties such as solubility, polarity, mechanical strength and conductivity in PPSH and PPSC can be modulated by changing the graft length, i. Larger values for i correspond to lower concentrations of polar groups X in the polymer. Similarly, smaller values for i, correspond to higher concentrations of polar groups X in the polymer.
- the concentration of polar groups 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, the dielectric constant, and the ability to dissolve salts. Conductivity and mechanical properties may have maxima at intermediate values of X concentration.
- Polymer properties such as polarity, ionic conductivity and mechanical strength in PPSH and PPSC can also be adjusted by careful choice of X group.
- sulfone groups have higher dipole moments than do sulfoxide groups, so polymers that contain sulfone groups have stronger polarity than do polymers that contain sulfoxide groups. It is also true that, polymers that contain sulfone groups have a higher Tg and greater mechanical strength than do polymers that contain sulfoxide groups.
- R there are many possible groups for R.
- Each R in the homopolymer and in the copolymer may be chosen independently from the groups shown below.
- R may be any of the following:
- - a saturated hydrocarbon.
- examples include but are not limited to methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, n-hexyl, 2-ethylhexyl, and cyclohexyl groups.
- -CH 3 (Methyl)
- an unsaturated hydrocarbon examples include but are not limited to vinyl, allyl, propargyl, norbomene, and cyclopentadienyl groups.
- an aromatic hydrocarbon examples include but are not limited to substituted and unsubstituted moieties of phenyl, benzyl, napthalene, and anthracene groups.
- Y may be a methyl, ethyl, propyl, n-butyl or t-butyl group.
- styrene examples include but are not limited to styrene, acylate, norbornene, and epoxide groups.
- styrene acrylate
- epoxide acrylate
- a polymerization initiator examples include but are not limited to nitroxide initiators such as 2,2,6,6-tetramethyl-l-piperidinyloxy and n-tertpbutyl-n-(2-methyl-l- phenylpropyl)-O-(l-phenylethyl)hudroxylamine) and atom transfer radical polymerization initiators such as bromo-isobutry bromide groups.
- nitroxide initiators such as 2,2,6,6-tetramethyl-l-piperidinyloxy and n-tertpbutyl-n-(2-methyl-l- phenylpropyl)-O-(l-phenylethyl)hudroxylamine
- atom transfer radical polymerization initiators such as bromo-isobutry bromide groups.
- cross-linkable group examples include but are not limited to hydride, vinyl, azidopropyl, aminopropyl, mercaptopropyl, and benzophenone groups.
- -H hydride
- R may be any of methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, n-hexyl, 2-ethylhexyl, cyclohexy, vinyl, allyl, propargyl, norbornene, cyclopentadienyl, bromo-isobutry bromide, 2,2,6,6- tetramethyl-1- piperidinyloxy, n-tertpbutyl- n-(2-methyl-l-phenylpropyl)-0-(l-phenylethyl)hudroxylamine), hydride, azido propyl, mercaptopropyl, benzophenone, aminopropyl, phenyl, benzyl, napthalene, anthracene styrene, acylate, norbornene, or epoxide groups or substitute
- any of the PPSH and PPSC polymers disclosed herein may be used as an electrolyte when combined with an appropriate electrolyte salt.
- a polar polysiloxane (random or block) copolymer PPSC has two different X groups, Xi and X 2 , as shown in the structure below.
- m and « is an integer that ranges from 2 to 1000.
- Xi and X2 are not the same, and each is chosen independently from the examples for X listed above.
- Each R is chosen independently from the examples for R listed above.
- a polar polysiloxane (random or block) copolymer PPSC is a terpolymer (polymer with three different repeat units) with two different R groups, Ri and R2, and only one X group as show in the structure below.
- Ri and R2 are not the same, and each is chosen from the examples for R listed above.
- Each X is chosen independently from the examples for X listed above.
- a polar polysiloxane (random or block) copolymer PPSC is a terpolymer with two different R groups, Ri and R2, and two different X groups, Xi and X 2 , as shown in the structure below.
- Ri and R2 are not the same, and each is chosen from the examples for R listed above.
- Xi and X2 are not the same, and each is chosen from the examples for X listed above.
- a copolymer can be formed from two distinct polar polysiloxane homopolymers and has two different R groups, Ri and R2, and only one X group as shown in the structure below.
- Ri and R2 are not the same, and each is chosen from the examples for R listed above.
- Each X is chosen independently from the examples for X listed above.
- a PPSH has two different X groups, Xi and X 2 , and only one R group as shown in the structure below.
- n ranges from 2 to 1000, and m and n are integers.
- Xi and X2 are not the same, and each is chosen from the examples for X listed above.
- Each R is chosen independently from the examples for R listed above.
- PPSH can either be a block or a random copolymer with two or more X and R groups.
- PPSC and PPSH are end-capped on both terminal chain ends with R groups that are identical to the pendant R groups used elsewhere in the structures as shown below.
- the sum of m and n ranges from 2 to 1000, m and « are integers, and z ranges from 2 to 1000.
- the R groups are all the same and are chosen from the examples for R listed above.
- the X groups may or may not be the same, and each X is chosen independently from the examples for X listed above.
- PPSC and PPSH are end-capped on both terminal chain ends with Ri groups that are different from the pendant R groups, as shown below.
- R and Ri are not the same and each is chosen from the examples for R listed above.
- the R groups themselves may or may not be the same.
- the X groups may or may not be the same, and each X is chosen independently from the examples for X listed above.
- PPSC and PPSH are capped on each end with two different R groups, Ri and R2, as shown below.
- m and « ranges from 2 to 1000
- m and n are integers
- z ranges from 2 to 1000.
- R, Ri, and R2 are not the same and each is chosen from the examples for R listed above.
- the X groups may or may not be the same, and each X is chosen independently from the examples for X listed above.
- PPSH and PPSC have any of the structures shown below, in which the pendant R groups are methyl (-CH3) groups and X is a cyanopropyl group (-CH2CH2CH2-CN).
- the PPSC may a random or a block copolymer.
- electrolyte salt such PPSH and PPSC polymer materials may be used as electrolytes.
- the sum of m and n ranges from 2 to 1000, m and n are integers, and z ranges from 2 to 1000.
- triblock copolymers based-on PPSC and PPSH have end-capping on both chain ends with initiator groups such as bromoisobutryl bromide as shown in the structures below.
- initiator groups can be used to grow mechanically robust polymers such as polymethylacrylates (PMA), polybutylacrylates (PBA), polymethylmethacrylates (PMMA), polystyrene (PS), polyvinylpyridine (PVP), polytert-butylstyrene (PtBS) from the end groups of PPSC and PPSH, resulting in tri- or multi-block copolymers.
- PMA polymethylacrylates
- PBA polybutylacrylates
- PMMA polymethylmethacrylates
- PS polystyrene
- PVP polyvinylpyridine
- PtBS polytert-butylstyrene
- diblock copolymers based-on PPSC and PPSH have end-capping on only one of the chain ends with an initiator group such as bromoisobutryl bromide as shown below.
- an initiator group such as bromoisobutryl bromide as shown below.
- Such initiator groups can be used to grow mechanically robust polymers such as polymethylacrylates (PMA), polybutylacrylates (PBA), polymethylmethacrylates (PMMA), polystyrene (PS), polyvinylpyridine (PVP), polytert-butylstyrene (PtBS) from PPSC and PPSH.
- PMA polymethylacrylates
- PBA polybutylacrylates
- PMMA polymethylmethacrylates
- PS polystyrene
- PVP polyvinylpyridine
- PtBS polytert-butylstyrene
- brush or comb type copolymers based-on PPSC and PPSH can be synthesized using two or more pendant initiator groups such as bromoisobutryl bromide as shown below.
- initiator groups can be used to grow mechanically robust polymers such as polymethylacrylates (PMA), polybutylacrylates (PBA), polymethylmethacrylates (PMMA), polystyrene (PS), polyvinylpyridine (PVP), polytert-butylstyrene (PtBS) from PPSC and PPSH.
- brush type polymers can be obtained by having two or more initiating groups as pendants in PPSC and PPSH molecules. The sum of m and n ranges from 2 to 1000, m and n are integers, and z ranges from 2 to 1000. 3
- PPSH and PPSCs can also form random copolymers, alternating copolymers, block copolymers or graft copolymers (when R is an atom transfer radical polymerization initiator) with non-siloxane based polymers such polybutadiene (PBD), polyethylene (PE),
- PBD polybutadiene
- PE polyethylene
- PPE polyphenyleneoxide
- PI polyimide
- ion-conducting polymers such as polyethyleneoxide (PEO), polyphosphonate (PPN), polycarbonate (PC), polydimethylsiloxame (PDMS) and polyacrylonitrile (PAN).
- PPSC and PPSH polymers form a cross-linkable network when R (the pendant or end cap) is a crosslinkable group such as benzophenone as shown below.
- R the pendant or end cap
- the benzophenone group can be activated by UV light to generate a ketyl radial that can undergo recombination to facilitate crosslinking of polymer chains.
- the X groups may or may not be the same, and each is chosen independently from examples shown above.
- the sum of m and n ranges from 2 to 1000, m and n are integers, and z ranges from 2 to 1000.
- PPSC and PPSH polymers form a cross-linkable network when the chain-ends are capped with a cross-linkable group such as benzophenone as shown below.
- R and X are each chosen independently from examples shown above. The sum of m and n ranges from 2 to 1000, m and n are integers, and z ranges from 2 to 1000.
- one or more PPSH or PPCS polymers form block copolymers with second polymers, and together they form an ordered nanostructure.
- the second polymers are not PPH or PPCS polymers.
- the ordered nanostructure may contain a matrix of first domains made up of PPCS or PPSH polymer blocks and second domains made up of second polymer blocks.
- the PPCS/PPSH blocks may also include an electrolyte salt.
- Impedance spectroscopy was used to measure conductivities of PPSH in which the pendant and end-capped R groups were methyl groups, X was a cyanopropyl group and z ranges from 10 to 500.
- the PPSH was mixed with various concentrations of LiTFSI and placed as the electrolyte in aluminum symmetric cells. The measurements were made at 80°C.
- the data in Table I shows that PPSH has sufficient lithium ion conductivity (on the order of 10 "4 S/cm between 10 to 30 wt.% LiTFSI) at 80°C to be useful in lithium battery cells.
- Impedance spectroscopy was used to measure conductivities of PSSC in which the pendant R groups were methyl groups, X was a cyanopropyl group, and the m:n ratio was 7:3.
- the PSSC was mixed with various concentrations of LiTFSI and placed as the electrolyte in aluminum symmetric cells. The measurements were made at 80°C.
- the data in Table II shows that PSSC has sufficient lithium ion conductivity (on the order of 10 "4 S/cm between 10 to 30 wt.% LiTFSI) at 80°C to be useful in lithium battery cells.
- Cyclic voltammetry was used to test the voltage stabilities of the PPSH and PPSC electrolyte materials whose conductivities are shown in Table I and II.
- the setup consisted of an aluminum working electrode, a lithium reference electrode, and a lithium counter electrode.
- Solutions of PPSH in propylene carbonate (10 wt%) with LiBF 4 (10 wt% with respect to PPSH) and solutions of PPSC in propylene carbonate (10 wt% ) with L1BF4 (10 wt% with respect to PPSC) were made. The solutions were subjected to voltage sweeps from 1.38 V (open circuit voltage) to 5 V at room temperature, and the current responses were monitored.
- the onset of surging current at a particular voltage is considered to be the voltage at which PPSH or PPSC undergoes oxidation.
- Both PPSH and PPSC electrolyte materials were found to be stable at least up to 4.2V, the standard lithium battery cell operating voltage.
- PPS polymer materials may be used as electrolytes when they are combined with appropriate electrolyte salts.
- electrolyte salt that can be used in such PPS electrolytes.
- Any electrolyte salt that includes the ion identified as the most desirable charge carrier for the application can be used. It is especially useful to use electrolyte salts that have a large dissociation constant within the polymer electrolyte.
- an electrolyte is used in the cathode, it can be referred to as a catholyte.
- Examples of appropriate salts for any electrolyte 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, thiocynates, perchlorates, borates, or selenides of alkali metals such as lithium, sodium, potassium and cesium, or silver, barium, lead, calcium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten or vanadium.
- metal salts selected from the group consisting of chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, sulfonamides, triflates, thiocynates, perchlorates, bor
- lithium salts examples include LiSCN, LiN(CN) 2 , L1CIO4, L1BF4, LiAsFe, LiPFe, L1CF3SO3, Li(CF 3 S0 2 ) 2 N, Li(CF 3 S0 2 ) 3 C,
- LiBOB lithium bis-(oxalato)borate
- LiDFOB lithium difluoro(oxalato)borate
- LiBETI lithium-bis (perfluoroethylsulfonyl)imide
- LiDFOB lithium difluoro(oxalato)borate
- LiTCB lithium tetracyanoborate
- electrolytes are made by combining the polymers disclosed herein with various kinds of non-lithium salts.
- non-lithium salts such as salts of aluminum, sodium, potassium, calcium, silver, barium, lead and magnesium can be used with their corresponding metals.
- Specific examples of such salts include, but are not limited to AgS0 3 CF 3 , NaSCN, NaS0 3 CF 3 , KTFSI, NaTFSI, Ba(TFSI) 2 , Pb(TFSI) 2 , and Ca(TFSI) 2 .
- Concentration of metal salts in the electrolytes disclosed herein range from 5 to 50 wt%, 5 to 30 wt%, 10 to 20 wt%, or any range subsumed therein.
- a lithium battery cell 100 has an anode 120 that is configured to absorb and release lithium ions.
- the anode 120 may be a lithium or lithium alloy foil or it may be made of a material into which lithium ions can be absorbed such as graphite or silicon.
- the lithium battery cell 100 also has a cathode 140 that includes cathode active material particles 142, an electronically-conductive additive (not shown), a current collector 144, a catholyte 146, and an optional binder (not shown).
- the catholyte 146 may be any of the PPS polymer electrolytes disclosed here.
- the separator region 160 contains an electrolyte that facilitates movement of lithium ions (or another metal ions that form the basis of the cell) back and forth between the anode 120 and the cathode 140 as the cell 100 cycles.
- the separator region 160 may include any electrolyte that is suitable for such use in a lithium battery cell.
- the separator region 160 contains a porous plastic material that is soaked with a liquid electrolyte.
- the separator region 160 contains a viscous liquid or gel electrolyte.
- the separator region 160 contains a solid polymer electrolyte.
- a solid polymer electrolyte for use in separator regionl60 can be any such electrolyte that is appropriate for use in a Li battery.
- electrolytes also include electrolyte salt(s) that help to provide ionic conductivity.
- electrolytes include, but are not limited to, block copolymers that contain ionically-conductive blocks and structural blocks that make up ionically-conductive phases and structural phases, respectively.
- the ionically-conductive phase contains one or more PPSs, as disclosed herein.
- the ionically-conductive phase may also contain PPSs in combination, such as in copolymers, with one or more other ionically-conductive polymers such as poly ethers, polyamines, polyimides, polyamides, poly alkyl carbonates, polynitriles, perfluoro polyethers, fluorocarbon polymers substituted with high dielectric constant groups such as nitriles, carbonates, and sulfones, and combinations thereof.
- PPSs in combination, such as in copolymers, with one or more other ionically-conductive polymers such as poly ethers, polyamines, polyimides, polyamides, poly alkyl carbonates, polynitriles, perfluoro polyethers, fluorocarbon polymers substituted with high dielectric constant groups such as nitriles, carbonates, and sulfones, and combinations thereof.
- the structural phase can be made of polymers such as polystyrene, hydrogenated polystyrene, polymethacrylate, poly(methyl methacrylate), polyvinylpyridine,
- polyvinylcyclohexane polyimide, polyamide, polypropylene, polyolefins, poly(t-butyl vinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), poly(t-butyl vinyl ether), polyethylene, poly(phenylene oxide), poly(2,6-dimethyl-l,4-phenylene oxide) (pxe), poly(phenylene sulfide), poly(phenylene sulfide sulfone), poly(phenylene sulfide ketone), poly(phenylene sulfide amide), polysulfone, fluorocarbons, such as polyvinylidene fluoride, or copolymers that contain styrene, methacrylate, or vinylpyridine.
- fluorocarbons such as polyvinylidene fluoride, or copolymers that contain styrene, methacrylate, or vinylpyridine.
- a battery cell with a second configuration is described.
- a lithium battery cell 200 has an anode 220 that is configured to absorb and release lithium ions.
- the anode 220 may be a lithium or lithium alloy foil or it may be made of a material into which lithium ions can be absorbed such as graphite or silicon.
- the lithium battery cell 200 also has a cathode 250 that includes cathode active material particles 252, an electronically-conductive additive (not shown), a current collector 254, a catholyte 256, an optional binder (not shown), and an overcoat layer 258.
- Both the electrolyte in the overcoat layer 258 and the catholyte 256 contain any of the PPS polymer electrolytes disclosed here. In one arrangement, the electrolyte in the overcoat layer 258 and the catholyte 256 are the same. In another arrangement, the electrolyte in the overcoat layer 258 and the catholyte 256 are different.
- the separator region 260 contains an electrolyte that facilitates movement of lithium ions back and forth between the anode 220 and the cathode 250 as the cell 200 cycles.
- the separator region may include any electrolyte that is suitable for such use in a lithium battery cell, as described above.
- a battery cell with a third configuration is described.
- a lithium battery cell 300 has an anode 320 that is configured to absorb and release lithium ions.
- the anode 320 may be a lithium or lithium alloy foil or it may be made of a material into which lithium ions can be absorbed such as graphite or silicon.
- the lithium battery cell 300 also has a cathode 340 that includes cathode active material particles 342, an electronically-conductive additive (not shown), a current collector 344, a catholyte 346, and an optional binder (not shown).
- the catholyte 346 may be any of the PPS polymer electrolytes disclosed here.
- the catholyte 346 extends into the separator region 360 and facilitates movement of lithium ions back and forth between the anode 320 and the cathode 340 as the cell 300 cycles.
- suitable cathode active materials include, but are not limited to, LFP (lithium iron phosphate), LMP (lithium metal phosphate in which 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 lithium manganese spinel.
- Suitable electronically- conductive additives include, but are not limited to, carbon black, graphite, vapor-grown carbon fiber, graphene, carbon nanotubes, and combinations thereof.
- a binder can be used to hold together the cathode active material particles and the electronically conductive additive.
- Suitable binders include, but are not limited to, PVDF (polyvinylidene difluoride), PVDF-HFP (poly(vinylidene fluoride-co-hexafluoropropylene), PAN (polyacrylonitrile), PAA (polyacrylic acid), PEO (polyethylene oxide), CMC (carboxymethyl cellulose), and SBR (styrene-butadiene rubber).
- PVDF polyvinylidene difluoride
- PVDF-HFP poly(vinylidene fluoride-co-hexafluoropropylene
- PAN polyacrylonitrile
- PAA polyacrylic acid
- PEO polyethylene oxide
- CMC carbboxymethyl cellulose
- SBR styrene-butadiene rubber
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