EP3685456A1 - Surface coatings for ceramic electrolyte particles - Google Patents
Surface coatings for ceramic electrolyte particlesInfo
- Publication number
- EP3685456A1 EP3685456A1 EP18853621.3A EP18853621A EP3685456A1 EP 3685456 A1 EP3685456 A1 EP 3685456A1 EP 18853621 A EP18853621 A EP 18853621A EP 3685456 A1 EP3685456 A1 EP 3685456A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- lithium
- ceramic
- electronically
- ceramic electrolyte
- 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
- 229910021525 ceramic electrolyte Inorganic materials 0.000 title claims abstract description 117
- 239000002245 particle Substances 0.000 title claims abstract description 35
- 238000000576 coating method Methods 0.000 title description 3
- 239000002131 composite material Substances 0.000 claims abstract description 57
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- 239000007771 core particle Substances 0.000 claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 33
- 239000010420 shell particle Substances 0.000 claims abstract description 19
- 239000002001 electrolyte material Substances 0.000 claims abstract description 7
- -1 lithium nitrides Chemical class 0.000 claims description 100
- 239000010410 layer Substances 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 239000011244 liquid electrolyte Substances 0.000 claims description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 239000005518 polymer electrolyte Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000002608 ionic liquid Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000006182 cathode active material Substances 0.000 claims description 13
- 239000011245 gel electrolyte Substances 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000002482 conductive additive Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 6
- 239000011029 spinel Substances 0.000 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 5
- 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 claims description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- 239000001989 lithium alloy Substances 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 4
- 125000005910 alkyl carbonate group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical group 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000002825 nitriles Chemical group 0.000 claims description 4
- 239000010702 perfluoropolyether Substances 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920005554 polynitrile Polymers 0.000 claims description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003457 sulfones Chemical group 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical group CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical class [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 3
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 3
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical class [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000329 polyazepine Polymers 0.000 claims description 3
- 229920000323 polyazulene Polymers 0.000 claims description 3
- 229920001088 polycarbazole Polymers 0.000 claims description 3
- 229920002098 polyfluorene Polymers 0.000 claims description 3
- 229920000417 polynaphthalene Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002227 LISICON Substances 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical class C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- RTSKNEFQDKQWGV-UHFFFAOYSA-N [Ge]=O.[V].[Li] Chemical class [Ge]=O.[V].[Li] RTSKNEFQDKQWGV-UHFFFAOYSA-N 0.000 claims description 2
- IPLCZXJSAIDLRI-UHFFFAOYSA-N [Ge]=S.[Li] Chemical class [Ge]=S.[Li] IPLCZXJSAIDLRI-UHFFFAOYSA-N 0.000 claims description 2
- NJVHJTQSGGRHGP-UHFFFAOYSA-K [Li].[Al+3].[Cl-].[Cl-].[Cl-] Chemical class [Li].[Al+3].[Cl-].[Cl-].[Cl-] NJVHJTQSGGRHGP-UHFFFAOYSA-K 0.000 claims description 2
- QLEJXAMHPYMIFG-UHFFFAOYSA-N [O-2].[Al+3].[Si+4].[Li+].[O-2].[O-2].[O-2] Chemical class [O-2].[Al+3].[Si+4].[Li+].[O-2].[O-2].[O-2] QLEJXAMHPYMIFG-UHFFFAOYSA-N 0.000 claims description 2
- ZOJZLMMAVKKSFE-UHFFFAOYSA-N [P]=S.[Li] Chemical class [P]=S.[Li] ZOJZLMMAVKKSFE-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical group N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical group N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 claims description 2
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 claims description 2
- VQYKQHDWCVUGBB-UHFFFAOYSA-N phosphanylidynezirconium Chemical compound [Zr]#P VQYKQHDWCVUGBB-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical group N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- ADDWXBZCQABCGO-UHFFFAOYSA-N titanium(iii) phosphide Chemical compound [Ti]#P ADDWXBZCQABCGO-UHFFFAOYSA-N 0.000 claims description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 claims description 2
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical class P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 claims 1
- 208000020960 lithium transport Diseases 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 43
- 229910010293 ceramic material Inorganic materials 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002776 polycyclohexyl methacrylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
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- 229920005604 random copolymer Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008367 Li-Pb Inorganic materials 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008405 Li-Zn Inorganic materials 0.000 description 1
- 229910011319 Li3xLa Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 229910008293 Li—C Inorganic materials 0.000 description 1
- 229910006614 Li—Hg Inorganic materials 0.000 description 1
- 229910006309 Li—Mg Inorganic materials 0.000 description 1
- 229910006738 Li—Pb Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910007049 Li—Zn Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- ZFHIUTYZUHQBFZ-UHFFFAOYSA-N [Dy].[Tb].[Eu].[Sm] Chemical compound [Dy].[Tb].[Eu].[Sm] ZFHIUTYZUHQBFZ-UHFFFAOYSA-N 0.000 description 1
- DBKXXXFJLUUZDD-UHFFFAOYSA-N [Hf].[W].[Ta] Chemical compound [Hf].[W].[Ta] DBKXXXFJLUUZDD-UHFFFAOYSA-N 0.000 description 1
- FVJYNQXNEKMSMW-UHFFFAOYSA-N [Mn].[Fe].[Cr].[Ca] Chemical compound [Mn].[Fe].[Cr].[Ca] FVJYNQXNEKMSMW-UHFFFAOYSA-N 0.000 description 1
- FLRYWTUGCYGPHE-UHFFFAOYSA-N [Nd].[Pr].[Ba].[Ag] Chemical compound [Nd].[Pr].[Ba].[Ag] FLRYWTUGCYGPHE-UHFFFAOYSA-N 0.000 description 1
- NMKIRVDMEAPBJY-UHFFFAOYSA-N [Ru].[Nb].[Zr].[Y] Chemical compound [Ru].[Nb].[Zr].[Y] NMKIRVDMEAPBJY-UHFFFAOYSA-N 0.000 description 1
- YWQISBLCWBMUCS-UHFFFAOYSA-N [Sr].[Rb].[Ge].[Gd] Chemical compound [Sr].[Rb].[Ge].[Gd] YWQISBLCWBMUCS-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical class [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0065—Solid electrolytes
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
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- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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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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- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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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- H01M2300/0091—Composites in the form of mixtures
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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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
- H01M4/38—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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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
- H01M4/624—Electric conductive fillers
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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, and, more specifically, to composite organic-ceramic electrolytes.
- a composite organic-ceramic electrolyte includes an organic electrolyte in which core/shell particles are dispersed.
- the core/shell particles have a core particle comprising an ionically-conductive ceramic electrolyte material that has a capacity less than 50 mAh/g between 3V and 4.5 V vs. Li/Li + , an electronic conductivity less than 10 "6 S/cm at 30°C, and an ionic conductivity greater than 10 "7 S/cm at 30°C.
- the core/shell particles also have an electronically-conductive outer shell around the core particle, and the electronically-conductive outer shell has an exterior surface that has an electronic conductivity greater than 0.1 S/cm at 30°C.
- the ionic conductivity of the ceramic electrolyte is greater than the ionic conductivity of the organic electrolyte.
- the ceramic electrolyte may be any of lithium lanthanum titanates, lithium lanthanum zirconium oxides, lithium nitrides, lithium aluminas, lithium vanadium germanium oxides, lithium silicon aluminum oxides, lithium aluminum chlorides, lithium phosphorous oxy -nitrides, LISICON, lithium aluminum titanium phosphates, thio-LISICONs, lithium phosphorus sulfides, lithium germanium sulfides, or combinations thereof.
- the organic electrolyte may be a solid polymer electrolyte, a gel electrolyte, or a liquid electrolyte.
- the solid polymer electrolyte includes an electrolyte salt and any of polyethers, polyamines, polyimides, polyamides, poly alkyl carbonates, polynitriles, perfluoro polyethers, polysiloxanes, polyalkoxysiloxanes, polyphosphazines, polyolefins, polydienes, polyesters, fluorocarbon polymers substituted with one or more groups selected from the group consisting of nitriles, carbonates, and sulfones, or combinations thereof.
- the solid electrolyte may have a molecular weight greater than 250 Da.
- the liquid electrolyte includes electrolyte salt and a solvent such as polyethylene glycol dimethyl ether (PEGDME), diethyl carbonate (DEC), ethylene carbonate (EC), propylene carbonate (PC), dimethylformamide (DMF), dimethylcarbonate, acetonitrile, succinonitrile, glutaronitrile, adiponitrile, or combinations thereof.
- a solvent such as polyethylene glycol dimethyl ether (PEGDME), diethyl carbonate (DEC), ethylene carbonate (EC), propylene carbonate (PC), dimethylformamide (DMF), dimethylcarbonate, acetonitrile, succinonitrile, glutaronitrile, adiponitrile, or combinations thereof.
- the liquid electrolyte includes electrolyte salt and an ionic liquid such as an alkyl substituted pyridinium-based ionic liquid, an alkyl substituted pryrolidinium-based ionic liquid, an alkyl substituted pryrolidinium-based ionic liquid, an alkyl substituted ammonium-based ionic liquid, and alkyl substituted piperidinium-based ionic liquid, or combinations thereof.
- an ionic liquid such as an alkyl substituted pyridinium-based ionic liquid, an alkyl substituted pryrolidinium-based ionic liquid, an alkyl substituted pryrolidinium-based ionic liquid, an alkyl substituted ammonium-based ionic liquid, and alkyl substituted piperidinium-based ionic liquid, or combinations thereof.
- anions that may be included in such ionic liquids include, but are not limited to, bis(trifluoromethane)sulfonamide (TFSI), fluoralkylphosphate (FAP), tetracyanoborate (TCB), bis(oxalato)borate (BOB), difluoro(oxalato)borate (DFOB), bis(fluorosulfonyl)imide (FSI), PF 6 , BF 4 anions and combinations thereof.
- TFSI bis(trifluoromethane)sulfonamide
- FAP fluoralkylphosphate
- TCB bis(oxalato)borate
- DFOB difluoro(oxalato)borate
- FSI bis(fluorosulfonyl)imide
- PF 6 PF 6 , BF 4 anions and combinations thereof.
- electrolyte salt that can be used in the organic electrolytes. Any electrolyte salt that includes a lithium i
- electrolyte salts that have a large dissociation constant within the organic electrolyte.
- electrolyte salts include LiPF 6 , LiN(CF 3 S02)2, LiN(FS02)2, Li(CF 3 S0 2 ) 3 C, LiN(S0 2 CF 2 CF 3 ) 2 , LiB(C 2 0 4 ) 2 , and mixtures thereof.
- the core/shell particles are approximately spherical and have average diameters between 10 nm and 100 ⁇ .
- the electronically-conductive outer shell is an electronically-conductive ceramic.
- the electronically-conductive ceramic is any of titanium nitride, zirconium nitride, titanium fluoride, titanium phosphide, zirconium phosphide, zirconium chloride, titanium chloride, titanium bromide, zirconium bromide, iron phosphide, indium tin oxide, lanthanum-doped strontium titanate, yttrium- doped strontium titanate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, or combinations thereof.
- the electronically- conductive ceramic comprises nitrogen.
- the electronically-conductive outer shell includes any of carbon, platinum, gold, silver, titanium, nickel, chrome, copper, aluminum, or combinations thereof.
- the electronically-conductive outer shell is an electronically-conductive polymer that may be any poly(ace ⁇ ylene)s, poly(p-phenylene vinylene)s, poly(pyrrole)s, polycarbazoles, polyindoles, polyazepines, polyanilines, poly(thiophene)s, poly(p-phenylene sulfide)s, poly(fluorene)s, polyphenylenes, polypyrenes, polyazulenes, polynaphthalenes, or combinations thereof.
- an electronically-conductive polymer that may be any poly(ace ⁇ ylene)s, poly(p-phenylene vinylene)s, poly(pyrrole)s, polycarbazoles, polyindoles, polyazepines, polyanilines, poly(thiophene)s, poly(p-phenylene sulfide)s, poly(fluorene)s, polyphenylenes, polypyrenes, polyazulenes, polynaphthalenes
- a composite organic-ceramic electrolyte includes an organic electrolyte in which core/shell particles are dispersed.
- the core/shell particles have a lithium lanthanum titanate core and a titanium nitride shell around the core.
- a cathode includes cathode active material particles, an electronically-conductive additive, a catholyte, and an optional binder material, and a current collector adjacent to an outside surface of the cathode.
- the catholyte may be any of the composite organic-ceramic electrolytes disclosed herein.
- the cathode active material particles may be any of lithium iron phosphate, lithium manganese phosphate, lithium cobalt phosphate, lithium nickel phosphate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese oxide, high-energy lithium nickel cobalt manganese oxide, lithium manganese spinel, lithium manganese nickel spinel, sulfur, vanadium pentoxide, or combinations thereof.
- an electrochemical cell includes an anode configured to absorb and release lithium ions, a cathode comprising cathode active material particles, an electronically-conductive additive, a first 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 contains a separator electrolyte that is configured to facilitate movement of lithium ions back and forth between the anode and the cathode.
- the first catholyte may be any of the composite organic-ceramic electrolytes disclosed herein.
- the anode includes graphite, silicon or lithium titanate
- the separator electrolyte includes any of the composite organic-ceramic electrolytes disclosed herein.
- the anode includes lithium or lithium alloy foil
- the separator electrolyte includes any of the composite organic-ceramic electrolytes electrolyte disclosed herein, and there is an anode overcoat layer adjacent to the anode.
- the anode overcoat layer includes an electrolyte that contains no core/shell ceramic electrolyte particles.
- the second catholyte there is a layer of second catholyte between the cathode and the separator electrolyte, and the second catholyte includes any of the composite organic-ceramic electrolytes disclosed herein.
- the first catholyte and the second catholyte are the same.
- the second catholyte layer comprises a ceramic electrolyte.
- the second catholyte layer may include one or more electronically-conductive surface layers, wherein the one or more electronically-conductive surface layers each has a thickness of 50 nm or less.
- Figure 1 is a schematic cross-section drawing of a core/shell ceramic electrolyte particle, according to an embodiment of the invention.
- Figure 2 is a schematic cross-section drawing of a composite organic-ceramic electrolyte, according to an embodiment of the invention.
- Figure 3 is a schematic cross-section drawing of a battery cell, according to an embodiment of the invention.
- Figure 4 is a schematic cross-section drawing of a battery cell, according to an embodiment of the invention.
- Figure 5 is a schematic cross-section drawing of a battery cell, according to an embodiment of the invention.
- Figure 6 is a schematic cross-section drawing of a battery cell, according to an embodiment of the invention.
- Figure 7 is Nyquist plot that shows AC impedance spectra for two lithium symmetric cells, according to an embodiment of the invention.
- negative electrode and “anode” are both used to mean “negative electrode”.
- positive electrode and “cathode” are both used to mean “positive electrode”.
- lithium metal or “lithium foil,” as used herein with respect to negative electrodes, are meant to include 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, Li-Mg 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.
- organic electrolyte is used throughout this disclosure. It should be understood that such organic electrolytes include organic liquid, gel and solid electrolytes. Some such electrolytes may be polymers, and some may not. Gel electrolytes may contain polymers combined with one or more liquid electrolytes. In a gel electrolyte, the polymer(s) may or may not itself be an electrolyte. It should be understood that such organic electrolytes usually contain electrolyte salts, such as lithium salts, even if it is not stated explicitly. There are no particular restrictions on the electrolyte salt that can be used in the organic electrolytes. Any electrolyte salt that includes a lithium ion can be used. It is especially useful to use electrolyte salts that have a large dissociation constant within the organic electrolyte.
- salts examples include LiPF 6 , LiN(CF 3 S0 2 ) 2 , LiN(FS0 2 ) 2 , Li(CF 3 S0 2 ) 3 C,
- the solid polymer electrolyte may be a dry polymer electrolyte, a block copolymer electrolyte and/or a non- aqueous electrolyte.
- Organic liquid and gel polymer electrolytes can also be used in the embodiments of the invention, either alone as a separator electrolyte in a lithium battery cell or as a component of a composite organic-ceramic electrolyte, according to embodiments of the invention.
- batteries with organic liquid electrolytes may be used with an inactive separator membrane that is distinct from the organic liquid electrolyte.
- ceramic electrolyte as used herein is used to refer to ceramic materials that have a capacity less than 50 mAh/g between 3V and 4.5 V vs.
- a ceramic electrolyte has an ionic conductivity greater than 10 "6 S/cm, greater than 10 "5 S/cm, greater than 10 "4 S/cm, or greater than 10 "3 S/cm at room temperature (30°C).
- the lithium ion diffusion coefficient of a ceramic electrolyte is greater than 1 x 10 "14 m 2 /s, greater than 1 x 10 "13 m 2 /s, or greater than 1 x 10 "12 m 2 /s at 30°C.
- Electrolytes with a high ionic conductivity, a transference number close to one, and good electrochemical stability at voltages larger than 4.0 V are useful for improving the charge and discharge rate performance of high energy density electrochemical cells.
- a variety of ceramic electrolytes including lithium lanthanum titanates (LLTO), lithium lanthanum zirconium oxides (LLZO), lithium ion conducting glass ceramics (e.g., lithium aluminum titanium phosphate (LATP) and lithium phosphorous oxy -nitride (LiPON)), and others have outstanding transport properties and stability at elevated voltages. Such properties are especially useful in a cathode of an electrochemical cell, where enhanced ionic transport may make it possible to use a thicker cathode and thus increase the energy density of the cell.
- LLTO lithium lanthanum titanates
- LLZO lithium lanthanum zirconium oxides
- Li ion conducting glass ceramics e.g., lithium aluminum titanium phosphate (LATP) and lithium phospho
- composites of lithium-ion-conducting ceramic and organic electrolyte materials make superior electrolytes for use in lithium batteries.
- Ceramic material particles provide high conductivity pathways for lithium-ions, enhancing the conductivity of such a composite organic-ceramic electrolyte as compared to less ionically-conductive organic electrolyte material alone.
- the organic electrolyte material provides flexibility, binding, and space-filling properties, mitigating the tendency of rigid ceramic materials to break or delaminate. Materials and techniques that reduce the resistance to charge transport across the interface between organic electrolytes and ceramic electrolytes are disclosed herein.
- a core/shell ceramic electrolyte particle has an outer shell whose electronic conductivity is greater than the electronic conductivity of the interior of the particle.
- a core/shell ceramic electrolyte particle 105 is shown in cross section in the schematic drawing in Figure 1.
- the core/shell ceramic electrolyte particle 105 has a ceramic electrolyte core particle 110 that is ionically conductive, and an outer shell 120 that is electronically-conductive.
- the ionic conductivity of the ceramic electrolyte core particle 110 is greater than 1 x 10 "7 S/cm, greater than 1 x 10 "5 S/cm, greater than 1 x 10 "3 S/cm, or any range subsumed therein at room temperature (30°C).
- the electronic conductivity at the outer shell is greater than 1 x 10 "4 S/cm, greater than 1 x 10 "3 S/cm, greater than 1 x 10 "2 S/cm, greater than 0.1 S/cm, greater than 10 S/cm, greater than 50 S/cm, greater than 100 S/cm, greater than 1000 S/cm, greater than 10,000 S/cm, or any range subsumed therein at room temperature (30°C).
- core/shell ceramic electrolyte particles are used in composite organic-ceramic electrolytes, they have been shown to have reduced interfacial resistance as compared with ceramic electrolyte particles that do not have enhanced electronic conductivity on their outer surfaces (i.e. , with no shell that has higher electronic conductivity than the ceramic electrolyte).
- the core/shell ceramic electrolyte particles are approximately spherical or equiaxed and have an average diameter between 10 nm and 100 ⁇ , between 300 nm and 10 ⁇ , between 500 nm and 2 ⁇ , or any range subsumed therein.
- the shell thickness of the core/shell ceramic electrolyte particle is between 1 nm and 50 nm, between 2 nm and 30 nm, between 5 nm and 10 nm, or any range subsumed therein.
- the shell is continuous and covers all or nearly all of the surface of the core particle. In other embodiments, the shell is discontinuous and covers between 75% and 50% of the surface of the core particle, between 50% and 25% of the surface of the core particle, or any range subsumed therein.
- Examples of ceramic electrolyte materials that can be used as the core for core/shell particles in the embodiments of the invention include, but are not limited to, materials listed in Table I below.
- the core in a core/shell particle has a crystalline morphology, and in some embodiments the core in a core/shell particle has an amorphous or glass morphology.
- lithium lanthanum titanate can be described by the formula, Li 3x La(2/3)- x Ti03.
- the values of x are given by 0 ⁇ x ⁇ 0.7, 0.02 ⁇ x ⁇ 0.30, 0.04 ⁇ x ⁇ 0.17, or 0.09 ⁇ x ⁇ 0.13.
- Various other ceramic electrolyte materials in Table I are shown as having chemical formulas in which the stoichiometries are shown with variables such as w, x, y, and z.
- each of the compounds listed in Table I may have a variety of stoichiometries. Those shown in Table I are meant to be examples only. It should be understood that the examples in Table I are representative only, and that the invention is not limited by any particular values of the stoichiometric variables.
- any of the ceramics listed in Table I also contains one or more of a variety of dopants.
- a list of exemplary dopants is shown below: sodium magnesium aluminum potassium
- electronically-conductive ceramic materials are used as the shells in the core/shell particles disclosed herein.
- examples of such electronically-conductive ceramic materials include, but are not limited to, materials listed in Table II below.
- the electronically-conductive ceramic material used in the shells in the core/shell particles disclosed herein is a material that has properties that may also make it useful as a cathode active material.
- the shell in a core/shell particle has a crystalline morphology, and in some embodiments the shell in a core/shell particle has an amorphous or glass morphology.
- the ceramic electrolyte core particle 110 is sintered in a nitrogen environment to form the outer shell 120.
- the outer shell 120 is formed from reaction of nitrogen with the ceramic electrolyte core particle material to form a new nitrogen-containing phase.
- the outer shell 120 is formed from diffusion of nitrogen into the surface of the ceramic electrolyte core particle 110 to form a nitrogen-doped region.
- a core particle of lithium lanthanum titanate (LLTO) is sintered in nitrogen, which produces either a nitrogen-doped LLTO shell or a shell of another phase such as TiN. Examples of other gases that can be used as environments for sintering ceramic electrolyte core particles to produce
- electronically-conductive outer shells include, but are not limited to, nitrogen, ammonia, hydrogen, chlorine-containing gases, fluorine-containing gases, phosphorus-containing gases, bromine-containing gases, and iodine-containing gases, either alone or combined with inert gas.
- the schematic drawing in Figure 1 shows a sharp boundary between the ceramic electrolyte core particle 1 10 and the outer shell 120 of the core/shell ceramic electrolyte particle 105, it should be understood that diffuse boundaries are also possible.
- the outermost surface 125 may contain electronically-conductive material that has the highest electronic conductivity (and lowest ionic conductivity), and the electronic conductivity (ionic conductivity) may decrease (increase) within the outer shell 120 as one gets closer to the ceramic electrolyte core particle 110.
- the outer shell 120 is applied to the ceramic electrolyte core particle 1 10 by sputtering an electronically-conductive ceramic material.
- materials that can be used to coat the particles include, but are not limited to, those shown in Table II above.
- the outer shell 120 is applied to the ceramic electrolyte core particle 1 10 using a sol-gel technique.
- metal alkoxides such as titanium(IV) tert-butoxide or tetraethyl orthosilicate, can dissolve in a solvent and form a gel. Core particles are suspended in the gel. The solvent can be removed and the core particles heated to remove the organic components, allowing a coating to density and/or crystallize into a ceramic outer shell 120.
- the electronically-conductive outer shell 120 is applied to the ceramic electrolyte core particle 110 using mechanical milling. Through mechanical impaction, the electronically-conductive material is applied and adhered to the surface of the ceramic electrolyte core particle.
- the outer shell 120 in the core/shell ceramic electrolyte particle 105 are used as the outer shell 120 in the core/shell ceramic electrolyte particle 105 disclosed herein.
- carbon or metals such as platinum, gold, silver, titanium, nickel, chrome, copper, aluminum, or combinations thereof may be used.
- Such materials may be applied to the ceramic electrolyte core particle 1 10 by sputtering, evaporation, or other metal and carbon coating methods.
- electronically-conductive polymers such as poly(acetylene)s, poly(p-phenylene vinylene)s, poly(pyrrole)s, polycarbazoles, polyindoles, polyazepines, polyanilines, poly(thiophene)s, poly(p-phenylene sulfide), poly(fluorene)s, polyphenylenes, polypyrenes, polyazulenes, polynaphthalenes, or combinations thereof are used as the outer shell 120 in the core/shell ceramic electrolyte particle 105 disclosed herein.
- Such materials may be dissolved in a solvent and applied to core particles by dipping the particles into the solution and evaporating the solvent.
- the core/shell ceramic electrolyte particles disclosed above can be mixed with an organic electrolyte to form a composite organic- ceramic electrolyte that has improved ionic transport properties and electrochemical stability in a battery cell, as compared to the organic electrolyte alone.
- a composite organic- ceramic electrolyte 200 is shown in cross section in the schematic drawing in Figure 2.
- the composite organic-ceramic electrolyte 200 contains core/shell ceramic electrolyte particles 205, as seen in Figure 1 , distributed within a solid, gel, or liquid organic electrolyte 230.
- the organic electrolyte 230 is any ionically- conductive solid polymer that is appropriate for use in a Li battery.
- solid polymer electrolytes include, but are not limited to, homopolymers, random copolymers, graft copolymers, and block copolymers that contain ionically-conductive blocks and structural blocks that make up ionically-conductive phases and structural phases,
- the ionically-conductive polymers or phases may contain one or more linear or non-linear polymers such as polyethers, polyamines, polyimides, polyamides, poly alkyl carbonates, polynitriles, perfluoro polyethers, polysiloxanes, polyalkoxysiloxanes, polyphosphazines, poly olefins, polydienes, polyesters, and fluorocarbon polymers substituted with high dielectric constant groups such as nitriles, carbonates, and sulfones, and combinations thereof.
- linear or non-linear polymers such as polyethers, polyamines, polyimides, polyamides, poly alkyl carbonates, polynitriles, perfluoro polyethers, polysiloxanes, polyalkoxysiloxanes, polyphosphazines, poly olefins, polydienes, polyesters, and fluorocarbon polymers substituted with high dielectric constant groups such as nitriles, carbonates,
- linear polymers can also be used in combination as graft copolymers with polysiloxanes, polyalkoxysiloxanes, polyphosphazines, poly olefins, and/or polydienes to form the conductive phase.
- the structural phase may be made of polymers such as polystyrene, hydrogenated polystyrene, polymethacrylate, poly(methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefins, poly(t-but l 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
- the organic electrolyte 230 is any ionically- conductive organic liquid electrolyte that is appropriate for use in a Li battery.
- liquid electrolytes that can be used in a composite organic-ceramic electrolyte include, but are not limited to, solvents with electrolyte salts, ionic liquids with electrolyte salts, and combinations thereof.
- organic electrolytes may be used in combination to form electrolyte mixtures.
- batteries with organic liquid electrolytes may be used with an inactive separator membrane that is distinct from the organic liquid electrolyte.
- electrolyte salt that can be used with the solvents and ionic liquids listed in Table III above. Any electrolyte salt that includes a lithium ion can be used. It is especially useful to use electrolyte salts that have a large dissociation constant within the organic electrolyte. Examples of such salts include LiPF 6 , LiN(CF 3 S0 2 ) 2 , LiN(FS0 2 ) 2 , Li(CF 3 S0 2 ) 3 C, LiN(S0 2 CF 2 CF 3 ) 2 , LiB(C 2 0 4 ) 2 , and mixtures thereof.
- anions that can be included in the ionic liquids listed in Table III above include, but are not limited to, bis(trifluoromethane)sulfonamide (TFSI), fluoralkylphosphate (FAP), tetracyanoborate (TCB), bis(oxalato)borate (BOB), difluoro(oxalato)borate (DFOB), bis(fluorosulfonyl)imide (FSI), PF 6 , BF4 anions and combinations thereof.
- TFSI bis(trifluoromethane)sulfonamide
- FAP fluoralkylphosphate
- TCB tetracyanoborate
- BOB bis(oxalato)borate
- DFOB difluoro(oxalato)borate
- FSI bis(fluorosulfonyl)imide
- the organic electrolyte 230 is any ionically- conductive gel electrolyte that is appropriate for use in a Li battery.
- gel electrolytes that can be used in a composite organic-ceramic electrolyte include, but are not limited to, polymers such as polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly(vinyl pyrrolidinone) (PVP), polyvinyl acetate) (PVAC), poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP), and combinations thereof mixed with a liquid electrolyte such as those listed above.
- PEO polyethylene oxide
- PAN polyacrylonitrile
- PMMA poly(methyl methacrylate)
- PVDF poly(vinylidene fluoride)
- PVDF poly(vinyl pyrrolidinone)
- PVAC poly
- 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 and released, such as graphite, silicon, or lithium titanate.
- the lithium battery cell 300 also has a cathode 340 that includes cathode active material particles 342, an optional 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 composite organic-ceramic electrolytes disclosed here.
- the separator region 360 contains an electrolyte that facilitates movement of lithium ions back and forth between the anode 320 and the cathode 340 as the cell 300 cycles.
- the separator region 360 may include any electrolyte that is suitable for such use in a lithium battery cell.
- the separator region 360 contains a porous plastic separator material that is soaked with a liquid electrolyte.
- the separator region 360 contains a liquid (in
- the separator region 360 contains a solid polymer electrolyte. In another arrangement, the separator region 360 contains a ceramic electrolyte or a composite organic- ceramic electrolyte.
- a battery cell with a second configuration is described.
- a lithium battery cell 400 has an anode 420 that is configured to absorb and release lithium ions.
- the anode 420 may be made of a material into which lithium ions can be absorbed and released, such as graphite, silicon, or lithium titanate.
- the lithium battery cell 400 also has a cathode 440 that includes cathode active material particles 442, an optional electronically-conductive additive (not shown), a current collector 444, a catholyte 446, and an optional binder (not shown).
- the catholyte 446 may be any of the composite organic-ceramic electrolytes disclosed here.
- the catholyte 446 extends from the cathode 440 into the separator region 460 and facilitates movement of lithium ions back and forth between the anode 420 and the cathode 440 as the cell 400 cycles.
- the catholyte 440 is a liquid composite organic-ceramic electrolyte and it is used in combination with an inactive separator membrane (not shown) in the separator region 460.
- a battery cell with a third configuration is described.
- a lithium battery cell 500 has an anode 520 that is configured to absorb and release lithium ions.
- the anode 520 may be a lithium or lithium alloy foil or it may be made of a material into which lithium ions can be absorbed and released, such as graphite, silicon, or lithium titanate.
- the lithium battery cell 500 also has a cathode 540 that includes cathode active material particles 542, an optional electronically- conductive additive (not shown), a current collector 544, a catholyte 546, and an optional binder (not shown).
- the catholyte 546 may be any of the composite organic-ceramic electrolytes disclosed here.
- the separator region 560 Between the anode 520 and the cathode 540.
- the catholyte 546 extends into the separator region 560.
- the catholyte 546 is a liquid composite organic-ceramic electrolyte and it is used in combination with an inactive separator membrane (not shown) in the separator region 560.
- the separator region 560 also contains an anode overcoat layer 562 adjacent to the anode 520, which contains an electrolyte that is different from the catholyte 546.
- the anode overcoat layer 562 may include any other electrolyte that is suitable for such use in a lithium battery cell.
- the anode overcoat layer 562 contains an inactive separator membrane (not shown) that is soaked with a liquid electrolyte. In another arrangement, the anode overcoat layer 562 contains a gel electrolyte. In another arrangement, the anode overcoat layer 562 contains a solid polymer electrolyte. In another arrangement, the anode overcoat layer 562 contains no ceramic electrolyte particles. The electrolytes in the separator region 560 facilitate movement of lithium ions back and forth between the anode 520 and the cathode 540 as the cell 500 cycles.
- a battery cell with a fourth configuration is described.
- a lithium battery cell 600 has an anode 620 that is configured to absorb and release lithium ions.
- the anode 620 may be a lithium or lithium alloy foil or it may be made of a material into which lithium ions can be absorbed and released, such as graphite, silicon, or lithium titanate.
- the lithium battery cell 600 also has a cathode 640 that includes cathode active material particles 642, an optional electronically- conductive additive (not shown), a current collector 644, a catholyte 646, an optional binder (not shown).
- the catholyte 646 may be any of the electrolytes disclosed here, including composite organic-ceramic electrolytes, or any other electrolyte appropriate for use as a catholyte in a lithium battery cell.
- the cathode overcoat layer 648 comprises a single-ion conducting material that allows transport of Li + ions, but not anions, such as any of the ionically-conductive ceramic materials listed in Table I.
- the cathode overcoat layer 648 also has one or more electronically-conductive surface layers (not shown).
- One such electronically- conductive surface layer may be on the surface of the cathode overcoat layer 648 that faces the cathode 640.
- Another such electronically-conductive surface layer may be on the surface of the cathode overcoat layer 648 that faces the separator region 660.
- the electronically- conductive surface layer(s) may include, for example, any of the electronically-conductive materials disclosed herein, such as those listed in Table II.
- the electronically-conductive surface layer(s) on layer 648 have a thickness of 50 nm or less.
- the separator region 660 is between the anode 620 and the cathode overcoat layer 648.
- the separator region 660 contains an electrolyte that facilitates movement of lithium ions back and forth between the anode 620 and the cathode 640 as the cell 600 cycles.
- the separator region 660 may include any electrolyte that is suitable for such use in a lithium battery cell.
- the separator region 660 contains an inactive separator membrane that is soaked with a liquid electrolyte.
- the separator region 660 contains a viscous liquid or gel electrolyte.
- the separator region 660 contains a solid polymer electrolyte.
- the separator region 660 contains a ceramic electrolyte or a composite organic-ceramic electrolyte, according to embodiments of the invention.
- suitable cathode active materials include, but are not limited to, lithium iron phosphate (LFP), lithium metal phosphate (LMP) in which the metal can be manganese, cobalt, or nickel, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), high-energy NCM, lithium manganese spinel, lithium manganese nickel spinel, sulfur, vanadium pentoxide, and combinations thereof.
- 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), SBR (styrene-butadiene rubber), and combinations thereof.
- solid polymer electrolytes for use in separator regions 360, 460, 560, 660, and as the anode overcoat layer 562 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.
- solid polymer electrolytes include, but are not limited to, homopolymers, random copolymers, graft copolymers, and block copolymers that contain ionically- conductive blocks and structural blocks that make up ionically-conductive phases and structural phases, respectively.
- the ionically-conductive polymers or phases may contain one or more linear or non-linear polymers such as poly ethers, polyamines, polyimides, polyamides, poly alkyl carbonates, polynitriles, perfluoro polyethers, polysiloxanes, polyalkoxysiloxanes, polyphosphazines, polyolefins, polydienes, polyesters, and
- fluorocarbon polymers substituted with high dielectric constant groups such as nitriles, carbonates, and sulfones, and combinations thereof.
- the linear polymers can also be used in combination as graft copolymers with polysiloxanes, polyalkoxysiloxanes, polyphosphazines, polyolefins, and/or polydienes to form the conductive phase.
- the structural phase may 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
- the polymer electrolyte 230 has a molecular weight greater than 250 Da, greater than 1,000 Da, greater than 5,000 Da, greater than 10,000 Da, greater than 20,000 Da, greater than 100,000 Da, or any range subsumed therein. Further information about such block copolymer electrolytes can be found in US Patent number 9,136,562, issued September 15, 2015, US Patent number 8,889,301, issued November 18, 2014, US Patent number 8,563,168, issued October 22, 2013, and US Patent number 8,268,197, issued September 18, 2012, all of which are included by reference herein.
- organic liquid electrolytes for use in separator regions 360, 460, 560, 660, and as the anode overcoat layer 562 can be any ionically-conductive liquid electrolyte that is appropriate for use in a Li battery.
- liquid electrolytes that can be used in a composite organic-ceramic electrolyte have been listed above with reference to Table III.
- liquid electrolytes may be used in combination to form electrolyte mixtures.
- batteries with organic liquid electrolytes may be used with an inactive separator membrane that is distinct from the organic liquid electrolyte.
- organic gel electrolytes for use in separator regions 360, 460, 560, 660, and as the anode overcoat layer 562 can any ionically-conductive gel electrolyte that is appropriate for use in a Li battery.
- gel electrolytes that can be used in a composite organic-ceramic electrolyte include, but are not limited to, polymers such as polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), polyvinyl pyrrolidinone) (PVP), poly(vinyl acetate) (PVAC), poly(vinylidene fluoride)-co- hexafluoropropylene (PVDF-HFP), and combinations thereof mixed with a liquid electrolyte such as those listed in Table III above.
- polymers such as polyethylene oxide (PEO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), polyvinyl pyrrolidinone) (PVP), poly(vinyl acetate) (PVAC), poly(vinylidene fluoride)-co- he
- Lithium symmetric cells were prepared with solid polymer electrolyte/ceramic electrolyte/solid polymer electrolyte stacks between lithium electrodes using three different types of ceramic electrolyte.
- the ceramic electrolyte in Cell 1 was an LLTO pellet that had been sintered in air at 1100°C for 12 hours.
- the ceramic electrolyte in Cell 2 was the same LLTO but had been sintered in nitrogen at 1100°C for 24 hours instead of in air.
- the solid polymer electrolytes were the same and were PEO/PS block copolymer electrolyte with LiTFSI salt.
- FIG. 7 is Nyquist plot that shows AC impedance spectra for the two lithium symmetric cells.
- the Nyquist plot shows the negative imaginary portion of the impedance, which is related to capacitance as a function of the real portion of impedance, which is related to resistance.
- the larger the diameter of the semicircular plot the larger the resistance to charge transfer through the cell.
- Cell 1 has the poorest charge transfer, and Cell 2 had much better charge transfer, indicating that resistance across the interface between the polymer electrolyte and the ceramic electrolyte was lower when the ceramic electrolyte material was sintered in nitrogen.
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