US20230163309A1 - Silicon based lithium ion battery and improved cycle life of same - Google Patents
Silicon based lithium ion battery and improved cycle life of same Download PDFInfo
- Publication number
- US20230163309A1 US20230163309A1 US17/532,549 US202117532549A US2023163309A1 US 20230163309 A1 US20230163309 A1 US 20230163309A1 US 202117532549 A US202117532549 A US 202117532549A US 2023163309 A1 US2023163309 A1 US 2023163309A1
- Authority
- US
- United States
- Prior art keywords
- active material
- material layer
- thickness
- current collector
- anode
- 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.)
- Abandoned
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 51
- 239000010703 silicon Substances 0.000 title claims abstract description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 56
- 229910001416 lithium ion Inorganic materials 0.000 title description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 13
- 239000011149 active material Substances 0.000 claims abstract description 84
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000002296 pyrolytic carbon Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 34
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 210000004027 cell Anatomy 0.000 description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 239000000243 solution Substances 0.000 description 47
- 229920002312 polyamide-imide Polymers 0.000 description 39
- 239000002002 slurry Substances 0.000 description 39
- 229920000642 polymer Polymers 0.000 description 38
- 239000004962 Polyamide-imide Substances 0.000 description 34
- 239000000203 mixture Substances 0.000 description 32
- 230000008569 process Effects 0.000 description 29
- 239000000654 additive Substances 0.000 description 28
- 239000010410 layer Substances 0.000 description 23
- 239000011247 coating layer Substances 0.000 description 22
- 239000002356 single layer Substances 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 229920002125 Sokalan® Polymers 0.000 description 18
- 230000002378 acidificating effect Effects 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 16
- -1 LiTDI Inorganic materials 0.000 description 14
- 238000009472 formulation Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 12
- 239000004584 polyacrylic acid Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000011888 foil Substances 0.000 description 11
- 239000011863 silicon-based powder Substances 0.000 description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- 229960004418 trolamine Drugs 0.000 description 10
- 238000000197 pyrolysis Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007833 carbon precursor Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000011856 silicon-based particle Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000003490 calendering Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000002482 conductive additive Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 3
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 3
- 239000004376 Sucralose Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- BAQAVOSOZGMPRM-QBMZZYIRSA-N sucralose Chemical compound O[C@@H]1[C@@H](O)[C@@H](Cl)[C@@H](CO)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 BAQAVOSOZGMPRM-QBMZZYIRSA-N 0.000 description 3
- 235000019408 sucralose Nutrition 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 2
- NBFWIISVIFCMDK-UHFFFAOYSA-N 2,3,4,5-tetrahydroxyhexanoic acid Chemical compound CC(O)C(O)C(O)C(O)C(O)=O NBFWIISVIFCMDK-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 102000004366 Glucosidases Human genes 0.000 description 2
- 108010056771 Glucosidases Proteins 0.000 description 2
- NYHBQMYGNKIUIF-UUOKFMHZSA-N Guanosine Chemical compound C1=NC=2C(=O)NC(N)=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O NYHBQMYGNKIUIF-UUOKFMHZSA-N 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 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 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 235000001727 glucose Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 235000010356 sorbitol Nutrition 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- XZKUCJJNNDINKX-HGLHLWFZSA-N (2r,3s,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4s)-3,4,5-trihydroxy-5-(hydroxymethyl)oxolan-2-yl]methoxy]oxane-3,4,5-triol;hydrate Chemical compound O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)C(O)(CO)O1 XZKUCJJNNDINKX-HGLHLWFZSA-N 0.000 description 1
- QCVNMNYRNIMDKV-QGZVFWFLSA-N (3r)-2'-[(4-bromo-2-fluorophenyl)methyl]spiro[pyrrolidine-3,4'-pyrrolo[1,2-a]pyrazine]-1',2,3',5-tetrone Chemical compound FC1=CC(Br)=CC=C1CN1C(=O)[C@@]2(C(NC(=O)C2)=O)N2C=CC=C2C1=O QCVNMNYRNIMDKV-QGZVFWFLSA-N 0.000 description 1
- DTRGDWOPRCXRET-UHFFFAOYSA-N (9Z,11E,13E)-4-Oxo-9,11,13-octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCC(=O)CCC(O)=O DTRGDWOPRCXRET-UHFFFAOYSA-N 0.000 description 1
- DTRGDWOPRCXRET-SUTYWZMXSA-N (9e,11e,13e)-4-oxooctadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCC(=O)CCC(O)=O DTRGDWOPRCXRET-SUTYWZMXSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- XHJGXOOOMKCJPP-UHFFFAOYSA-N 2-[tert-butyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(C(C)(C)C)CCO XHJGXOOOMKCJPP-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- MIKUYHXYGGJMLM-GIMIYPNGSA-N Crotonoside Natural products C1=NC2=C(N)NC(=O)N=C2N1[C@H]1O[C@@H](CO)[C@H](O)[C@@H]1O MIKUYHXYGGJMLM-GIMIYPNGSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- LKDRXBCSQODPBY-JDJSBBGDSA-N D-allulose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@H]1O LKDRXBCSQODPBY-JDJSBBGDSA-N 0.000 description 1
- NYHBQMYGNKIUIF-UHFFFAOYSA-N D-guanosine Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(CO)C(O)C1O NYHBQMYGNKIUIF-UHFFFAOYSA-N 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- PNNNRSAQSRJVSB-SLPGGIOYSA-N Fucose Natural products C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O PNNNRSAQSRJVSB-SLPGGIOYSA-N 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 102000005548 Hexokinase Human genes 0.000 description 1
- 108700040460 Hexokinases Proteins 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- SHZGCJCMOBCMKK-DHVFOXMCSA-N L-fucopyranose Chemical compound C[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-DHVFOXMCSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- YXVXMURDCBMPRH-UHFFFAOYSA-N Lirinidine Natural products C1C2=CC=CC=C2C2=C(O)C(OC)=CC3=C2C1N(C)CC3 YXVXMURDCBMPRH-UHFFFAOYSA-N 0.000 description 1
- 239000005913 Maltodextrin Substances 0.000 description 1
- 229920002774 Maltodextrin Polymers 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- ORJVQPIHKOARKV-UHFFFAOYSA-N Nuciferine Natural products C1C2=CC=CC=C2C2=C(OC)C(OC)=CC3=C2C1N(C)CC3 ORJVQPIHKOARKV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- 229920005740 STYROFAN® Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 108020000005 Sucrose phosphorylase Proteins 0.000 description 1
- KJADKKWYZYXHBB-XBWDGYHZSA-N Topiramic acid Chemical compound C1O[C@@]2(COS(N)(=O)=O)OC(C)(C)O[C@H]2[C@@H]2OC(C)(C)O[C@@H]21 KJADKKWYZYXHBB-XBWDGYHZSA-N 0.000 description 1
- 239000004963 Torlon Substances 0.000 description 1
- 229920003997 Torlon® Polymers 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- GBXZONVFWYCRPT-JGWLITMVSA-N [(2r,3s,4r,5r)-3,4,5,6-tetrahydroxy-1-oxohexan-2-yl] dihydrogen phosphate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](C=O)OP(O)(O)=O GBXZONVFWYCRPT-JGWLITMVSA-N 0.000 description 1
- GBXZONVFWYCRPT-KVTDHHQDSA-N [(2s,3s,4r,5r)-3,4,5,6-tetrahydroxy-1-oxohexan-2-yl] dihydrogen phosphate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](C=O)OP(O)(O)=O GBXZONVFWYCRPT-KVTDHHQDSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 210000004712 air sac Anatomy 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- ILOJFJBXXANEQW-UHFFFAOYSA-N aminooxy(phenyl)borinic acid Chemical compound NOB(O)C1=CC=CC=C1 ILOJFJBXXANEQW-UHFFFAOYSA-N 0.000 description 1
- 229920005550 ammonium lignosulfonate Polymers 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WXNRAKRZUCLRBP-UHFFFAOYSA-N avridine Chemical compound CCCCCCCCCCCCCCCCCCN(CCCN(CCO)CCO)CCCCCCCCCCCCCCCCCC WXNRAKRZUCLRBP-UHFFFAOYSA-N 0.000 description 1
- 229950010555 avridine Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 108010042194 dextransucrase Proteins 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 229960000304 folic acid Drugs 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 1
- 150000002270 gangliosides Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229940029575 guanosine Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229940035034 maltodextrin Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- WYLLBTPEHIVUKV-UHFFFAOYSA-N n,2-dimethyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)(C)C WYLLBTPEHIVUKV-UHFFFAOYSA-N 0.000 description 1
- ZYWUVGFIXPNBDL-UHFFFAOYSA-N n,n-diisopropylaminoethanol Chemical compound CC(C)N(C(C)C)CCO ZYWUVGFIXPNBDL-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- ORJVQPIHKOARKV-OAHLLOKOSA-N nuciferine Chemical compound C1C2=CC=CC=C2C2=C(OC)C(OC)=CC3=C2[C@@H]1N(C)CC3 ORJVQPIHKOARKV-OAHLLOKOSA-N 0.000 description 1
- XCOHAFVJQZPUKF-UHFFFAOYSA-M octyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)C XCOHAFVJQZPUKF-UHFFFAOYSA-M 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940095574 propionic acid Drugs 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 229950004123 ranirestat Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229960004394 topiramate Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-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
- 239000002966 varnish Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
-
- 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
- aspects of the present disclosure relate to energy generation and storage. More specifically, certain embodiments of the disclosure are directed to battery electrodes, battery cells, and/or batteries with improved cycle life.
- a rechargeable battery experiences periods of charging and periods discharging. These charge-discharge cycles reduce a storage capacity of the of battery and thus reduce the life of the battery.
- a battery and/or battery anode are substantially shown in and/or described in connection with at least one of the figures, as set forth more completely in the claims.
- FIG. 1 is a diagram of a battery with a silicon-dominant anode, in accordance with an example embodiment of the disclosure.
- FIG. 2 A is a flow diagram of a direct coating process for fabricating a cell with a silicon-dominant electrode, in accordance with an example embodiment of the disclosure.
- FIG. 2 B is a flow diagram for of an alternative process for lamination of electrodes, in accordance with an example embodiment of the disclosure.
- FIG. 3 illustrates slurry viscosity versus mixing time, in accordance with an example embodiment of the disclosure.
- FIG. 4 illustrates the results of thermal gravimetric analysis (TGA) of dry WPAI, in accordance with an example embodiment of the disclosure.
- FIG. 5 illustrates an adhesion test for a silicon-dominant anode with water-soluble acidified PAI and water-based acidic polymer solution additive, in accordance with an example embodiment of the disclosure.
- FIG. 6 illustrates a silicon-dominant anode after a winding test, in accordance with an example embodiment of the disclosure.
- FIG. 7 illustrates normalized discharge capacity of a cell with water-soluble acidified PAI and water-based acidic polymer solution additive anode compared to a standard cell with NMP-based slurry laminated anode, in accordance with an example embodiment of the disclosure.
- FIG. 8 illustrates slurry viscosity versus temperature, in accordance with an example embodiment of the disclosure.
- FIG. 9 illustrates electrochemical performance of anodes in pouch cells, in accordance with an example embodiment of the disclosure.
- FIG. 10 illustrates capacity retention of single-layer and five-layer pouch cells during cycle life based on 2 C(4.2 V)/0.5 C(2.75 V) cycles.
- FIG. 11 illustrates capacity retention of single-layer and five-layer pouch cells during cycle life based on 4 C (4.2 V)/0.5 C (3.2 V) cycles.
- FIG. 12 illustrates capacity retention of pressed and not pressed pouch cells during cycle life based on 2 C (4.2 V)/0.5 C (2.75 V) cycles.
- FIG. 13 illustrates capacity retention of single-layer pouch cells having anodes manufacture per three different formulations.
- FIG. 1 is a diagram of a battery with silicon-dominant anodes, in accordance with an example embodiment of the disclosure.
- a battery 100 comprising a separator 103 sandwiched between an anode 101 and a cathode 105 , with current collectors 107 A and 107 B.
- a load 109 coupled to the battery 100 illustrating instances when the battery 100 is in discharge mode.
- the term “battery” may be used to indicate a single electrochemical cell, a plurality of electrochemical cells formed into a module, and/or a plurality of modules formed into a pack.
- FIG. 1 is a very simplified example merely to show the principle of operation of a lithium ion cell. Examples of realistic structures are shown to the right in FIG. 1 , where stacks of electrodes and separators are utilized, with electrode coatings typically on both sides of the current collectors.
- the stacks may be formed into different shapes, such as a coin cell, cylindrical cell, or prismatic cell, for example.
- the anode 101 and cathode 105 may comprise the electrodes, which may comprise plates or films within, or containing, an electrolyte material, where the plates may provide a physical barrier for containing the electrolyte as well as a conductive contact to external structures.
- the anode/cathode plates are immersed in electrolyte while an outer casing provides electrolyte containment.
- the anode 101 and cathode are electrically coupled to the current collectors 107 A and 1078 , which comprise metal or other conductive material for providing electrical contact to the electrodes as well as physical support for the electrode coating layer in forming electrodes.
- the separator 103 is generally a film material, made of an electrically insulating polymer, for example, that prevents electrons from flowing from anode 101 to cathode 105 , or vice versa, while being porous enough to allow ions to pass through the separator 103 .
- the separator 103 , cathode 105 , and anode 101 materials are individually formed into sheets, films, or coated foils.
- the separator 103 is a sheet and generally utilizes winding methods and stacking in its manufacture.
- the anodes, cathodes, and current collectors may comprise films.
- one or more of the electrodes is a silicon-dominant electrode.
- the electrode comprises a self-supporting composite material film.
- the composite material film comprises greater than 0% and less than about 90% by weight of silicon particles, and greater than 0% and less than about 90% by weight of one or more types of carbon phases, wherein at least one of the one or more types of carbon phases is a substantially continuous phase that holds the composite material film together such that the silicon particles are distributed throughout the composite material film.
- the amount of silicon in the composite material can be greater than zero percent by weight of the mixture and composite material.
- the mixture comprises an amount of silicon, the amount being within a range of from about 0% to about 90% by weight, such as greater than 70%, or including from about 30% to about 80% by weight of the mixture.
- the amount of silicon in the composite material can be within a range of from about 0% to about 35% by weight, including from about 0% to about 25% by weight, from about 10% to about 35% by weight, and about 20% by weight. In further certain embodiments, the amount of silicon in the mixture is at least about 30% by weight.
- the amount of silicon in the composite material include more than about 50% by weight, between about 30% and about 80% by weight, between about 50% and about 70% by weight, and between about 60% and about 80% by weight.
- the silicon particles may or may not be pure silicon.
- the silicon particles may be substantially silicon or may be a silicon alloy.
- the silicon alloy includes silicon as the primary constituent along with one or more other elements.
- the battery 100 may comprise a solid, liquid, or gel electrolyte.
- the separator 103 preferably does not dissolve in typical battery electrolytes such as compositions that may comprise: Ethylene Carbonate (EC), Fluoroethylene Carbonate (FEC), F2EC, VC, Propylene Carbonate (PC), Dimethyl Carbonate (DMC), Ethyl Methyl Carbonate (EMC), Diethyl Carbonate (DEC), etc. with dissolved LiBF 4 , LiAsF 6 , LiPF 6 , LiTFSI, LiFSI, LiDFOB, LiBOB, LiTDI, and LiClO 4 etc.
- the separator 103 may be wet or soaked with a liquid or gel electrolyte.
- the separator 103 does not melt below about 100 to 120° C., and exhibits sufficient mechanical properties for battery applications.
- a battery, in operation, can experience expansion and contraction of the anode and/or the cathode.
- the separator 103 can expand and contract by at least about 5 to 10% without failing, and may also be flexible.
- the separator 103 may be sufficiently porous so that ions can pass through the separator once wet with, for example, a liquid or gel electrolyte. Alternatively (or additionally), the separator 103 may absorb the electrolyte through a gelling or other process even without significant porosity.
- the porosity of the separator 103 is also generally not too porous to allow the anode 101 and cathode 105 to transfer electrons through the separator 103 .
- the anode 101 and cathode 105 comprise electrodes for the battery 100 , providing electrical connections to the device for transfer of electrical charge in charge and discharge states.
- the anode 101 may comprise silicon, carbon, or combinations of these materials, for example.
- Typical anode electrodes comprise a carbon material that includes a current collector such as a copper sheet. Carbon is often used because it has excellent electrochemical properties and is also electrically conductive.
- Anode electrodes currently used in rechargeable lithium-ion cells typically have a specific capacity of approximately 200 milliamp hours per gram (mAh/g).
- Graphite the active material used in most lithium ion battery anodes, has a theoretical energy density of 372 mAh/g. In comparison, silicon has a high theoretical capacity of 4200 mAh/g.
- silicon may be used as the active material for the cathode or anode.
- Silicon anodes may be formed from silicon composites, with more than 50% silicon, for example.
- the anode 101 and cathode 105 store the ion used for separation of charge, such as lithium.
- the electrolyte carries positively charged lithium ions from the anode 101 to the cathode 105 in discharge mode, as shown in FIG. 1 for example, and vice versa through the separator 105 in charge mode.
- the movement of the lithium ions creates free electrons in the anode 101 which creates a charge at the positive current collector 1078 .
- the electrical current then flows from the current collector through the load 109 to the negative current collector 107 A.
- the separator 103 blocks the flow of electrons inside the battery 100 , allows the flow of lithium ions, and prevents direct contact between the electrodes.
- the anode 101 releases lithium ions to the cathode 105 via the separator 103 , generating a flow of electrons from one side to the other via the coupled load 109 .
- Reliability and energy density of the battery 100 are dependent upon the materials selected for the anode 101 and cathode 105 .
- the energy, power, cost, and safety of current Li-ion batteries need to be improved in order to, for example, compete with internal combustion engine (ICE) technology and allow for the widespread adoption of electric vehicles (EVs).
- High energy density, high power density, and improved safety of lithium-ion batteries may be achieved with the development of high-capacity and high-voltage cathodes, high-capacity anodes, and functionally non-flammable electrolytes with high voltage stability and interfacial compatibility with electrodes.
- materials with low toxicity are beneficial as battery materials to reduce process cost and promote consumer safety.
- the performance of electrochemical electrodes are depending upon many factors including the robustness of electrical contact between electrode particles, as well as between the current collector and the electrode particles.
- the electrical conductivity of silicon anode electrodes may be manipulated by incorporating conductive additives with different morphological properties. Carbon black (SuperP), vapor grown carbon fibers (VGCF), and a mixture of the two have may be incorporated separately into the anode electrode resulting in improved performance of the anode.
- the synergistic interactions between the two carbon materials may facilitate electrical contact throughout the large volume changes of the silicon anode during charge and discharge.
- State-of-the-art lithium-ion batteries typically employ a graphite-dominant anode as an intercalation material for lithium.
- silicon may be added as an active material or even completely replacing graphite as a dominant anode material.
- Most electrodes that are considered “silicon anodes” in the industry are graphite anodes with silicon added in small quantities (typically ⁇ 20%). These graphite-silicon mixture anodes must utilize the graphite, which has a lower lithiation voltage compared to silicon; the silicon has to be nearly fully lithiated in order to utilize the graphite.
- these electrodes do not have the advantage of a silicon or silicon composite anode where the voltage of the electrode is substantially above 0 V vs Li/Li+ and thus are less susceptible to lithium plating. Furthermore, these electrodes can have significantly higher excess capacity on the silicon versus the opposite electrode to further increase the robustness to high rates.
- Silicon-based anodes have a lithiation/delithiation voltage plateau at about 0.3-0.4 V vs. Li/Li+, which allows it to maintain an open circuit potential that avoids undesirable Li plating and dendrite formation. While silicon shows excellent electrochemical activity, achieving a stable cycle life for silicon-based anodes is challenging due to silicon's large volume changes during lithiation and delithiation. Silicon regions may lose electrical contact from the anode as large volume changes coupled with its low electrical conductivity separate the silicon from surrounding materials in the anode.
- SEI solid electrolyte interphase
- PAI water soluble acidified polyamide-imide
- PAA polyacrylic acid
- PAA polyacrylic acid
- PAA poly (maleic acid, methyl methacrylate/methacrylic acid, butadiene/maleic acid) solutions
- water soluble carboxyl acid group containing (co)polyimide solution water soluble polymers containing carboxyl acid groups.
- these polymeric stabilizing additives may assist in the stabilizing the slurry, and may also serve as a carbon source.
- the primary resin carbon precursor comprises an aqueous solution of two or more polymers.
- polysaccharide polymer examples include, but are not limited to, one or more of Polyamide-imide ⁇ Includes International-innotek (GT-720W, GT-721W, GT-722W), China-innotek (PIW-015, PIW-025, PIW-026), Elantas (Elan-bind 1015, Elan-bind 1015 NF), Solvay Torlon AI series (AI30, AI30-LM, AI10, AI10-LM) ⁇ ; Polyimide; Ammonium Lignosulfonate; Kraft Lignin; Dextran; Pullulan (polysaccharide polymer); Phenolic resins ⁇ Includes(Plenco (Novolac Resins), Resol Resins, polymethylol phenol, ERPENE PHENOLIC RESIN (emulsion) ⁇ ; Formaldehyde based Resins; Melamine-formaldehyde based resins; Silane based resins (gel
- additives may be used in order to modify the characteristics of the polymer solution.
- Suitable additives include, but are not limited to, one or more of Poly(acrylic acid), Carboxymethylcellulose (CMC), Polyvinylpyrrolidone, Myo-Inositol, Mannitol, Pinitol, Ribose, Sorbitol, Fucose, Maltodextrin, Ganglioside, Maltose, Sucrose, Glucose, Sucralose, Xylitol, Fructose, Palatinose hydrate, Dextran sucrase, Guanosine, Inulin, Sucrose phosphorylase, Glucosidases, AmberLite, Raffinose, Mannose, Psicose, Hexokinase, NADHs, Phosphoglucose, Phosphomannose, Topiramate, Furfurals, Nuciferine, Galactose, and Maltose.
- WPAI Water-soluble PAI
- PAI polyamide-imide
- WPAI is a PAI analog with acidic functional groups added to the chemical formula.
- Water soluble PAI is similar in chemical structure to PAI, however acid groups such as carboxylic acid or amic acid are embedded into the polymer backbone.
- Water-soluble acidified PAI and water-based acidic polymer solution additive anodes provide the benefits of improved cycle life, increased energy density, increased power density, improved flexibility, improved adhesion, and reduced cost. Water-soluble acidified PAI and water-based acidic polymer solution additive electrodes may also provide improved safety.
- WPAI polymers can contain water; for example, WPAI polymer can have a water content of 45-75%, in some embodiments, the water content is 65%. Additional water may still be needed to dissolve the polymer above the water content already present in the polymer.
- water soluble acidified PAI is a WPAI having a PAI backbone, functionalized with acidic groups to allow the polymer to dissolve in water.
- Acidic functional groups that may be used to functionalize PAI include, but are not limited to, one or more of Amic acid, Butane tetracarboxylic acid (BTC), Tetracarboxylic acid (TC), Carboxylic acid, Licanic acid, Methacrylic acid, Acetic acid, Aminomethanesulfonic acid, Anthranilic acid, Benzenesulfonic acid, Benzoic acid, Camphor-10-sulfonic acid, Citric acid, Folic acid, Formic acid, Fumaric acid, Gallic acids, Lactic acid, Maleic acid, Malonic acid, Methanesulfonic acid, Nitrilotriacetic acid, Oxalic acid, Peracetic acid, Phthalic acid, Propionic acid, Salicylic acid, Sorbic acid, Succinic acid, Sulfamic acid, Sul
- FIG. 2 A is a flow diagram of a direct coating process for fabricating a cell with a silicon-dominant electrode, in accordance with an example embodiment of the disclosure.
- This process comprises physically mixing the electrode coating layer and conductive additive together, and coating it directly on a current collector as opposed to forming the electrode coating layer on a substrate and then laminating it on a current collector.
- This strategy may also be adopted by other anode-based cells, such as graphite, conversion type anodes, such as transition metal oxides, transition metal phosphides, and other alloy type anodes, such as Sn, Sb, Al, P, etc.
- the raw electrode coating layer may be mixed to form a slurry with stable viscosities of more than 1500 cp by using water-soluble acidified PAIs (WPAI) and water-based acidic polymer solution additives.
- WPAI water-soluble acidified PAIs
- the addition of the polymer solution additive enables the adjustment of the viscosity of the polymer and homogenization of the slurry.
- the fabricated anode shows superior adhesion to copper, a remarkable cohesion, and exceptional flexibility. This anode is shown to be capable of fast charging and performs similar or better than current anodes.
- cathode electrode coating layers may be mixed in step 201 , where the electrode coating layer may comprise lithium cobalt oxide (LCO), lithium iron phosphate, lithium nickel cobalt manganese oxide (NMC), Ni-rich lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium nickel manganese spinel, LFP, Li-rich layer cathodes, LNMO or similar materials or combinations thereof, mixed with carbon precursor and additive as described above for the anode electrode coating layer.
- LCO lithium cobalt oxide
- NMC lithium nickel cobalt manganese oxide
- NCA Ni-rich lithium nickel cobalt aluminum oxide
- LMO lithium manganese oxide
- LFP lithium nickel manganese spinel
- Li-rich layer cathodes Li-rich layer cathodes, LNMO or similar materials or combinations thereof
- aqueous-based polyamide-imide resins used to fabricate silicon dominant anodes are disclosed.
- Environmentally friendly bases may be used in the slurry and stabilizers may also be used.
- water soluble PAI 5-20% in water
- triethanolamine is used as base
- PAA stabilizer to create high silicon content anodes.
- the slurry may be made in water and may have varying composition.
- the slurry may contain one or more of the following components in the following ranges:
- Bases that can be used in the slurry include, but are not limited to, one or more of Triethanolamine, Triethylamine, N-Methyldiethanolamine, Butyldiethanolamine, Diethylamine, Ethylamine, Tetrabutylammonium hydroxide, Tetramethylammonium hydroxide, Tetramethylammonium hydroxide, Triisopropanolamine, Trolamine, Amino-2-propanol, Triisobutylamine, N-Isopropyl-N-methyl-tert-butylamine, 2-Amino-2-methyl-1-propanol, 1-Amino-2-butanol, 2-Amino-1-butanol, Diethanolamine, Ethanolamine, 2-Dimethylaminoethanol, N-Phenyldiethanolamine, 2-(Dibutylamino)ethanol, 2-(Butylamino)ethanol, N-tert-Butyldiethanolamine, N-Eth
- aqueous-based polyamide-imide resins are used to create a slurry containing an environmentally friendly base (such as triethanolamine) along with polyacrylic acid (PAA).
- PAI is used as the main carbon source
- triethanolamine is used as the base
- PAA both as the slurry stabilizer and as carbon source.
- the environmentally friendly base (such as triethanolamine) is a non-corrosive amine base which facilitates the dissolution of the PAI in water.
- the slurry contains an optional surfactant. Addition of a surfactant may improve the coating quality.
- Suitable surfactants include, but are not limited to, octyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide, Polyvinylpyrrolidone ⁇ -fluoro homoallylic alcohols, ⁇ -Cyclodextrin, TritonX-100, FluorN 561 and FluorN 562, ETI 929 (from EnvTech), alkyl glycosides, and TEGO® Surten E.
- a silicon-dominant anode for a silicon-dominant anode, 30-40 grams of dry WPAI, 15-25 grams of a basic amine such as butyldiethanolamine or triethanolamine, and 400-500 grams of water may be mixed at high temperature to form a solution. Then, 30-50 grams of this solution may be mixed with 5-20 grams of silicon microparticles ( ⁇ 10-12 ⁇ m) plus 0.2-0.5 grams of PAA 12% solution in water as additive, and 4-8 grams of water. The mixture may be mixed using a low shear mixer or a centrifugal speed mixer, where FIG. 3 shows the changes in the viscosity of the solution versus mixing time.
- a basic amine such as butyldiethanolamine or triethanolamine
- a WPAI solution was made using the following example formulation in Table 1.
- the polymer powder (water content 45-75%) may be dissolved in a mixture of 458 grams of DI water and 27 grams of triethanolamine. Then the temperature of the mixture may be raised to >80° C. under vigorous stirring overnight to allow the polymer to dissolve in the solution. Then the solution may be filtered to form the WPAI solution used to make the slurry.
- WPAI-resin may be used to make a slurry with various formulations having different types of silicon to illustrate that different silicon particles may be used.
- the formulation of the slurry was as follows in Table 2.
- silicon powders with different particle size (D50 of 5 ⁇ m and D50 of 12 ⁇ m) may be added to a solution of the resin pre-mixed with the surfactant in the proportions set forth above in Table 2. Then PAA solution may be added to the mixture and further mixed to form the slurry.
- the as-prepared slurry may be coated on a copper foil, 20 ⁇ m thick in this example, and in step 205 may be dried at 130° C. in a convection oven to dry the coating and form the green anode.
- cathode electrode coating layers may be coated on a foil material, such as aluminum, for example.
- An optional calendering process may be utilized in step 207 where a series of hard pressure rollers may be used to finish the film/substrate into a smoother and denser sheet of material.
- the slurries from Samples 1-3 above may be coated separately on 15 ⁇ m copper foils and pyrolyzed under Argon gas at 650° C. for 3 hours to form silicon dominant anodes. Testing may be performed between 4.2 V-2 V using the sample anodes and NMC cathode. The electrochemical performance of the anodes in pouch cells is shown in FIG. 9 .
- the electrode coating layer may be pyrolyzed by heating to 500-800° C., 650° C. in this example, in an inert atmosphere such that carbon precursors are partially or completely converted into conductive carbon.
- the pyrolysis step may result in an anode electrode coating layer having silicon content greater than or equal to 50% by weight, where the anode has been subjected to heating at or above 400 degrees Celsius.
- the pyrolysis conditions may be between 450-800° C., under Argon, Nitrogen, or Forming gas.
- Pyrolysis can be done either in roll form or after punching in step 211 . If done in roll form, the punching is done after the pyrolysis process. In instances where the current collector foil is not pre-punched/pre-perforated, the formed electrode may be perforated with a punching roller, for example. The punched electrodes may then be sandwiched with a separator and electrolyte to form a cell. In step 213 , the cell may be subjected to a formation process, comprising initial charge and discharge steps to lithiate the anode, with some residual lithium remaining, and the cell capacity may be assessed.
- FIG. 2 B is a flow diagram of an alternative process for lamination of electrodes, in accordance with an example embodiment of the disclosure. While the previous process to fabricate composite anodes employs a direct coating process, this process physically mixes the active material, conductive additive, and binder together coupled with peeling and lamination processes.
- step 221 where the raw electrode coating layer may be mixed to form a slurry with stable viscosities of more than 1500 cp by using water-soluble acidified PAIs (WPAI) and water-based acidic polymer solution additives.
- WPAI water-soluble acidified PAIs
- the addition of the polymer solution additive enables the adjustment of the viscosity of the polymer and homogenization of the slurry.
- cathode electrode coating layers may be mixed in step 221 , where the electrode coating layer may comprise lithium cobalt oxide (LCO), lithium iron phosphate, lithium nickel cobalt manganese oxide (NMC), Ni-rich lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium nickel manganese spinel, LFP, Li-rich layer cathodes, LNMO or similar materials or combinations thereof, mixed with carbon precursor and additive as described above for the anode electrode coating layer.
- LCO lithium cobalt oxide
- NMC lithium nickel cobalt manganese oxide
- NCA Ni-rich lithium nickel cobalt aluminum oxide
- LMO lithium manganese oxide
- LFP lithium nickel manganese spinel
- Li-rich layer cathodes Li-rich layer cathodes, LNMO or similar materials or combinations thereof
- a silicon-dominant anode for a silicon-dominant anode, 30-40 grams of dry WPAI, 15-25 grams of a basic amine such as butyldiethanolamine or triethanolamine, and 400-500 grams of water may be mixed at high temperature to form a solution. Then, 30-50 grams of this solution may be mixed with 5-20 grams of silicon microparticles ( ⁇ 10-12 ⁇ m) plus 0.2-0.5 grams of PAA 12% solution in water as additive, and 4-8 grams of water. The mixture may be mixed using a low shear mixer or a centrifugal speed mixer, where FIG. 3 shows the changes in the viscosity of the solution versus mixing time.
- a basic amine such as butyldiethanolamine or triethanolamine
- the slurry may be coated on a polymer substrate, such as polyethylene terephthalate (PET), polypropylene (PP), or Mylar.
- PET polyethylene terephthalate
- PP polypropylene
- Mylar The slurry may be coated on the PET/PP/Mylar film at a loading of 3-6 mg/cm 2 for the anode and 15-35 mg/cm 2 for the cathode, and then dried in step 225 .
- An optional calendering process may be utilized where a series of hard pressure rollers may be used to finish the film/substrate into a smoothed and denser sheet of material.
- the green film may then be removed from the PET, where the active material may be peeled off the polymer substrate, the peeling process being optional for a polypropylene (PP) substrate, since PP can leave ⁇ 2% char residue upon pyrolysis.
- the peeling may be followed by a cure and pyrolysis step 229 where the film may be cut into sheets, and vacuum dried using a two-stage process (100-140° C. for 14-16 hours, 200-240° C. for 4-6 hours).
- the dry film may be thermally treated at 1000-1300° C. to convert the polymer matrix into carbon.
- the pyrolyzed material may be flat press or roll press laminated on the current collector, where for aluminum foil for the cathode and copper foil for the anode may be pre-coated with polyamide-imide with a nominal loading of 0.35-0.75 mg/cm 2 (applied as a 5-7 wt % varnish in NMP, dried 10-20 hour at 100-140° C. under vacuum).
- the active material composite film may be laminated to the coated aluminum or copper using a heated hydraulic press (30-70 seconds, 250-350° C., and 3000-5000 psi), thereby forming the finished composite electrode.
- the pyrolyzed material may be roll-press laminated to the current collector.
- the electrodes may then be sandwiched with a separator and electrolyte to form a cell.
- the cell may be subjected to a formation process, comprising initial charge and discharge steps to lithiate the anode, with some residual lithium remaining, and testing to assess cell performance.
- FIG. 3 illustrates slurry viscosity versus mixing time, in accordance with an example embodiment of the disclosure.
- the plot indicates that a slurry with stable viscosity can be achieved using WPAI as the carbon precursor, where a viscosity of 1500 centipoise (cp) may be obtained after ⁇ 15 hours with this mixture.
- the polymer additive may play a role in linking long chain PAIs together and as a result increases the viscosity of the solution.
- FIG. 4 illustrates the results of thermal gravimetric analysis (TGA) of dry WPAI, in accordance with an example embodiment of the disclosure.
- the TGA analysis may be performed under nitrogen atmosphere with a flow rate of 100 sccm and temperature ramp rate of 5° C./min.
- the plot shows the weight percentage remaining and the normalized heat flow provided to the material in W/g over a temperature range up to 800° C.
- the TGA analysis indicates that the polymer has ⁇ 58% char yield at 650° C. and more than 53% char yield at 800° C.
- FIG. 5 illustrates an adhesion test for a silicon-dominant anode with water-soluble acidified PAI and water-based acidic polymer solution additive, in accordance with an example embodiment of the disclosure.
- the test setup includes a clamp 501 for holding an electrode 505 fastened to a glass slide 503 using adhesive tape (not visible) holding the anode on one side on the other is a double sided adhesive tape (not visible) for coupling to weights.
- the anode shows a superior adhesion strength, with capability of holding 350 grams of weights before the coating detaches from the copper. Such adhesion is much higher than most anodes which mostly fail to hold more than 50 grams of weights.
- FIG. 6 illustrates a silicon-dominant anode after a winding test, in accordance with an example embodiment of the disclosure.
- the anode is wrapped around a 4 mm mandrel in order to test the feasibility of using it for cylindrical cells.
- the anode shows only minor cracks, no copper exposures due to carbon detachments, and no flaking. Therefore, such a remarkable flexibility and anode integrity indicates that the water-based slurry anode is appropriate for use in cylindrical cells.
- FIG. 7 illustrates normalized discharge capacity of a cell with water-soluble acidified PAI and water-based acidic polymer solution additive anode compared to a standard cell with NMP-based resin laminated anode, in accordance with an example embodiment of the disclosure.
- the plot compares the normalized capacity retention of the standard anode (solid line—anode laminated on a current collector with an adhesive) versus the water-soluble acidified PAI and water-based acidic polymer solution additive anode (dashed line).
- the NMP-based resin anode may be laminated on a copper foil coated with PAI adhesive, as opposed to the direct-coated water-based resin anode.
- the normalized capacity values shown indicate that the water-soluble acidified PAI anode demonstrates a better capacity retention compared with the standard anode.
- the standard anode in this example is a free standing pyrolyzed coupon that is laminated on adhesive-coated copper.
- the water-soluble acidified PAI anode is still at near 100% discharge capacity after 60 cycles.
- water-soluble acidified PAI and water-based acidic polymer solution additive anodes demonstrate increased energy density, increased power density, improved flexibility, improved adhesion, and reduced cost using water soluble acidified PAI.
- FIG. 8 illustrates slurry viscosity against temperature for a sample containing silicon powder with D50 of 5 ⁇ m at 20.92%, PAI-resin at 66.90%, Polyacrylic acid (12% in water)—PAA at 12.07% and surfactant at 0.10%, at 60 and 100 RPM.
- FIG. 9 illustrates electrochemical performance of the anodes in pouch cells, where the anodes are made from slurries according to Samples 1-3 above.
- the cycling may be performed at 2 C charge and 0.5 C discharge between 4.2-2.5 V.
- silicon-dominant anodes and processes for manufacturing such silicon-dominant anodes.
- the silicon-dominate anodes are described below as being manufactured per the direct coating process of FIG. 2 A .
- each of the below silicon-dominant anodes may be manufactured per the direct coating process of FIG. 2 A or the laminating process of FIG. 2 B .
- a silicon-dominate anode was prepared based on the following slurry formulation, which is presented in mass units in Table 3 and as weight percentages in Table 4:
- the slurry was formed at 201 of FIG. 2 A from the above components by adding the surfactant and PAI solution to a mixer.
- the mixer mixed the surfactant and PAI solution at 2000 rpm for 1 minute.
- the silicon powder was then added to the mixer and mixed at 2000 rpm for another minute.
- the PAA solution was added to the mixer and mixed at 2000 rpm for another minute.
- the mixture was filtered through a 120 ⁇ m mesh to remove agglomerates and returned to the mixer.
- the mixer further mixed the slurry at 2000 rpm for a minute and then at 2200 rpm for another minute.
- the slurry was coated on a foil.
- the slurry was hand coated using a 9 mil doctor blade on one side of a 20 ⁇ m copper foil.
- the copper foil was a rolled copper foil made of C15500 alloy and the slurry was applied to a thickness of about 30 ⁇ m, resulting in a copper foil to active material thickness ratio of about 0.66 (20 ⁇ m/30 ⁇ m).
- Some embodiments may utilize a copper foil made of C15500, C19400, C26000, or C51000 copper alloys.
- the slurry coated copper foil was dried at about 90° C. in a gravity convection oven for 10 to 15 minutes, then slit into 2-inch wide anode stripes. The anode stripes were further dried at 80° C. under vacuum overnight before calendering.
- the anode stripes were calendered using a fixed gap calendering machine at 60° C. to reach designed thickness of 50-65 ⁇ m including 20 ⁇ m Cu foil and density of approximately 1.0-1.1. After calendering, the anode stripes were punched to form anode coupons and the anode coupons at 209 were pyrolyzed at 650° C. with 5° C./min ramp and 180 minute dwell time in an Argon atmosphere.
- Such process resulted in single-side anodes having an active material layer of about 30 ⁇ m on one side of the copper foil.
- the final composition of the anode active material after pyrolysis was about 86% silicon and about 14% pyrolytic carbon. Moreover the active material had a porosity of about 50-56%.
- Some embodiments of a silicon-dominant anode may utilize a foil thickness to active material layer thickness of over 0.5, wherein the porosity of the active material layer is below 70%. Some embodiments of a silicon-dominant anode may utilize a foil thickness to active material layer thickness of 0.15, about 0.15, over 0.15, 0.25, about 0.25, over 0.25, 0.5, about 0.5, over 0.5, 0.66, about 0.66, or over 0.66, wherein the porosity of the active material layer is 70%, about 70%, below about 70%, 60%, about 60%, below about 60%, 50%, about 50%, below about 50%, 40%, about 40%, below about 40%, 30%, about 30%, or below about 30%.
- a silicon dominant anode may utilize a foil thickness to porosity-adjusted active material layer thickness ratio of 0.25, about 0.25, over 0.25, 0.33, about 0.33, over 0.33, 0.5, about 0.5, over 0.5, 0.6, about 0.6, over 0.6, 1, about 1, over 1, 1.3, about 1.3, or over 1.3. Such ratio may be calculated per Equation 1:
- each pouch cell included one single-layer anode, one double layer cathode, and about 1 mL of electrolyte, providing an approximate capacity of 78 mAh.
- the cathode facing pouch side was taped using Kapton tape to avoid/minimize electrochemical reactions.
- Each single-layer pouch cell was subject to a hot pressing step, a cold pressing step, or skipped the pressing step, before going through formation and degassing.
- each single-layer pouch cell was clamped between a bottom metal plate and top metal plate and tested in a battery tester. In particular, each single-layer cell was clamped in the order of a bottom metal plate, paper, cell, foam pad, top metal plate using fixed gap.
- the single-layer pouch cells may be assembled using a fixture where the pressure is maintained by clamping the cell at a certain gap or using springs, actuators or other means to achieve a pressure within about 10%, about 11%, about 15%, or about 20% of original pressure (about 120 kPa).
- the pressure may be applied using compressible foam, metal springs, air bladder, paper, or fabric.
- Some embodiments of the single-layer pouch cells may have an electrolyte to Ah ratio of about 2 g/Ah, over 2 g/Ah, about 2.4 g/Ah, over 2.4 g/Ah, about 5 g/Ah, over 5 g/Ah, about 10 g/Ah, over 10 g/Ah, about 16 g/Ah, over 16 g/Ah.
- the single-layer pouch cells may be sealed with excess pouch material on at least one side.
- the seal may be at least 5 mm, at least 3 mm, or at least 2 mm from an edge of the cell stack.
- the silicon-dominate anode may have an areal capacity between 9 mAh/cm 2 and 15 mAh/cm 2 . Moreover, the amount of electrolyte per active area of the electrode may be between 0.02 and 0.1 mL/cm 2 . The active area of the electrode corresponds to the area of the silicon-dominate anode in cm 2 that participates in the electrochemical reaction. In some embodiments, the silicon-dominate anode may have an areal capacity between 5 mAh/cm 2 and 11 mAh/cm 2 with the amount of electrolyte per active area of electrode between 0.005 and 0.05 m L/cm 2 .
- Each of the five-layer pouch cells included six layers of double-sided anodes and five layers of double-sided cathodes.
- the anodes of the five-layer pouch cells were made using the same formulation and mixing method as the single-layer pouch cells.
- the anodes of the five-layer pouch cells used a 15 ⁇ m foil with an active material thickness of about 30 ⁇ m on each side, thus resulting in a copper foil to active material thickness ratio of about 0.66 (20 ⁇ m/30 20 ⁇ m).
- Each single-layer pouch cell provided 78 mAh measured between 4.2 V and 2.75 V at 0.5 C.
- each five-layer pouch cell provided 780 mAh measured between 4.2 V and 2.75 V at 0.5 C.
- FIG. 10 capacity retention of single-layer pouch cells (enhanced cells) and five-layer pouch cells (baseline cells) are depicted for cycle life based on 2 C (4.2 V)/0.5 C (2.75 V) cycles.
- the enhanced cells and baseline cells of FIG. 10 include anodes manufactured per the formulation of Table 3 and process described above. As shown by lines 1000 , the baseline cells reached their 80% retention mark at about 160 cycles. However, as shown by lines 1010 , the enhanced cells reached their 80% retention mark at about 220 cycles.
- FIG. 11 capacity retention of single-layer pouch cells (enhanced cells) and five-layer pouch cells (baseline cells) are depicted for cycle life based on 4 C (4.2 V)/0.5 C (3.2 V) cycles.
- the enhanced cells and baseline cells of FIG. 11 include anodes manufactured per the formulation of Table 3 and process described above. Lines 1100 depict capacity retention of the baseline cells, whereas lines 1110 depict capacity retention of the enhanced cells. As shown, the enhanced cells retained a greater amount of the original capacity after about 120 cycles than the baseline cells.
- pressed and not pressed pouch cells include anodes manufactured per the formulation of Table 3 and process described above.
- the pressed cells (shown by lines 1200 ) include single-layer pouch cells subjected to a hot pressing process in which the cells were pressed at 140 psi at 100° C. for 2 minutes and single-layer pouch cells subject to a cold pressing process in which the cells were pressed at 140 psi at room temperature.
- the not pressed cells (shown by lines 1210 ) were not subjected to either hot pressing or cold pressing processes.
- the lines 1210 of the not pressed cells closely track the lines 1200 for the pressed cells for the first 30 cycles.
- FIG. 12 does not include data for the not pressed cells beyond the first 30 cycles.
- pressing does provide a significant factor of capacity retention for at least the first 30 cycles of cycle life based on 2 C(4.2 V)/0.5 C(2.75 V) cycles.
- FIG. 13 a comparison is presented for capacity retention of single-layer pouch cells having anodes manufactured per three different formulations, which are referred to as enhanced cell, enhanced cell 2 , and enhanced cell 3 in FIG. 13 .
- the enhanced cells are represented by lines 1310 in FIG. 13 .
- Each enhanced cell includes an anode manufacture per the formulation of Table 3 and the above described process.
- the enhanced cells 2 are represented by lines 1320 in FIG. 13 .
- Each enhanced cell 2 includes an anode manufactured per the formulation of Table 5 and the above described process.
- the enhanced cells 3 are represented by lines 1330 in FIG. 13 .
- Each enhanced cell 3 includes an anode manufactured per the formulation of Table 6 and the above described process.
- the composition for the anode active material of enhance cell 3 was about 90% silicon, about 8% pyrolytic carbon, and about 2% carbon additive. Moreover, the active material of each enhanced cell 3 had a porosity of about 50-56%.
- the single-layer pouch cells improve normalized capacity retention by about 50% for 2 C (4.2 V)/0.5 C (2.75 V) cycling when compared to the five-layer pouch cells (e.g., baseline cells).
- the single-layer pouch cells e.g., enhanced cell, enhanced cell 2 , and enhanced cell 3
- reduce degradation by more than a factor of 3 i.e., has less than 1 ⁇ 3 the degradation
- the battery electrode may comprise an electrode coating layer on a current collector, where the electrode coating layer is formed from silicon and pyrolyzed water-soluble acidic polyamide imide resin carbon precursor.
- the electrode coating layer may comprise a pyrolyzed water-based acidic polymer solution additive.
- the polymer solution additive may comprise one or more of: polyacrylic acid (PAA) solution, poly (maleic acid, methyl methacrylate/methacrylic acid, butadiene/maleic acid) solutions, and water soluble PAA.
- PAA polyacrylic acid
- the electrode coating layer may comprise conductive additives.
- the current collector may comprise a metal foil, where the metal current collector comprises one or more of a copper, tungsten, stainless steel, and nickel foil in electrical contact with the electrode coating layer.
- the electrode coating layer may comprise more than 70% silicon.
- the electrode may be in electrical and physical contact with an electrolyte, where the electrolyte comprises a liquid, solid, or gel.
- the battery electrode may be in a lithium ion battery.
- “and/or” means any one or more of the items in the list joined by “and/or”.
- “x and/or y” means any element of the three-element set ⁇ (x), (y), (x, y) ⁇ . In other words, “x and/or y” means “one or both of x and y”.
- “x, y, and/or z” means any element of the seven-element set ⁇ (x), (y), (z), (x, y), (x, z), (y,z), (x, y, z) ⁇ . In other words, “x, y and/or z” means “one or more of x, y and z”.
- exemplary means serving as a non-limiting example, instance, or illustration.
- terms “e.g.,” and “for example” set off lists of one or more non-limiting examples, instances, or illustrations.
- a battery, circuitry or a device is “operable” to perform a function whenever the battery, circuitry or device comprises the necessary hardware and code (if any is necessary) or other elements to perform the function, regardless of whether performance of the function is disabled or not enabled (e.g., by a user-configurable setting, factory trim, configuration, etc.).
Abstract
Silicon-dominate battery electrodes, battery cells utilizing the silicon-dominate battery electrodes, and methods of manufacturing are disclosed. Such a battery electrode includes a current collector and an active material layer on the current collector. The active material layer comprises at least 50% silicon. In some embodiments, a ratio of a thickness of the current collector to a thickness of the active material layer is over 0.5, and a porosity of the active material layer is below 70%.
Description
- Aspects of the present disclosure relate to energy generation and storage. More specifically, certain embodiments of the disclosure are directed to battery electrodes, battery cells, and/or batteries with improved cycle life.
- A rechargeable battery experiences periods of charging and periods discharging. These charge-discharge cycles reduce a storage capacity of the of battery and thus reduce the life of the battery.
- Further limitations and disadvantages of conventional and traditional approaches will become apparent to one of skill in the art, through comparison of such systems with some aspects of the present disclosure as set forth in the remainder of the present application with reference to the drawings.
- A battery and/or battery anode are substantially shown in and/or described in connection with at least one of the figures, as set forth more completely in the claims.
- These and other advantages, aspects and novel features of the present disclosure, as well as details of an illustrated embodiment thereof, will be more fully understood from the following description and drawings.
-
FIG. 1 is a diagram of a battery with a silicon-dominant anode, in accordance with an example embodiment of the disclosure. -
FIG. 2A is a flow diagram of a direct coating process for fabricating a cell with a silicon-dominant electrode, in accordance with an example embodiment of the disclosure. -
FIG. 2B is a flow diagram for of an alternative process for lamination of electrodes, in accordance with an example embodiment of the disclosure. -
FIG. 3 illustrates slurry viscosity versus mixing time, in accordance with an example embodiment of the disclosure. -
FIG. 4 illustrates the results of thermal gravimetric analysis (TGA) of dry WPAI, in accordance with an example embodiment of the disclosure. -
FIG. 5 illustrates an adhesion test for a silicon-dominant anode with water-soluble acidified PAI and water-based acidic polymer solution additive, in accordance with an example embodiment of the disclosure. -
FIG. 6 illustrates a silicon-dominant anode after a winding test, in accordance with an example embodiment of the disclosure. -
FIG. 7 illustrates normalized discharge capacity of a cell with water-soluble acidified PAI and water-based acidic polymer solution additive anode compared to a standard cell with NMP-based slurry laminated anode, in accordance with an example embodiment of the disclosure. -
FIG. 8 illustrates slurry viscosity versus temperature, in accordance with an example embodiment of the disclosure. -
FIG. 9 illustrates electrochemical performance of anodes in pouch cells, in accordance with an example embodiment of the disclosure. -
FIG. 10 illustrates capacity retention of single-layer and five-layer pouch cells during cycle life based on 2 C(4.2 V)/0.5 C(2.75 V) cycles. -
FIG. 11 illustrates capacity retention of single-layer and five-layer pouch cells during cycle life based on 4 C (4.2 V)/0.5 C (3.2 V) cycles. -
FIG. 12 illustrates capacity retention of pressed and not pressed pouch cells during cycle life based on 2 C (4.2 V)/0.5 C (2.75 V) cycles. -
FIG. 13 illustrates capacity retention of single-layer pouch cells having anodes manufacture per three different formulations. -
FIG. 1 is a diagram of a battery with silicon-dominant anodes, in accordance with an example embodiment of the disclosure. Referring toFIG. 1 , there is shown abattery 100 comprising aseparator 103 sandwiched between ananode 101 and acathode 105, withcurrent collectors load 109 coupled to thebattery 100 illustrating instances when thebattery 100 is in discharge mode. In this disclosure, the term “battery” may be used to indicate a single electrochemical cell, a plurality of electrochemical cells formed into a module, and/or a plurality of modules formed into a pack. Furthermore, the cell shown inFIG. 1 is a very simplified example merely to show the principle of operation of a lithium ion cell. Examples of realistic structures are shown to the right inFIG. 1 , where stacks of electrodes and separators are utilized, with electrode coatings typically on both sides of the current collectors. The stacks may be formed into different shapes, such as a coin cell, cylindrical cell, or prismatic cell, for example. - The development of portable electronic devices and electrification of transportation drive the need for high performance electrochemical energy storage. Small-scale (<100 Wh) to large-scale (>10 KWh) devices primarily use lithium-ion (Li-ion) batteries over other rechargeable battery chemistries due to their high-performance.
- The
anode 101 andcathode 105, along with thecurrent collectors anode 101 and cathode are electrically coupled to thecurrent collectors 107A and 1078, which comprise metal or other conductive material for providing electrical contact to the electrodes as well as physical support for the electrode coating layer in forming electrodes. - The configuration shown in
FIG. 1 illustrates thebattery 100 in discharge mode, whereas in a charging configuration, theload 109 may be replaced with a charger to reverse the process. In one class of batteries, theseparator 103 is generally a film material, made of an electrically insulating polymer, for example, that prevents electrons from flowing fromanode 101 tocathode 105, or vice versa, while being porous enough to allow ions to pass through theseparator 103. Typically, theseparator 103,cathode 105, andanode 101 materials are individually formed into sheets, films, or coated foils. Sheets of the cathode, separator and anode are subsequently stacked or rolled with theseparator 103 separating thecathode 105 andanode 101 to form thebattery 100. In some embodiments, theseparator 103 is a sheet and generally utilizes winding methods and stacking in its manufacture. In these methods, the anodes, cathodes, and current collectors (e.g., electrodes) may comprise films. - In some embodiments, one or more of the electrodes is a silicon-dominant electrode. In some embodiments, the electrode comprises a self-supporting composite material film. In some embodiments, the composite material film comprises greater than 0% and less than about 90% by weight of silicon particles, and greater than 0% and less than about 90% by weight of one or more types of carbon phases, wherein at least one of the one or more types of carbon phases is a substantially continuous phase that holds the composite material film together such that the silicon particles are distributed throughout the composite material film.
- The amount of silicon in the composite material can be greater than zero percent by weight of the mixture and composite material. In certain embodiments, the mixture comprises an amount of silicon, the amount being within a range of from about 0% to about 90% by weight, such as greater than 70%, or including from about 30% to about 80% by weight of the mixture. The amount of silicon in the composite material can be within a range of from about 0% to about 35% by weight, including from about 0% to about 25% by weight, from about 10% to about 35% by weight, and about 20% by weight. In further certain embodiments, the amount of silicon in the mixture is at least about 30% by weight. Additional embodiments of the amount of silicon in the composite material include more than about 50% by weight, between about 30% and about 80% by weight, between about 50% and about 70% by weight, and between about 60% and about 80% by weight. Furthermore, the silicon particles may or may not be pure silicon. For example, the silicon particles may be substantially silicon or may be a silicon alloy. In one embodiment, the silicon alloy includes silicon as the primary constituent along with one or more other elements.
- In an example scenario, the
battery 100 may comprise a solid, liquid, or gel electrolyte. Theseparator 103 preferably does not dissolve in typical battery electrolytes such as compositions that may comprise: Ethylene Carbonate (EC), Fluoroethylene Carbonate (FEC), F2EC, VC, Propylene Carbonate (PC), Dimethyl Carbonate (DMC), Ethyl Methyl Carbonate (EMC), Diethyl Carbonate (DEC), etc. with dissolved LiBF4, LiAsF6, LiPF6, LiTFSI, LiFSI, LiDFOB, LiBOB, LiTDI, and LiClO4 etc. Theseparator 103 may be wet or soaked with a liquid or gel electrolyte. In addition, in an example embodiment, theseparator 103 does not melt below about 100 to 120° C., and exhibits sufficient mechanical properties for battery applications. A battery, in operation, can experience expansion and contraction of the anode and/or the cathode. In an example embodiment, theseparator 103 can expand and contract by at least about 5 to 10% without failing, and may also be flexible. - The
separator 103 may be sufficiently porous so that ions can pass through the separator once wet with, for example, a liquid or gel electrolyte. Alternatively (or additionally), theseparator 103 may absorb the electrolyte through a gelling or other process even without significant porosity. The porosity of theseparator 103 is also generally not too porous to allow theanode 101 andcathode 105 to transfer electrons through theseparator 103. - The
anode 101 andcathode 105 comprise electrodes for thebattery 100, providing electrical connections to the device for transfer of electrical charge in charge and discharge states. Theanode 101 may comprise silicon, carbon, or combinations of these materials, for example. Typical anode electrodes comprise a carbon material that includes a current collector such as a copper sheet. Carbon is often used because it has excellent electrochemical properties and is also electrically conductive. Anode electrodes currently used in rechargeable lithium-ion cells typically have a specific capacity of approximately 200 milliamp hours per gram (mAh/g). Graphite, the active material used in most lithium ion battery anodes, has a theoretical energy density of 372 mAh/g. In comparison, silicon has a high theoretical capacity of 4200 mAh/g. In order to increase volumetric and gravimetric energy density of lithium-ion batteries, silicon may be used as the active material for the cathode or anode. Silicon anodes may be formed from silicon composites, with more than 50% silicon, for example. - In an example scenario, the
anode 101 andcathode 105 store the ion used for separation of charge, such as lithium. In this example, the electrolyte carries positively charged lithium ions from theanode 101 to thecathode 105 in discharge mode, as shown inFIG. 1 for example, and vice versa through theseparator 105 in charge mode. The movement of the lithium ions creates free electrons in theanode 101 which creates a charge at the positive current collector 1078. The electrical current then flows from the current collector through theload 109 to the negativecurrent collector 107A. Theseparator 103 blocks the flow of electrons inside thebattery 100, allows the flow of lithium ions, and prevents direct contact between the electrodes. - While the
battery 100 is discharging and providing an electric current, theanode 101 releases lithium ions to thecathode 105 via theseparator 103, generating a flow of electrons from one side to the other via the coupledload 109. When the battery is being charged, the opposite happens where lithium ions are released by thecathode 105 and received by theanode 101. - Reliability and energy density of the
battery 100 are dependent upon the materials selected for theanode 101 andcathode 105. The energy, power, cost, and safety of current Li-ion batteries need to be improved in order to, for example, compete with internal combustion engine (ICE) technology and allow for the widespread adoption of electric vehicles (EVs). High energy density, high power density, and improved safety of lithium-ion batteries may be achieved with the development of high-capacity and high-voltage cathodes, high-capacity anodes, and functionally non-flammable electrolytes with high voltage stability and interfacial compatibility with electrodes. In addition, materials with low toxicity are beneficial as battery materials to reduce process cost and promote consumer safety. - The performance of electrochemical electrodes are depending upon many factors including the robustness of electrical contact between electrode particles, as well as between the current collector and the electrode particles. The electrical conductivity of silicon anode electrodes may be manipulated by incorporating conductive additives with different morphological properties. Carbon black (SuperP), vapor grown carbon fibers (VGCF), and a mixture of the two have may be incorporated separately into the anode electrode resulting in improved performance of the anode. The synergistic interactions between the two carbon materials may facilitate electrical contact throughout the large volume changes of the silicon anode during charge and discharge.
- State-of-the-art lithium-ion batteries typically employ a graphite-dominant anode as an intercalation material for lithium. With demand for lithium-ion battery performance improvements such as higher energy density and fast-charging, silicon may be added as an active material or even completely replacing graphite as a dominant anode material. Most electrodes that are considered “silicon anodes” in the industry are graphite anodes with silicon added in small quantities (typically <20%). These graphite-silicon mixture anodes must utilize the graphite, which has a lower lithiation voltage compared to silicon; the silicon has to be nearly fully lithiated in order to utilize the graphite. Therefore, these electrodes do not have the advantage of a silicon or silicon composite anode where the voltage of the electrode is substantially above 0 V vs Li/Li+ and thus are less susceptible to lithium plating. Furthermore, these electrodes can have significantly higher excess capacity on the silicon versus the opposite electrode to further increase the robustness to high rates.
- Silicon-based anodes have a lithiation/delithiation voltage plateau at about 0.3-0.4 V vs. Li/Li+, which allows it to maintain an open circuit potential that avoids undesirable Li plating and dendrite formation. While silicon shows excellent electrochemical activity, achieving a stable cycle life for silicon-based anodes is challenging due to silicon's large volume changes during lithiation and delithiation. Silicon regions may lose electrical contact from the anode as large volume changes coupled with its low electrical conductivity separate the silicon from surrounding materials in the anode.
- In addition, the large silicon volume changes exacerbate solid electrolyte interphase (SEI) formation, which can further lead to electrical isolation and, thus, capacity loss. Expansion and shrinkage of silicon particles upon charge-discharge cycling causes pulverization of silicon particles, which increases their specific surface area. As the silicon surface area changes and increases during cycling, SEI formation repeatedly breaks apart and reforms. The SEI formation thus continually builds up around the pulverizing silicon regions during cycling into a thick electronic and ionic insulating layer. This accumulating SEI formation increases the impedance of the electrode and reduces the electrode electrochemical reactivity, which is detrimental to cycle life.
- Therefore, there is a trade-off among the functions of active materials, conductive additives, and polymer binders. The balance may be adversely impacted by high energy density silicon anodes with low conductivity and huge volume variations described above. This disclosure address this issue through the use of primary resin carbon precursors comprising water soluble acidified polyamide-imide (PAI) (e.g. 5-8%) and various polymeric stabilizing additives such as polyacrylic acid (PAA) solution, poly (maleic acid, methyl methacrylate/methacrylic acid, butadiene/maleic acid) solutions, water soluble carboxyl acid group containing (co)polyimide solution, and other soluble polymers containing carboxyl acid groups. These polymeric stabilizing additives may assist in the stabilizing the slurry, and may also serve as a carbon source. In some embodiments, the primary resin carbon precursor comprises an aqueous solution of two or more polymers.
- Further water soluble polymers that may be used as polymeric stabilizing additives include, but are not limited to, one or more of Polyamide-imide {Includes International-innotek (GT-720W, GT-721W, GT-722W), China-innotek (PIW-015, PIW-025, PIW-026), Elantas (Elan-bind 1015, Elan-bind 1015 NF), Solvay Torlon AI series (AI30, AI30-LM, AI10, AI10-LM)}; Polyimide; Ammonium Lignosulfonate; Kraft Lignin; Dextran; Pullulan (polysaccharide polymer); Phenolic resins {Includes(Plenco (Novolac Resins), Resol Resins, polymethylol phenol, ERPENE PHENOLIC RESIN (emulsion)}; Formaldehyde based Resins; Melamine-formaldehyde based resins; Silane based resins (gelest); Polyurethanes; TOCRYL (acrylic emulsion); Chitosan; Helios Resins {Includes (DOMOPOL, DOMACRYL, DOMALKYD and DOMEMUL}; Polymethyl methacrylate; Poly(methacrylic acid); Poly(vinyl acetate)/poly(vinyl alcohol) complexes; ACRONAL water-based acrylic and stryrene-acrylic emulsion polymers; STYROFAN carboxylated styrene-butadiene binders; Solic Acrylic Resin; Rotaxane; Poly(acrylic acid); Cellulose; Starch; Polysacharides; Glycogen; Carbohydrates (other); and polymers with the following backbones Sucrose, Glucose, Sucralose, Xylitol, Sorbitol, Sucralose, Glucosidases, Galactose, and Maltose.
- Further additives may be used in order to modify the characteristics of the polymer solution. Suitable additives include, but are not limited to, one or more of Poly(acrylic acid), Carboxymethylcellulose (CMC), Polyvinylpyrrolidone, Myo-Inositol, Mannitol, Pinitol, Ribose, Sorbitol, Fucose, Maltodextrin, Ganglioside, Maltose, Sucrose, Glucose, Sucralose, Xylitol, Fructose, Palatinose hydrate, Dextran sucrase, Guanosine, Inulin, Sucrose phosphorylase, Glucosidases, AmberLite, Raffinose, Mannose, Psicose, Hexokinase, NADHs, Phosphoglucose, Phosphomannose, Topiramate, Furfurals, Nuciferine, Galactose, and Maltose. In some embodiments these additives may be added to the resin to increase its viscosity (e.g. by >10%) to facilitate the processing of the slurry and improve the coating quality.
- Water-soluble PAI (WPAI) material has a polyamide-imide (PAI) backbone, but the polymer is functionalized with acidic groups (such as carboxylic acid) to allow the polymer to dissolve in water, so WPAI is a PAI analog with acidic functional groups added to the chemical formula. Water soluble PAI is similar in chemical structure to PAI, however acid groups such as carboxylic acid or amic acid are embedded into the polymer backbone.
- Water-soluble acidified PAI and water-based acidic polymer solution additive anodes provide the benefits of improved cycle life, increased energy density, increased power density, improved flexibility, improved adhesion, and reduced cost. Water-soluble acidified PAI and water-based acidic polymer solution additive electrodes may also provide improved safety. WPAI polymers can contain water; for example, WPAI polymer can have a water content of 45-75%, in some embodiments, the water content is 65%. Additional water may still be needed to dissolve the polymer above the water content already present in the polymer.
- As discussed above, water soluble acidified PAI is a WPAI having a PAI backbone, functionalized with acidic groups to allow the polymer to dissolve in water. Acidic functional groups that may be used to functionalize PAI include, but are not limited to, one or more of Amic acid, Butane tetracarboxylic acid (BTC), Tetracarboxylic acid (TC), Carboxylic acid, Licanic acid, Methacrylic acid, Acetic acid, Aminomethanesulfonic acid, Anthranilic acid, Benzenesulfonic acid, Benzoic acid, Camphor-10-sulfonic acid, Citric acid, Folic acid, Formic acid, Fumaric acid, Gallic acids, Lactic acid, Maleic acid, Malonic acid, Methanesulfonic acid, Nitrilotriacetic acid, Oxalic acid, Peracetic acid, Phthalic acid, Propionic acid, Salicylic acid, Sorbic acid, Succinic acid, Sulfamic acid, Sulfanilic acid, Tannic acid, Thioacetic acid, Trifluoromethanesulfonic acid, Acrylic acids, Aminophenylboronic acid, and Fuconic acid. In further embodiments, non-acidic groups may be used to functionalize the PAI such as Phosphates (including phosphate esters and phosohate diesters), Ranirestat, and Phosphatase.
-
FIG. 2A is a flow diagram of a direct coating process for fabricating a cell with a silicon-dominant electrode, in accordance with an example embodiment of the disclosure. This process comprises physically mixing the electrode coating layer and conductive additive together, and coating it directly on a current collector as opposed to forming the electrode coating layer on a substrate and then laminating it on a current collector. This strategy may also be adopted by other anode-based cells, such as graphite, conversion type anodes, such as transition metal oxides, transition metal phosphides, and other alloy type anodes, such as Sn, Sb, Al, P, etc. - In
step 201, the raw electrode coating layer may be mixed to form a slurry with stable viscosities of more than 1500 cp by using water-soluble acidified PAIs (WPAI) and water-based acidic polymer solution additives. The addition of the polymer solution additive enables the adjustment of the viscosity of the polymer and homogenization of the slurry. The fabricated anode shows superior adhesion to copper, a remarkable cohesion, and exceptional flexibility. This anode is shown to be capable of fast charging and performs similar or better than current anodes. - The particle size and mixing times may be varied to configure the electrode coating layer density and/or roughness. Furthermore, cathode electrode coating layers may be mixed in
step 201, where the electrode coating layer may comprise lithium cobalt oxide (LCO), lithium iron phosphate, lithium nickel cobalt manganese oxide (NMC), Ni-rich lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium nickel manganese spinel, LFP, Li-rich layer cathodes, LNMO or similar materials or combinations thereof, mixed with carbon precursor and additive as described above for the anode electrode coating layer. - As described herein, aqueous-based polyamide-imide resins used to fabricate silicon dominant anodes are disclosed. Environmentally friendly bases may be used in the slurry and stabilizers may also be used. In some embodiments, water soluble PAI (5-20% in water) is used as a carbon source (precursor), triethanolamine is used as base and PAA as stabilizer to create high silicon content anodes.
- The slurry may be made in water and may have varying composition. In one embodiment, the slurry may contain one or more of the following components in the following ranges:
-
- DI water: 30-70%
- Polymer solids: between 5-35%
- Base: less than 30%
- Acid: less than 25%
- Surfactant: less than 5%
- Other polymer additives: less than 40%.
- Bases that can be used in the slurry include, but are not limited to, one or more of Triethanolamine, Triethylamine, N-Methyldiethanolamine, Butyldiethanolamine, Diethylamine, Ethylamine, Tetrabutylammonium hydroxide, Tetramethylammonium hydroxide, Tetramethylammonium hydroxide, Triisopropanolamine, Trolamine, Amino-2-propanol, Triisobutylamine, N-Isopropyl-N-methyl-tert-butylamine, 2-Amino-2-methyl-1-propanol, 1-Amino-2-butanol, 2-Amino-1-butanol, Diethanolamine, Ethanolamine, 2-Dimethylaminoethanol, N-Phenyldiethanolamine, 2-(Dibutylamino)ethanol, 2-(Butylamino)ethanol, N-tert-Butyldiethanolamine, N-Ethyldiethanolamine, Avridine, and 2-(Diisopropylamino)ethanol.
- In some embodiments, aqueous-based polyamide-imide resins are used to create a slurry containing an environmentally friendly base (such as triethanolamine) along with polyacrylic acid (PAA). In this slurry, PAI is used as the main carbon source, triethanolamine as the base, and PAA both as the slurry stabilizer and as carbon source. The environmentally friendly base (such as triethanolamine) is a non-corrosive amine base which facilitates the dissolution of the PAI in water.
- In some embodiments, the slurry contains an optional surfactant. Addition of a surfactant may improve the coating quality. Suitable surfactants include, but are not limited to, octyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide, Polyvinylpyrrolidone α-fluoro homoallylic alcohols, α-Cyclodextrin, TritonX-100, FluorN 561 and FluorN 562, ETI 929 (from EnvTech), alkyl glycosides, and TEGO® Surten E.
- In an example embodiment, for a silicon-dominant anode, 30-40 grams of dry WPAI, 15-25 grams of a basic amine such as butyldiethanolamine or triethanolamine, and 400-500 grams of water may be mixed at high temperature to form a solution. Then, 30-50 grams of this solution may be mixed with 5-20 grams of silicon microparticles (˜10-12 μm) plus 0.2-0.5 grams of PAA 12% solution in water as additive, and 4-8 grams of water. The mixture may be mixed using a low shear mixer or a centrifugal speed mixer, where
FIG. 3 shows the changes in the viscosity of the solution versus mixing time. - In a further example embodiment, for a silicon-dominant anode, a WPAI solution was made using the following example formulation in Table 1.
-
TABLE 1 WPAI solution grams WPAI polymer 100 Water 458 triethanolamine 27 - To prepare the WPAI solution, 100 grams of the polymer powder (water content 45-75%) may be dissolved in a mixture of 458 grams of DI water and 27 grams of triethanolamine. Then the temperature of the mixture may be raised to >80° C. under vigorous stirring overnight to allow the polymer to dissolve in the solution. Then the solution may be filtered to form the WPAI solution used to make the slurry.
- In another example embodiment, WPAI-resin may be used to make a slurry with various formulations having different types of silicon to illustrate that different silicon particles may be used. The formulation of the slurry was as follows in Table 2.
-
TABLE 2 Si 20.92% PAI-resin 66.90% Polyacrylic acid (12% in water) - 12.07% PAA surfactant 0.10% - To prepare the slurries with different silicon particles, silicon powders with different particle size (D50 of 5 μm and D50 of 12 μm) may be added to a solution of the resin pre-mixed with the surfactant in the proportions set forth above in Table 2. Then PAA solution may be added to the mixture and further mixed to form the slurry.
- Three separate slurries may be prepared using the Table 2 formulation with the following silicon powders:
-
- Sample 1: Silicon powder with D50 of 12 μm
- Sample 2: Silicon powder with D50 of 12 μm (80%) and D50 of 5 μm (20%)
- Sample 3: Silicon powder with D50 of 5 μm.
FIG. 8 shows the changes in the viscosity of the solution versus temperature forSample 3, above.
- In
step 203, the as-prepared slurry may be coated on a copper foil, 20 μm thick in this example, and instep 205 may be dried at 130° C. in a convection oven to dry the coating and form the green anode. Similarly, cathode electrode coating layers may be coated on a foil material, such as aluminum, for example. - An optional calendering process may be utilized in
step 207 where a series of hard pressure rollers may be used to finish the film/substrate into a smoother and denser sheet of material. - The slurries from Samples 1-3 above may be coated separately on 15 μm copper foils and pyrolyzed under Argon gas at 650° C. for 3 hours to form silicon dominant anodes. Testing may be performed between 4.2 V-2 V using the sample anodes and NMC cathode. The electrochemical performance of the anodes in pouch cells is shown in
FIG. 9 . - In
step 209, the electrode coating layer may be pyrolyzed by heating to 500-800° C., 650° C. in this example, in an inert atmosphere such that carbon precursors are partially or completely converted into conductive carbon. The pyrolysis step may result in an anode electrode coating layer having silicon content greater than or equal to 50% by weight, where the anode has been subjected to heating at or above 400 degrees Celsius. In one embodiment the pyrolysis conditions may be between 450-800° C., under Argon, Nitrogen, or Forming gas. - Pyrolysis can be done either in roll form or after punching in
step 211. If done in roll form, the punching is done after the pyrolysis process. In instances where the current collector foil is not pre-punched/pre-perforated, the formed electrode may be perforated with a punching roller, for example. The punched electrodes may then be sandwiched with a separator and electrolyte to form a cell. Instep 213, the cell may be subjected to a formation process, comprising initial charge and discharge steps to lithiate the anode, with some residual lithium remaining, and the cell capacity may be assessed. -
FIG. 2B is a flow diagram of an alternative process for lamination of electrodes, in accordance with an example embodiment of the disclosure. While the previous process to fabricate composite anodes employs a direct coating process, this process physically mixes the active material, conductive additive, and binder together coupled with peeling and lamination processes. - This process is shown in the flow diagram of
FIG. 2B , starting withstep 221 where the raw electrode coating layer may be mixed to form a slurry with stable viscosities of more than 1500 cp by using water-soluble acidified PAIs (WPAI) and water-based acidic polymer solution additives. The addition of the polymer solution additive enables the adjustment of the viscosity of the polymer and homogenization of the slurry. - The particle size and mixing times may be varied to configure the electrode coating layer density and/or roughness. Furthermore, cathode electrode coating layers may be mixed in
step 221, where the electrode coating layer may comprise lithium cobalt oxide (LCO), lithium iron phosphate, lithium nickel cobalt manganese oxide (NMC), Ni-rich lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium nickel manganese spinel, LFP, Li-rich layer cathodes, LNMO or similar materials or combinations thereof, mixed with carbon precursor and additive as described above for the anode electrode coating layer. - In an example embodiment, for a silicon-dominant anode, 30-40 grams of dry WPAI, 15-25 grams of a basic amine such as butyldiethanolamine or triethanolamine, and 400-500 grams of water may be mixed at high temperature to form a solution. Then, 30-50 grams of this solution may be mixed with 5-20 grams of silicon microparticles (˜10-12 μm) plus 0.2-0.5 grams of PAA 12% solution in water as additive, and 4-8 grams of water. The mixture may be mixed using a low shear mixer or a centrifugal speed mixer, where
FIG. 3 shows the changes in the viscosity of the solution versus mixing time. - In
step 223, the slurry may be coated on a polymer substrate, such as polyethylene terephthalate (PET), polypropylene (PP), or Mylar. The slurry may be coated on the PET/PP/Mylar film at a loading of 3-6 mg/cm2 for the anode and 15-35 mg/cm2 for the cathode, and then dried instep 225. An optional calendering process may be utilized where a series of hard pressure rollers may be used to finish the film/substrate into a smoothed and denser sheet of material. - In
step 227, the green film may then be removed from the PET, where the active material may be peeled off the polymer substrate, the peeling process being optional for a polypropylene (PP) substrate, since PP can leave ˜2% char residue upon pyrolysis. The peeling may be followed by a cure andpyrolysis step 229 where the film may be cut into sheets, and vacuum dried using a two-stage process (100-140° C. for 14-16 hours, 200-240° C. for 4-6 hours). The dry film may be thermally treated at 1000-1300° C. to convert the polymer matrix into carbon. - In
step 231, the pyrolyzed material may be flat press or roll press laminated on the current collector, where for aluminum foil for the cathode and copper foil for the anode may be pre-coated with polyamide-imide with a nominal loading of 0.35-0.75 mg/cm2 (applied as a 5-7 wt % varnish in NMP, dried 10-20 hour at 100-140° C. under vacuum). In flat press lamination, the active material composite film may be laminated to the coated aluminum or copper using a heated hydraulic press (30-70 seconds, 250-350° C., and 3000-5000 psi), thereby forming the finished composite electrode. In another embodiment, the pyrolyzed material may be roll-press laminated to the current collector. - In
step 233, the electrodes may then be sandwiched with a separator and electrolyte to form a cell. The cell may be subjected to a formation process, comprising initial charge and discharge steps to lithiate the anode, with some residual lithium remaining, and testing to assess cell performance. -
FIG. 3 illustrates slurry viscosity versus mixing time, in accordance with an example embodiment of the disclosure. The plot indicates that a slurry with stable viscosity can be achieved using WPAI as the carbon precursor, where a viscosity of 1500 centipoise (cp) may be obtained after ˜15 hours with this mixture. The polymer additive may play a role in linking long chain PAIs together and as a result increases the viscosity of the solution. -
FIG. 4 illustrates the results of thermal gravimetric analysis (TGA) of dry WPAI, in accordance with an example embodiment of the disclosure. The TGA analysis may be performed under nitrogen atmosphere with a flow rate of 100 sccm and temperature ramp rate of 5° C./min. The plot shows the weight percentage remaining and the normalized heat flow provided to the material in W/g over a temperature range up to 800° C. The TGA analysis indicates that the polymer has ˜58% char yield at 650° C. and more than 53% char yield at 800° C. -
FIG. 5 illustrates an adhesion test for a silicon-dominant anode with water-soluble acidified PAI and water-based acidic polymer solution additive, in accordance with an example embodiment of the disclosure. The test setup includes aclamp 501 for holding anelectrode 505 fastened to aglass slide 503 using adhesive tape (not visible) holding the anode on one side on the other is a double sided adhesive tape (not visible) for coupling to weights. - The anode shows a superior adhesion strength, with capability of holding 350 grams of weights before the coating detaches from the copper. Such adhesion is much higher than most anodes which mostly fail to hold more than 50 grams of weights.
-
FIG. 6 illustrates a silicon-dominant anode after a winding test, in accordance with an example embodiment of the disclosure. In this example, the anode is wrapped around a 4 mm mandrel in order to test the feasibility of using it for cylindrical cells. As it can be seen fromFIG. 6 , the anode shows only minor cracks, no copper exposures due to carbon detachments, and no flaking. Therefore, such a remarkable flexibility and anode integrity indicates that the water-based slurry anode is appropriate for use in cylindrical cells. -
FIG. 7 illustrates normalized discharge capacity of a cell with water-soluble acidified PAI and water-based acidic polymer solution additive anode compared to a standard cell with NMP-based resin laminated anode, in accordance with an example embodiment of the disclosure. The plot compares the normalized capacity retention of the standard anode (solid line—anode laminated on a current collector with an adhesive) versus the water-soluble acidified PAI and water-based acidic polymer solution additive anode (dashed line). The NMP-based resin anode may be laminated on a copper foil coated with PAI adhesive, as opposed to the direct-coated water-based resin anode. - While the absolute capacity values indicate that both anodes have similar capacities, the normalized capacity values shown indicate that the water-soluble acidified PAI anode demonstrates a better capacity retention compared with the standard anode. The standard anode in this example is a free standing pyrolyzed coupon that is laminated on adhesive-coated copper. As can be seen in
FIG. 7 , the water-soluble acidified PAI anode is still at near 100% discharge capacity after 60 cycles. In addition to improved cycle life, water-soluble acidified PAI and water-based acidic polymer solution additive anodes demonstrate increased energy density, increased power density, improved flexibility, improved adhesion, and reduced cost using water soluble acidified PAI. -
FIG. 8 illustrates slurry viscosity against temperature for a sample containing silicon powder with D50 of 5 μm at 20.92%, PAI-resin at 66.90%, Polyacrylic acid (12% in water)—PAA at 12.07% and surfactant at 0.10%, at 60 and 100 RPM. -
FIG. 9 illustrates electrochemical performance of the anodes in pouch cells, where the anodes are made from slurries according to Samples 1-3 above. The cycling may be performed at 2 C charge and 0.5 C discharge between 4.2-2.5 V. - The following provides further examples and/or embodiments of silicon-dominant anodes and processes for manufacturing such silicon-dominant anodes. In the interest of brevity, the silicon-dominate anodes are described below as being manufactured per the direct coating process of
FIG. 2A . However, each of the below silicon-dominant anodes may be manufactured per the direct coating process ofFIG. 2A or the laminating process ofFIG. 2B . - A silicon-dominate anode was prepared based on the following slurry formulation, which is presented in mass units in Table 3 and as weight percentages in Table 4:
-
TABLE 3 Silicon powder 10.461 g PAI solution in DI water (6%) 33.457 g Polyacrylic acid solution in water (12%) 6.037 g Surfactant 0.045 g -
TABLE 4 Silicon powder 20.9% PAI solution in DI water (6%) 66.9% Polyacrylic acid solution in water (12%) 12.1% Surfactant 0.1% - In particular, the slurry was formed at 201 of
FIG. 2A from the above components by adding the surfactant and PAI solution to a mixer. The mixer mixed the surfactant and PAI solution at 2000 rpm for 1 minute. The silicon powder was then added to the mixer and mixed at 2000 rpm for another minute. Then, the PAA solution was added to the mixer and mixed at 2000 rpm for another minute. At which point, the mixture was filtered through a 120 μm mesh to remove agglomerates and returned to the mixer. The mixer further mixed the slurry at 2000 rpm for a minute and then at 2200 rpm for another minute. - At 203, the slurry was coated on a foil. In particular, the slurry was hand coated using a 9 mil doctor blade on one side of a 20 μm copper foil. In particular, the copper foil was a rolled copper foil made of C15500 alloy and the slurry was applied to a thickness of about 30 μm, resulting in a copper foil to active material thickness ratio of about 0.66 (20 μm/30 μm). Some embodiments may utilize a copper foil made of C15500, C19400, C26000, or C51000 copper alloys.
- At 205, the slurry coated copper foil was dried at about 90° C. in a gravity convection oven for 10 to 15 minutes, then slit into 2-inch wide anode stripes. The anode stripes were further dried at 80° C. under vacuum overnight before calendering. At 207, the anode stripes were calendered using a fixed gap calendering machine at 60° C. to reach designed thickness of 50-65 μm including 20 μm Cu foil and density of approximately 1.0-1.1. After calendering, the anode stripes were punched to form anode coupons and the anode coupons at 209 were pyrolyzed at 650° C. with 5° C./min ramp and 180 minute dwell time in an Argon atmosphere. Such process resulted in single-side anodes having an active material layer of about 30 μm on one side of the copper foil. The final composition of the anode active material after pyrolysis was about 86% silicon and about 14% pyrolytic carbon. Moreover the active material had a porosity of about 50-56%.
- Some embodiments of a silicon-dominant anode may utilize a foil thickness to active material layer thickness of over 0.5, wherein the porosity of the active material layer is below 70%. Some embodiments of a silicon-dominant anode may utilize a foil thickness to active material layer thickness of 0.15, about 0.15, over 0.15, 0.25, about 0.25, over 0.25, 0.5, about 0.5, over 0.5, 0.66, about 0.66, or over 0.66, wherein the porosity of the active material layer is 70%, about 70%, below about 70%, 60%, about 60%, below about 60%, 50%, about 50%, below about 50%, 40%, about 40%, below about 40%, 30%, about 30%, or below about 30%.
- Moreover, some embodiments of a silicon dominant anode may utilize a foil thickness to porosity-adjusted active material layer thickness ratio of 0.25, about 0.25, over 0.25, 0.33, about 0.33, over 0.33, 0.5, about 0.5, over 0.5, 0.6, about 0.6, over 0.6, 1, about 1, over 1, 1.3, about 1.3, or over 1.3. Such ratio may be calculated per Equation 1:
-
- Single-layer pouch cells were then constructed from the single-sided anodes. In particular, each pouch cell included one single-layer anode, one double layer cathode, and about 1 mL of electrolyte, providing an approximate capacity of 78 mAh. The cathode facing pouch side was taped using Kapton tape to avoid/minimize electrochemical reactions. Each single-layer pouch cell was subject to a hot pressing step, a cold pressing step, or skipped the pressing step, before going through formation and degassing. Afterwards, each single-layer pouch cell was clamped between a bottom metal plate and top metal plate and tested in a battery tester. In particular, each single-layer cell was clamped in the order of a bottom metal plate, paper, cell, foam pad, top metal plate using fixed gap.
- Some embodiments of the single-layer pouch cells may be assembled using a fixture where the pressure is maintained by clamping the cell at a certain gap or using springs, actuators or other means to achieve a pressure within about 10%, about 11%, about 15%, or about 20% of original pressure (about 120 kPa). In some embodiments, the pressure may be applied using compressible foam, metal springs, air bladder, paper, or fabric.
- Some embodiments of the single-layer pouch cells may have an electrolyte to Ah ratio of about 2 g/Ah, over 2 g/Ah, about 2.4 g/Ah, over 2.4 g/Ah, about 5 g/Ah, over 5 g/Ah, about 10 g/Ah, over 10 g/Ah, about 16 g/Ah, over 16 g/Ah.
- Some embodiments of the single-layer pouch cells may be sealed with excess pouch material on at least one side. For example, the seal may be at least 5 mm, at least 3 mm, or at least 2 mm from an edge of the cell stack.
- In some embodiments of the single-layer pouch cells, the silicon-dominate anode may have an areal capacity between 9 mAh/cm2 and 15 mAh/cm2. Moreover, the amount of electrolyte per active area of the electrode may be between 0.02 and 0.1 mL/cm2. The active area of the electrode corresponds to the area of the silicon-dominate anode in cm2 that participates in the electrochemical reaction. In some embodiments, the silicon-dominate anode may have an areal capacity between 5 mAh/cm2 and 11 mAh/cm2 with the amount of electrolyte per active area of electrode between 0.005 and 0.05 m L/cm2.
- The performance of the single-layer pouch cells were then compared to five-layer pouch cells. Each of the five-layer pouch cells included six layers of double-sided anodes and five layers of double-sided cathodes. The anodes of the five-layer pouch cells were made using the same formulation and mixing method as the single-layer pouch cells. The anodes of the five-layer pouch cells used a 15 μm foil with an active material thickness of about 30 μm on each side, thus resulting in a copper foil to active material thickness ratio of about 0.66 (20 μm/30 20 μm). Each single-layer pouch cell provided 78 mAh measured between 4.2 V and 2.75 V at 0.5 C. Conversely, each five-layer pouch cell provided 780 mAh measured between 4.2 V and 2.75 V at 0.5 C.
- Referring now to
FIG. 10 , capacity retention of single-layer pouch cells (enhanced cells) and five-layer pouch cells (baseline cells) are depicted for cycle life based on 2 C (4.2 V)/0.5 C (2.75 V) cycles. In particular, the enhanced cells and baseline cells ofFIG. 10 include anodes manufactured per the formulation of Table 3 and process described above. As shown bylines 1000, the baseline cells reached their 80% retention mark at about 160 cycles. However, as shown bylines 1010, the enhanced cells reached their 80% retention mark at about 220 cycles. - Referring now to
FIG. 11 , capacity retention of single-layer pouch cells (enhanced cells) and five-layer pouch cells (baseline cells) are depicted for cycle life based on 4 C (4.2 V)/0.5 C (3.2 V) cycles. In particular, the enhanced cells and baseline cells ofFIG. 11 include anodes manufactured per the formulation of Table 3 and process described above.Lines 1100 depict capacity retention of the baseline cells, whereaslines 1110 depict capacity retention of the enhanced cells. As shown, the enhanced cells retained a greater amount of the original capacity after about 120 cycles than the baseline cells. - Referring now to
FIG. 12 , a comparison is presented for capacity retention of pressed and not pressed pouch cells during cycle life based on 2 C (4.2 V)/0.5 C (2.75 V) cycles. In particular, pressed and not pressed pouch cells include anodes manufactured per the formulation of Table 3 and process described above. The pressed cells (shown by lines 1200) include single-layer pouch cells subjected to a hot pressing process in which the cells were pressed at 140 psi at 100° C. for 2 minutes and single-layer pouch cells subject to a cold pressing process in which the cells were pressed at 140 psi at room temperature. The not pressed cells (shown by lines 1210) were not subjected to either hot pressing or cold pressing processes. While a bit difficult to see, thelines 1210 of the not pressed cells closely track thelines 1200 for the pressed cells for the first 30 cycles.FIG. 12 does not include data for the not pressed cells beyond the first 30 cycles. PerFIG. 12 , pressing does provide a significant factor of capacity retention for at least the first 30 cycles of cycle life based on 2 C(4.2 V)/0.5 C(2.75 V) cycles. - Referring now to
FIG. 13 , a comparison is presented for capacity retention of single-layer pouch cells having anodes manufactured per three different formulations, which are referred to as enhanced cell,enhanced cell 2, andenhanced cell 3 inFIG. 13 . The enhanced cells are represented bylines 1310 inFIG. 13 . Each enhanced cell includes an anode manufacture per the formulation of Table 3 and the above described process. - The
enhanced cells 2 are represented bylines 1320 inFIG. 13 . Eachenhanced cell 2 includes an anode manufactured per the formulation of Table 5 and the above described process. -
TABLE 5 Silicon powder 29.90% PAI solution (9.5%) in DI water 69.95% Surfactant 0.15%
After pyrolysis, the composition for the anode active material ofenhanced cell 2 was about 90% silicon and about 10% pyrolytic carbon. Moreover, the active material of eachenhanced cell 2 had a porosity of about 50-56%. - The
enhanced cells 3 are represented bylines 1330 inFIG. 13 . Eachenhanced cell 3 includes an anode manufactured per the formulation of Table 6 and the above described process. -
TABLE 6 Silicon powder 34.50% PAI solution (9.5%) in DI water 64.56 Carbon additives 0.77% Surfactant 0.17%
After pyrolysis, the composition for the anode active material of enhancecell 3 was about 90% silicon, about 8% pyrolytic carbon, and about 2% carbon additive. Moreover, the active material of eachenhanced cell 3 had a porosity of about 50-56%. - In view of the above results, the single-layer pouch cells (e.g., enhanced cell,
enhanced cell 2, and enhanced cell 3) improve normalized capacity retention by about 50% for 2 C (4.2 V)/0.5 C (2.75 V) cycling when compared to the five-layer pouch cells (e.g., baseline cells). Moreover, the single-layer pouch cells (e.g., enhanced cell,enhanced cell 2, and enhanced cell 3) reduce degradation by more than a factor of 3 (i.e., has less than ⅓ the degradation) up to about 120 cycles for 4 C (4.2 V)/0.5 C (3.2 V) cycling when compared to the five-layer pouch cells (e.g., baseline cells). - In an example embodiment of the disclosure, a method and system is described for water soluble weak acidic resins as carbon precursors for silicon-dominant anodes. The battery electrode may comprise an electrode coating layer on a current collector, where the electrode coating layer is formed from silicon and pyrolyzed water-soluble acidic polyamide imide resin carbon precursor. The electrode coating layer may comprise a pyrolyzed water-based acidic polymer solution additive. The polymer solution additive may comprise one or more of: polyacrylic acid (PAA) solution, poly (maleic acid, methyl methacrylate/methacrylic acid, butadiene/maleic acid) solutions, and water soluble PAA. The electrode coating layer may comprise conductive additives. The current collector may comprise a metal foil, where the metal current collector comprises one or more of a copper, tungsten, stainless steel, and nickel foil in electrical contact with the electrode coating layer. The electrode coating layer may comprise more than 70% silicon. The electrode may be in electrical and physical contact with an electrolyte, where the electrolyte comprises a liquid, solid, or gel. The battery electrode may be in a lithium ion battery.
- As utilized herein, “and/or” means any one or more of the items in the list joined by “and/or”. As an example, “x and/or y” means any element of the three-element set {(x), (y), (x, y)}. In other words, “x and/or y” means “one or both of x and y”. As another example, “x, y, and/or z” means any element of the seven-element set {(x), (y), (z), (x, y), (x, z), (y,z), (x, y, z)}. In other words, “x, y and/or z” means “one or more of x, y and z”. As utilized herein, the term “exemplary” means serving as a non-limiting example, instance, or illustration. As utilized herein, the terms “e.g.,” and “for example” set off lists of one or more non-limiting examples, instances, or illustrations. As utilized herein, a battery, circuitry or a device is “operable” to perform a function whenever the battery, circuitry or device comprises the necessary hardware and code (if any is necessary) or other elements to perform the function, regardless of whether performance of the function is disabled or not enabled (e.g., by a user-configurable setting, factory trim, configuration, etc.).
- While the present invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from its scope. Therefore, it is intended that the present invention not be limited to the particular embodiment disclosed, but that the present invention will include all embodiments falling within the scope of the appended claims.
Claims (32)
1. A battery anode, comprising:
a current collector comprising a current collector top side and a current collector bottom side separated from the current collector top side by a thickness of the current collector; and
an active material layer comprising an active material layer top side and an active material layer bottom side on the current collector top side,
wherein the active material layer comprises pyrolytic carbon and at least 50% silicon;
wherein the active material layer top side is separated from the active material layer bottom side by a thickness of the active material layer; and
wherein a ratio of the thickness of the current collector to the thickness of the active material layer is; between 0.15 and 0.66.
2. The battery anode of claim 1 , wherein a porosity of the active material layer is below 70%.
3. The battery anode of claim 1 , wherein a porosity of the active material layer is below 60%.
4. The battery anode of claim 1 , wherein a porosity of the active material layer is below 50%.
5. The battery anode of claim 1 , wherein a porosity of the active material layer is below 40%.
6. The battery anode of claim 1 , wherein a porosity of the active material layer is below 30%.
7. The battery anode of claim 1 , wherein the first ratio of the thickness of the current collector to the thickness of the active material layer is between 0.25 and 0.66.
8. (canceled)
9. The battery anode of claim 1 , wherein:
a ratio of the thickness of the current collector to a porosity-adjusted active material layer thickness of the active material layer is over 0.25; and
wherein the porosity-adjusted active material layer thickness is determined per T×(1−P/100), where Tis the thickness of the active material layer and P is a porosity percentage of the active material layer.
10. The battery anode of claim 9 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is over 0.5.
11. The battery anode of claim 9 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is over 0.6.
12. The battery anode of claim 9 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is over 1.
13. The battery anode of claim 9 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is over 1.3.
14. (canceled)
15. A battery cell comprising:
a cathode;
a separator;
an electrolyte; and
an anode comprising a current collector and an active material layer;
wherein the current collector comprises a current collector top side and a current collector bottom side separated from the current collector top side by a thickness of the current collector;
wherein the active material layer comprises an active material layer top side and an active material layer bottom side on the current collector top side;
wherein the active material layer comprises pyrolytic carbon and at least 50% silicon;
wherein the active material layer top side is separated from the active material layer bottom side by a thickness of the active material layer;
wherein a ratio of the thickness of the current collector to a porosity-adjusted active material layer thickness of the active material layer is between 0.25 and 1; and
wherein the porosity-adjusted active material layer thickness is determined per T×(1−P/100), where T is the thickness of the active material layer and P is a porosity percentage of the active material layer.
16. The battery cell of claim 15 , wherein a porosity of the active material layer is below 70%.
17. The battery cell of claim 15 , wherein a porosity of the active material layer is below 60%.
18. The battery cell of claim 15 , wherein a porosity of the active material layer is below 50%.
19. The battery cell of claim 15 , wherein a porosity of the active material layer is below 40%.
20. The battery cell of claim 15 , wherein a porosity of the active material layer is below 30%.
21. The battery cell of claim 15 , wherein a ratio of the thickness of the current collector to the thickness of the active material layer is between 0.15 and 0.66.
22. (canceled)
23. The battery cell of claim 15 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is between 0.33 and 1.
24. The battery cell of claim 15 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is between 0.5 and 1.
25. The battery cell of claim 15 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is between 0.6 and 1.
26. The battery cell of claim 15 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is between 0.25 and 0.6
27. The battery cell of claim 15 , wherein the ratio of the thickness of the current collector to porosity-adjusted active material layer thickness of the active material layer is between 0.25 and 0.5.
28. (canceled)
29. The battery anode of claim 1 , wherein the ratio of the thickness of the current collector to the thickness of the active material layer is between 0.25 and 0.66.
30. The battery anode of claim 1 , wherein the ratio of the thickness of the current collector to the thickness of the active material layer is between 0.5 and 0.66.
31. The battery anode of claim 1 , wherein the ratio of the thickness of the current collector to the thickness of the active material layer is between 0.25 and 0.5.
32. The battery anode of claim 9 , wherein the ratio of the thickness of the current collector to the porosity-adjusted active material layer thickness of the active material layer is between 0.25 and 1.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/532,549 US20230163309A1 (en) | 2021-11-22 | 2021-11-22 | Silicon based lithium ion battery and improved cycle life of same |
US17/532,739 US11387443B1 (en) | 2021-11-22 | 2021-11-22 | Silicon based lithium ion battery and improved cycle life of same |
US17/856,035 US20230163269A1 (en) | 2021-11-22 | 2022-07-01 | Silicon based lithium ion battery and improved cycle life of same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/532,549 US20230163309A1 (en) | 2021-11-22 | 2021-11-22 | Silicon based lithium ion battery and improved cycle life of same |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/532,739 Division US11387443B1 (en) | 2021-11-22 | 2021-11-22 | Silicon based lithium ion battery and improved cycle life of same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20230163309A1 true US20230163309A1 (en) | 2023-05-25 |
Family
ID=82323890
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/532,549 Abandoned US20230163309A1 (en) | 2021-11-22 | 2021-11-22 | Silicon based lithium ion battery and improved cycle life of same |
US17/532,739 Active US11387443B1 (en) | 2021-11-22 | 2021-11-22 | Silicon based lithium ion battery and improved cycle life of same |
US17/856,035 Pending US20230163269A1 (en) | 2021-11-22 | 2022-07-01 | Silicon based lithium ion battery and improved cycle life of same |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/532,739 Active US11387443B1 (en) | 2021-11-22 | 2021-11-22 | Silicon based lithium ion battery and improved cycle life of same |
US17/856,035 Pending US20230163269A1 (en) | 2021-11-22 | 2022-07-01 | Silicon based lithium ion battery and improved cycle life of same |
Country Status (1)
Country | Link |
---|---|
US (3) | US20230163309A1 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130316229A1 (en) * | 2011-01-31 | 2013-11-28 | Mitsubishi Chemical Corporation | Non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery employing the same |
US20180198114A1 (en) * | 2010-12-22 | 2018-07-12 | Enevate Corporation | Methods of reducing occurrences of short circuits and/or lithium plating in batteries |
Family Cites Families (115)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3990098A (en) | 1972-12-22 | 1976-11-02 | E. I. Du Pont De Nemours And Co. | Structure capable of forming a diode and associated conductive path |
US4435444A (en) | 1981-11-10 | 1984-03-06 | Superior Graphite Co. | Method of making ultra-microcrystallite silicon carbide product |
JPS58171502A (en) | 1982-04-02 | 1983-10-08 | Toyota Motor Corp | Pulverized composite powder of ceramic and metal |
FR2671546B1 (en) | 1991-01-11 | 1993-03-12 | Pechiney Electrometallurgie | LOW SURFACE OXIDATION METALLURGICAL SILICON POWDER. |
CA2122770C (en) | 1994-05-03 | 2000-10-03 | Moli Energy (1990) Limited | Carbonaceous host compounds and use as anodes in rechargeable batteries |
EP0896374B1 (en) | 1996-12-24 | 2011-12-07 | Kao Corporation | Nonaqueous electrolyte secondary battery |
JP2948205B1 (en) | 1998-05-25 | 1999-09-13 | 花王株式会社 | Method for producing negative electrode for secondary battery |
JP3291260B2 (en) | 1998-12-03 | 2002-06-10 | 花王株式会社 | Lithium secondary battery |
JP3078800B1 (en) | 1999-06-23 | 2000-08-21 | 花王株式会社 | Method for producing negative electrode for non-aqueous secondary battery |
WO2000033404A1 (en) | 1998-12-03 | 2000-06-08 | Kao Corporation | Lithium secondary cell and method for manufacturing the same |
JP4281099B2 (en) | 1999-03-24 | 2009-06-17 | 日立化成工業株式会社 | Metal-carbon composite particles |
CA2305837C (en) | 1999-04-14 | 2011-05-31 | Sony Corporation | Material for negative electrode and nonaqueous-electrolyte battery incorporating the same |
US6743549B1 (en) | 1999-07-02 | 2004-06-01 | E.I. Du Pont De Nemours And Company | Nonaqueous electrolyte lithium secondary batteries |
JP3124272B1 (en) | 1999-12-01 | 2001-01-15 | 花王株式会社 | Non-aqueous secondary battery |
US6489061B1 (en) | 2000-05-24 | 2002-12-03 | Litech, L.L.C. | Secondary non-aquenous electrochemical cell configured to improve overcharge and overdischarge acceptance ability |
US6436576B1 (en) | 2000-05-24 | 2002-08-20 | Litech, L.L.C. | Carbon-carbon composite as an anode for lithium secondary non-aqueous electrochemical cells |
JP4137350B2 (en) | 2000-06-16 | 2008-08-20 | 三星エスディアイ株式会社 | Negative electrode material for lithium secondary battery, electrode for lithium secondary battery, lithium secondary battery, and method for producing negative electrode material for lithium secondary battery |
JP3466576B2 (en) | 2000-11-14 | 2003-11-10 | 三井鉱山株式会社 | Composite material for negative electrode of lithium secondary battery and lithium secondary battery |
JP4415241B2 (en) | 2001-07-31 | 2010-02-17 | 日本電気株式会社 | Negative electrode for secondary battery, secondary battery using the same, and method for producing negative electrode |
EP1313158A3 (en) | 2001-11-20 | 2004-09-08 | Canon Kabushiki Kaisha | Electrode material for rechargeable lithium battery, electrode comprising said electrode material, rechargeable lithium battery having said electrode , and process for the production thereof |
JP4189569B2 (en) | 2001-11-29 | 2008-12-03 | 東レ・デュポン株式会社 | Carbon film manufacturing method |
JP4225727B2 (en) | 2001-12-28 | 2009-02-18 | 三洋電機株式会社 | Negative electrode for lithium secondary battery and lithium secondary battery |
TWI278429B (en) | 2002-05-17 | 2007-04-11 | Shinetsu Chemical Co | Conductive silicon composite, preparation thereof, and negative electrode material for non-aqueous electrolyte secondary cell |
US6949314B1 (en) | 2002-08-19 | 2005-09-27 | Litech, L.L.C. | Carbon-carbon composite anode for secondary non-aqueous electrochemical cells |
JP2004103405A (en) | 2002-09-10 | 2004-04-02 | Sumitomo Bakelite Co Ltd | Raw material for carbonaceous material, silicon-containing carbonaceous material, negative electrode material of secondary battery, and lithium secondary battery |
JP2004119176A (en) | 2002-09-26 | 2004-04-15 | Toshiba Corp | Negative electrode active material for nonaqueous electrolyte rechargeable battery, and nonaqueous electrolyte rechargeable battery |
EP1573835B1 (en) | 2002-11-26 | 2017-05-03 | Showa Denko K.K. | Electrode material comprising silicon and/or tin particles and production method and use thereof |
BR0315457B1 (en) | 2002-11-29 | 2012-06-26 | negative electrode for non-aqueous secondary battery, negative electrode production process, and non-aqueous secondary battery. | |
US20040137327A1 (en) | 2003-01-13 | 2004-07-15 | Gross Karl J. | Synthesis of carbon/silicon composites |
KR100754258B1 (en) | 2003-02-20 | 2007-09-03 | 미쓰비시 가가꾸 가부시키가이샤 | Active substance for negative electrode of lithium secondary battery, negative electrode of lithium secondary battery and lithium secondary battery |
JP4729716B2 (en) | 2003-02-20 | 2011-07-20 | 三菱化学株式会社 | Lithium secondary battery negative electrode and lithium secondary battery |
CN100382362C (en) | 2003-03-26 | 2008-04-16 | 佳能株式会社 | Electrode material for lithium secondary battery and electrode structure having the electrode material |
CN100459273C (en) | 2003-07-15 | 2009-02-04 | 三星Sdi株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
JP4171904B2 (en) | 2003-08-05 | 2008-10-29 | 信越化学工業株式会社 | Lithium ion secondary battery negative electrode material and method for producing the same |
KR100657225B1 (en) | 2003-09-05 | 2006-12-14 | 주식회사 엘지화학 | Electrolyte solvent for improving safety of battery and lithium secondary battery comprising the same |
JPWO2005036690A1 (en) | 2003-10-07 | 2006-12-28 | 株式会社ジーエス・ユアサコーポレーション | Nonaqueous electrolyte secondary battery |
US7479351B2 (en) | 2003-10-09 | 2009-01-20 | Samsung Sdi Co., Ltd. | Electrode material for a lithium secondary battery, lithium secondary battery, and preparation method for the electrode material for a lithium secondary battery |
TWI261639B (en) | 2003-12-03 | 2006-09-11 | Univ Feng Chia | Method for making carbon fiber fabric and product thereof |
CN100547830C (en) | 2004-03-08 | 2009-10-07 | 三星Sdi株式会社 | The negative electrode active material of chargeable lithium cell and method for making thereof and the chargeable lithium cell that comprises it |
JP4474184B2 (en) | 2004-03-26 | 2010-06-02 | トヨタ自動車株式会社 | Method for producing active material for lithium secondary battery and method for producing lithium secondary battery |
JP4836781B2 (en) | 2004-03-30 | 2011-12-14 | 株式会社クレハ | Method for producing spherical carbon material |
DE102004016766A1 (en) | 2004-04-01 | 2005-10-20 | Degussa | Nanoscale silicon particles in negative electrode materials for lithium-ion batteries |
JP4736345B2 (en) * | 2004-04-23 | 2011-07-27 | パナソニック株式会社 | Alkaline battery |
JP4450192B2 (en) | 2004-07-01 | 2010-04-14 | 信越化学工業株式会社 | Silicon composite, method for producing the same, and negative electrode material for non-aqueous electrolyte secondary battery |
CN100553016C (en) | 2004-08-26 | 2009-10-21 | 松下电器产业株式会社 | Composite particles for electrode use and manufacture method thereof and secondary cell |
US20060051670A1 (en) | 2004-09-03 | 2006-03-09 | Shin-Etsu Chemical Co., Ltd. | Non-aqueous electrolyte secondary cell negative electrode material and metallic silicon power therefor |
JP4519592B2 (en) | 2004-09-24 | 2010-08-04 | 株式会社東芝 | Negative electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
US7615314B2 (en) | 2004-12-10 | 2009-11-10 | Canon Kabushiki Kaisha | Electrode structure for lithium secondary battery and secondary battery having such electrode structure |
JP5094013B2 (en) | 2004-12-10 | 2012-12-12 | キヤノン株式会社 | ELECTRODE STRUCTURE FOR LITHIUM SECONDARY BATTERY AND SECONDARY BATTERY HAVING THE ELECTRODE STRUCTURE |
KR100738054B1 (en) | 2004-12-18 | 2007-07-12 | 삼성에스디아이 주식회사 | Anode active material, method of preparing the same, and anode and lithium battery containing the material |
US20060147802A1 (en) | 2005-01-05 | 2006-07-06 | Kiyotaka Yasuda | Anode for nonaqueous secondary battery, process of producing the anode, and nonaqueous secondary battery |
DE102005011940A1 (en) | 2005-03-14 | 2006-09-21 | Degussa Ag | Process for the preparation of coated carbon particles and their use in anode materials for lithium-ion batteries |
FR2885734B1 (en) | 2005-05-13 | 2013-07-05 | Accumulateurs Fixes | NANOCOMPOSITE MATERIAL FOR LITHIUM ACCUMULATOR ANODE |
JP5217433B2 (en) | 2005-05-16 | 2013-06-19 | 三菱化学株式会社 | Nonaqueous electrolyte secondary battery, negative electrode thereof, and material thereof |
JP4942319B2 (en) | 2005-09-07 | 2012-05-30 | 三洋電機株式会社 | Lithium secondary battery |
KR100745733B1 (en) | 2005-09-23 | 2007-08-02 | 삼성에스디아이 주식회사 | Anode active material, producing method thereof and lithium battery using the same |
JP2007123242A (en) | 2005-09-28 | 2007-05-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
JP5162825B2 (en) | 2005-12-13 | 2013-03-13 | パナソニック株式会社 | Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same |
FR2895572B1 (en) | 2005-12-23 | 2008-02-15 | Commissariat Energie Atomique | MATERIAL BASED ON CARBON AND SILICON NANOTUBES FOR USE IN NEGATIVE ELECTRODES FOR LITHIUM ACCUMULATOR |
KR100784589B1 (en) | 2006-01-04 | 2007-12-10 | 엘에스전선 주식회사 | Carbonaceous electrode material for secondary battery and process for production thereof and secondary batteries using the same |
KR101328982B1 (en) | 2006-04-17 | 2013-11-13 | 삼성에스디아이 주식회사 | Anode active material and method of preparing the same |
KR100830612B1 (en) | 2006-05-23 | 2008-05-21 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same |
ATE525761T1 (en) | 2006-07-14 | 2011-10-15 | Korea Kumho Petrochem Co Ltd | ANODE ACTIVE MATERIAL FOR A LITHIUM SECONDARY BATTERY HYBRIDIZED WITH CARBON NANOFIBERS |
JP5173181B2 (en) | 2006-11-01 | 2013-03-27 | パナソニック株式会社 | Lithium ion secondary battery and method for producing negative electrode plate for lithium ion secondary battery |
JP5131429B2 (en) | 2006-12-15 | 2013-01-30 | 信越化学工業株式会社 | Negative electrode for nonaqueous electrolyte secondary battery and method for producing the same |
KR100818263B1 (en) | 2006-12-19 | 2008-03-31 | 삼성에스디아이 주식회사 | Porous anode active material, method of preparing the same, and anode and lithium battery containing the material |
US20090053589A1 (en) | 2007-08-22 | 2009-02-26 | 3M Innovative Properties Company | Electrolytes, electrode compositions, and electrochemical cells made therefrom |
US20080286657A1 (en) | 2007-05-16 | 2008-11-20 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery |
KR100998618B1 (en) | 2007-06-29 | 2010-12-07 | (주)넥센나노텍 | Anode electrode material hybridizing carbon nanofiber for lithium secondary battery |
KR101386163B1 (en) | 2007-07-19 | 2014-04-17 | 삼성에스디아이 주식회사 | Composite anode material, and anode and lithium battery using the same |
KR101375328B1 (en) | 2007-07-27 | 2014-03-19 | 삼성에스디아이 주식회사 | Si/C composite, anode materials and lithium battery using the same |
KR101440883B1 (en) | 2007-10-02 | 2014-09-18 | 삼성에스디아이 주식회사 | An electrode, a method for preparing the same and a lithium battery using the same |
KR100903503B1 (en) | 2007-11-02 | 2009-06-17 | 삼성에스디아이 주식회사 | Negative electrode active material, method for manufacturing the same and lithium secondary battery using the negative electrode active material |
US7745047B2 (en) | 2007-11-05 | 2010-06-29 | Nanotek Instruments, Inc. | Nano graphene platelet-base composite anode compositions for lithium ion batteries |
WO2009063801A1 (en) | 2007-11-12 | 2009-05-22 | Sanyo Electric Co., Ltd. | Negative electrode material for rechargeable battery with nonaqueous electrolyte, negative electrode for rechargeable battery with nonaqueous electrolyte, rechargeable battery with nonaqueous electrolyte, and process for producing polycrystalline silicon particles for active material for negative electrode material for rechargeable battery with nonaqueous electrolyte |
US20090186267A1 (en) | 2008-01-23 | 2009-07-23 | Tiegs Terry N | Porous silicon particulates for lithium batteries |
JP5196149B2 (en) | 2008-02-07 | 2013-05-15 | 信越化学工業株式会社 | Anode material for non-aqueous electrolyte secondary battery, method for producing the same, lithium ion secondary battery and electrochemical capacitor |
US8105718B2 (en) | 2008-03-17 | 2012-01-31 | Shin-Etsu Chemical Co., Ltd. | Non-aqueous electrolyte secondary battery, negative electrode material, and making method |
KR100981909B1 (en) | 2008-04-15 | 2010-09-13 | 애경유화 주식회사 | Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same |
KR101002539B1 (en) | 2008-04-29 | 2010-12-17 | 삼성에스디아이 주식회사 | Negative electrode active material for lithium rechargeable battery and lithium rechargeable battery comprising the same |
FR2931297B1 (en) | 2008-05-16 | 2010-08-27 | Commissariat Energie Atomique | AUTOSUPPORTE FILM AND SINTERED SILICON PLATEBOARD |
WO2009140791A1 (en) | 2008-05-21 | 2009-11-26 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Process for producing silicon carbide |
US8936874B2 (en) | 2008-06-04 | 2015-01-20 | Nanotek Instruments, Inc. | Conductive nanocomposite-based electrodes for lithium batteries |
JP5320847B2 (en) | 2008-06-23 | 2013-10-23 | 信越化学工業株式会社 | Method for producing 31P-converted polycrystalline silicon particles |
WO2010036648A1 (en) | 2008-09-26 | 2010-04-01 | University Of Pittsburgh - Of The Commonwealth System Of Higher Education | Nanoscale silicon-based compositions and methods of preparation |
US8580432B2 (en) | 2008-12-04 | 2013-11-12 | Nanotek Instruments, Inc. | Nano graphene reinforced nanocomposite particles for lithium battery electrodes |
WO2010090029A1 (en) | 2009-02-06 | 2010-08-12 | パナソニック株式会社 | Lithium ion secondary battery and method for manufacturing lithium ion secondary battery |
US20100255376A1 (en) | 2009-03-19 | 2010-10-07 | Carbon Micro Battery Corporation | Gas phase deposition of battery separators |
GB2470190B (en) | 2009-05-11 | 2011-07-13 | Nexeon Ltd | A binder for lithium ion rechargeable battery cells |
US20110020701A1 (en) | 2009-07-16 | 2011-01-27 | Carbon Micro Battery Corporation | Carbon electrode structures for batteries |
KR20120093275A (en) | 2009-10-09 | 2012-08-22 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Method for producing carbon material coated with silicon carbide |
US20140170498A1 (en) | 2010-01-18 | 2014-06-19 | Enevate Corporation | Silicon particles for battery electrodes |
US9553303B2 (en) | 2010-01-18 | 2017-01-24 | Enevate Corporation | Silicon particles for battery electrodes |
US20170040598A1 (en) | 2015-08-07 | 2017-02-09 | Enevate Corporation | Surface modification of silicon particles for electrochemical storage |
KR101823672B1 (en) | 2010-01-18 | 2018-03-14 | 에네베이트 코포레이션 | Composite materials for electrochemical storage |
JP5411780B2 (en) | 2010-04-05 | 2014-02-12 | 信越化学工業株式会社 | Anode material for non-aqueous electrolyte secondary battery, method for producing anode material for non-aqueous electrolyte secondary battery, and lithium ion secondary battery |
JP5666287B2 (en) * | 2010-07-16 | 2015-02-12 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
US9397338B2 (en) | 2010-12-22 | 2016-07-19 | Enevate Corporation | Electrodes, electrochemical cells, and methods of forming electrodes and electrochemical cells |
US9583757B2 (en) | 2010-12-22 | 2017-02-28 | Enevate Corporation | Electrodes, electrochemical cells, and methods of forming electrodes and electrochemical cells |
KR101242529B1 (en) | 2011-02-22 | 2013-03-12 | 주식회사 대유신소재 | Method of Interface Hardening of Carbon Material Using Nano Silicon Carbarde Coating |
CN102157731B (en) | 2011-03-18 | 2015-03-04 | 上海交通大学 | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material |
CN103636055B (en) * | 2011-06-20 | 2016-01-13 | 丰田自动车株式会社 | The manufacture method of secondary cell |
EP2546180A1 (en) * | 2011-07-13 | 2013-01-16 | Inventio AG | Elevator installation and method for detecting the elevator car position. |
EP2797143B1 (en) | 2012-07-06 | 2016-11-30 | Toray Industries, Inc. | Negative electrode material for lithium ion secondary batteries, composite negative electrode material for lithium ion secondary batteries, resin composition for negative electrodes of lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary battery |
CN103633306B (en) | 2012-08-28 | 2016-01-20 | 华为技术有限公司 | A kind of silicon-carbon composite cathode material and preparation method thereof and lithium ion battery |
WO2014158729A1 (en) | 2013-03-13 | 2014-10-02 | Enevate Corporation | Silicon particles for battery electrodes |
CN109148935A (en) | 2013-03-14 | 2019-01-04 | 新强能电池公司 | Chucking device for electrochemical cell stack |
KR101439422B1 (en) | 2014-04-15 | 2014-09-12 | 문갑영 | Using a plasma method for producing a silicon-nano-particles colloid and cathode active material, lithium secondary cell using thereof |
US20180287129A1 (en) | 2017-03-28 | 2018-10-04 | Enevate Corporation | Methods of forming carbon-silicon composite material on a current collector |
US11152639B2 (en) * | 2016-01-15 | 2021-10-19 | Global Graphene Group, Inc. | Alkali metal-sulfur batteries having high volumetric and gravimetric energy densities |
US11171375B2 (en) | 2016-03-25 | 2021-11-09 | Enevate Corporation | Stepped electrochemical cells with folded sealed portion |
US10910629B2 (en) | 2016-07-18 | 2021-02-02 | Lg Chem, Ltd. | Method for manufacturing electrode and current collector for electrochemical device |
KR102069213B1 (en) * | 2017-01-23 | 2020-01-22 | 주식회사 엘지화학 | Method for preparing lithium secondary battery having high-temperature storage properties |
US11545656B2 (en) * | 2019-11-07 | 2023-01-03 | Enevate Corporation | Method and system for battery electrode lamination using overlapped irregular shaped active material and adhesive |
CN111370656B (en) * | 2018-12-26 | 2021-12-17 | 国家纳米科学中心 | Silicon-carbon composite material and preparation method and application thereof |
-
2021
- 2021-11-22 US US17/532,549 patent/US20230163309A1/en not_active Abandoned
- 2021-11-22 US US17/532,739 patent/US11387443B1/en active Active
-
2022
- 2022-07-01 US US17/856,035 patent/US20230163269A1/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180198114A1 (en) * | 2010-12-22 | 2018-07-12 | Enevate Corporation | Methods of reducing occurrences of short circuits and/or lithium plating in batteries |
US20130316229A1 (en) * | 2011-01-31 | 2013-11-28 | Mitsubishi Chemical Corporation | Non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery employing the same |
Also Published As
Publication number | Publication date |
---|---|
US20230163269A1 (en) | 2023-05-25 |
US11387443B1 (en) | 2022-07-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11710829B2 (en) | Method and system for water based phenolic binders for silicon-dominant anodes | |
US11699786B2 (en) | Method and system for water soluble weak acidic resins as carbon precursors for silicon-dominant anodes | |
US11114660B1 (en) | Silicon anodes with water-soluble maleic anhydride-, and/or maleic acid-containing polymers/copolymers, derivatives, and/or combinations (with or without additives) as binders | |
US20220115651A1 (en) | Aqueous based polymers for silicon dominant anodes | |
US20210384487A1 (en) | Method and system for water soluble weak acidic resins as carbon precursors for silicon-dominant anodes | |
US11923531B2 (en) | Method and system for water soluble weak acidic resins as carbon precursors for silicon-dominant anodes | |
US20230352669A1 (en) | Si-based anodes with cross-linked carbon nanotubes | |
US11387443B1 (en) | Silicon based lithium ion battery and improved cycle life of same | |
US20210194055A1 (en) | Solid-state polymer electrolyte for use in production of all-solid-state alkali-ion batteries | |
US20240030401A1 (en) | Systems and methods for thermal curing of water soluble polymers for silicon dominant anodes | |
US20240113281A1 (en) | Aqueous based anode with mechanical enhancement additives | |
US11522193B1 (en) | Water soluble PAA-based polymer blends as binders for Si dominant anodes | |
US20230268555A1 (en) | Prevention of gassing in si dominant lithium-ion batteries | |
US20230395887A1 (en) | Recycling silicon from batteries with silicon-based active materials | |
US11777078B2 (en) | Silicon carbon composite powder active material | |
US20230275230A1 (en) | Aqueous based polymers for silicon anodes | |
US20210143400A1 (en) | Use of perforated electrodes in silicon-dominant anode cells | |
US11777098B2 (en) | Method and system for functional conductive polymer initiated cathode electrolyte interface for silicon anode-based lithium ion batteries | |
US20240136506A1 (en) | Silicon with carbon-based coating for lithium-ion battery electrodes | |
US20220336871A1 (en) | Method and System for Periodic Deep Discharge To Extract Lithium In Silicon-Dominant Anodes | |
US20210143431A1 (en) | High Speed Formation Of Cells For Configuring Anisotropic Expansion Of Silicon-Dominant Anodes | |
WO2021096705A1 (en) | Lower pyrolysis temperature binder for silicon-dominant anodes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ENEVATE CORPORATION, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHAO, HONG;ANSARI, YOUNES;GIORDANI, VINCENT;AND OTHERS;SIGNING DATES FROM 20211119 TO 20211122;REEL/FRAME:058191/0157 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |