GB2622411A - Electrode precursor composition - Google Patents
Electrode precursor composition Download PDFInfo
- Publication number
- GB2622411A GB2622411A GB2213546.1A GB202213546A GB2622411A GB 2622411 A GB2622411 A GB 2622411A GB 202213546 A GB202213546 A GB 202213546A GB 2622411 A GB2622411 A GB 2622411A
- Authority
- GB
- United Kingdom
- Prior art keywords
- precursor composition
- electrode
- electrode precursor
- vol
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 116
- 239000002243 precursor Substances 0.000 title claims abstract description 99
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- -1 alkali metal salt Chemical class 0.000 claims abstract description 33
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 31
- 238000012545 processing Methods 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002033 PVDF binder Substances 0.000 claims abstract description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims abstract description 6
- 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 claims abstract description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 6
- 229910010941 LiFSI Inorganic materials 0.000 claims abstract description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims abstract description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical group 0.000 claims abstract description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 4
- 229920000767 polyaniline Polymers 0.000 claims abstract description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 4
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 36
- 239000011262 electrochemically active material Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000012983 electrochemical energy storage Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 2
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000144 PEDOT:PSS Polymers 0.000 abstract description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract 1
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 239000002482 conductive additive Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000012856 packing Methods 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- KCALAFIVPCAXJI-UHFFFAOYSA-N 1,10-phenanthroline-5,6-dione Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CN=C3C2=N1 KCALAFIVPCAXJI-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- BUPLCMMXKFWTTA-UHFFFAOYSA-N 4-methylidene-1,3-dioxetan-2-one Chemical compound C=C1OC(=O)O1 BUPLCMMXKFWTTA-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910014549 LiMn204 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- VNIGOEWLNPGGQW-UHFFFAOYSA-N lithium;imidazol-3-ide Chemical compound [Li+].C1=C[N-]C=N1 VNIGOEWLNPGGQW-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001465 mixed metal phosphate Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002907 osmium Chemical class 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0411—Methods of deposition of the material by extrusion
-
- 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
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Abstract
An electrode precursor composition suitable for preparing a gel electrode comprises an organic solvent, an alkali metal salt, an electronically insulating polymer and an organic redox-active component, wherein the redox-active component is present in a smaller volume fraction than the electronically insulating polymer. The redox-active component, which may be a polymer, may be present in the electrode precursor composition in an amount of between 1 to 20 vol%, most preferably in an amount of up to 8 vol%, based on the total volume of the electrode precursor composition. The redox-active component may comprise one or more of poly(3,4-ethylenedioxythiophene), polyaniline, polypyrrole, and doped derivatives thereof, such as poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate. The electronically insulating polymer may comprise PVDF, PEO, PMMA or PAN. The alkali metal salt is preferably a lithium salt such as LiBF4, LiPF6, LiTFSI, LiFSI or LiTDI, and the electrode may include a positive active material for use as a cathode in a Li-ion cell. A method of making the electrode is also disclosed in which the precursor composition is subjected to a thermal processing and/or extrusion step.
Description
Intellectual Property Office Application No GI32213546.1 RTM Date:28 February 2023 The following terms are registered trade marks and should be read as such wherever they occur in this document: Ketjen Black Intellectual Property Office is an operating name of the Patent Office www.gov.uk/ipo
ELECTRODE PRECURSOR COMPOSITION
Field of the Invention
The present invention relates to an electrode precursor composition for an alkali metal ion secondary cell. The invention also relates to electrodes, cells and energy storage devices made from such precursor compositions, along with methods of preparing electrodes for alkali metal ion secondary cells.
Background of the Invention
Lithium-ion secondary batteries are the leading battery technology currently used in applications from small personal devices to electric vehicles. Lithium-ion batteries are favoured for their high energy density and long cycle life, among other benefits. They contain a plurality of lithium-ion secondary cells.
Traditional lithium ion battery components such as electrodes are made from a solvent cast process that uses sacrificial solvent. This is an energetically expensive step, and a process that avoids using sacrificial solvent is therefore desirable.
One approach to avoiding the use of sacrificial solvent is preparing gel electrodes.
These electrodes can be formed from a composition prepared by mixing the necessary components such as electrochemically active material, polymer (typically an electronically insulating polymer), and a solvent or liquid electrolyte, and subsequently subjecting the composition to a processing treatment such as extrusion, to form the electrode.
The use of a gel in the preparation of an electrode using such processing treatments must balance at least two opposing requirements. On the one hand, the electrode must have sufficiently high energy density to be of practical use. For this, a higher solids content (higher content of electrochemically active material) is desirable. On the other hand, the gel must be sufficiently soft to be processed to form the electrode. For this, a lower solids content (lower content of electrochemically active material) is desirable, so that the material behaves sufficiently fluidly to be processable.
There is a need for electrode precursor compositions which satisfy the above criteria.
Summary of the Invention
In general, the present inventors propose to address the above problems by making use of redox active organic molecules as a fraction of the electrode precursor composition. In particular, the inventors generally propose to replace a portion of the usual electronically insulating polymer with redox active organic molecules. Since the electronically insulating polymer is a structural component, which is typically swellable, the volume fraction of the redox active organic component should be smaller than the volume fraction of the electronically insulating polymer.
In this way, the inventors believe it is possible to increase the energy density of a gel electrode compared to a corresponding gel electrode without the redox active organic component. For example, if the electrode precursor composition requires a reduced amount of electrochemically active material for processability, then the presence of a redox active organic component can at least partially compensate for the expected corresponding reduction in energy density. Similarly, if the electrode precursor composition does not require a reduced amount of electrochemically active material for processability, then the use of a redox active organic component can add capacity and result in an electrode with higher energy density than expected for a gel electrode without the redox active organic component. The present invention is based on this finding.
Use of redox active polymers in electrodes are known, as discussed by e.g. Poizot et al. (Chem. Rev. 2020, 120, 14, 6490-6557). For example, Duc et al. (ACS Appl. Polym. Mater. 2020, 2,6,2366-2379) discloses a long-range electronic conductor based on PEO and PEDOT:PSS. The authors report that extrusion of these blends introduced phase segregation phenomena requiring an acidic post-treatment to restore electronic conductivities. US 9,722,249 B2 and DE 102012022976 Al disclose compositions comprising complexes of polythiophene and polyanions, at least one lithium-containing compound, and at least one solvent, wherein the composition comprises less than 1 g of a material comprising elemental carbon, based on 1 g of the polythiophenes, or comprises no material at all comprising elemental carbon. JP 2004-158286 A discloses electrodes containing PEDOT and PVDF as binder produced by molding. JP 2011100594 A discloses a composition comprising a conductive polymer, formed by polymerizing ethylenedioxy thiophene or a derivative in the presence of at least one kind of polymeric sulfonic acid selected from the group consisting of polystyrene sulfonic acid, sulfonated polyester, and phenolsulfonic acid novolak resin, containing the polymeric sulfonic acid as a dopant, and an organic solvent and a carbonaceous conductive material, as well as an electrode mixture composition which also includes a binder an electrode active material. CN 110429279 A discloses an organic positive electrode material formed by copolymerization of a ruthenium or osmium derivative as a comonomer and which contains a conjugated aromatic fused ring as an electrochemical redox site.
However, these documents do not describe the concept of increasing the energy density of gel electrodes by using redox active organic molecules in a lower volume fraction than electronically insulating polymer.
Accordingly, a general proposal of the present invention is to provide a processable gel electrode precursor composition containing a redox active organic component, an electronically insulating polymer, an alkali metal salt, and an organic solvent. This composition may be subsequently combined with electrochemically active material and a conductive additive, before being further processed to form an electrode. Using this general procedure, the inventors find that the electrode precursor composition is highly processable while also forming an electrode with increased energy density.
A first aspect of the invention concerns an electrode precursor composition suitable for preparing a gel electrode, the composition comprising an organic solvent, an alkali metal salt, an electronically insulating polymer, and a redox active organic component, wherein the redox active organic component is present in a smaller volume fraction than the electronically insulating polymer.
The resulting electrode precursor composition typically contains a polymeric gel matrix phase. In this way, the electrode precursor composition typically has a gel-like quality and can be processed into a thin-film electrode.
In general, it is difficult to obtain dense electrodes having more than 70% by volume solids content and this results in limitation of the energy density of the electrode.
Advantageously, the use of the organic fraction as a processing aid and active material as a way of solving this problem, as is disclosed in the present application, has not been described previously.
According to a second aspect, the present invention concerns a method of preparing an electrode for an alkali metal ion secondary cell, the method comprising a providing step, comprising providing an electrode precursor composition according to the first aspect; and a processing step, comprising processing the electrode precursor composition to form an electrode.
Further aspects concern an electrode for an alkali metal ion secondary cell prepared from an electrode precursor composition or method according to the present invention, an electrochemical secondary cell, such as an alkali metal ion secondary cell, comprising an electrode according to the present invention, an electrochemical energy storage device comprising an electrochemical cell according to the present invention, and use of a redox active organic component in a method of preparing an electrode for an alkali metal ion secondary cell using a high temperature processing step.
Brief Description of the Drawings
Figure 1 is a schematic diagram of theoretical electrodes having (a),(b) ideal packing of electrochemically active material and (c),(d) non-ideal packing of electrochemically active material.
Detailed Description and Preferred Embodiments
Preferred and/or optional features of the invention will now be set out. Any aspect of the invention may be combined with any other aspect of the invention unless the context demands otherwise. Any of the preferred and/or optional features of any aspect may be combined, either singly or in combination, with any aspect of the invention unless the context demands otherwise.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Methods and materials are described herein for use in the present disclosure; other, suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control.
Methods described herein usually employ ambient temperature of a typical laboratory, which is typically between 20 and 30°C and preferably around 25°C, at atmospheric pressure, unless a different condition is defined herein or is more usually employed e.g. for a particular apparatus.
The present invention generally describes the use of a redox active organic component in electrode precursor compositions. The redox active organic component comprises molecules which can undergo reversible oxidation and reduction processes. The redox active organic component may comprise one or more of redox active small organic molecules, and/or redox active organic polymers. Depending on the nature of the redox active organic component, particularly polymer, a dopant may be used to achieve practically useful effects.
It will be understood that the redox active organic component should be present in the electrode precursor composition in an amount which is sufficient to achieve the desired amount of increase in energy density. Accordingly, in some embodiments, the redox active organic component is present in the electrode precursor composition in an amount of at least 1 vol%, based on the total volume of the electrode precursor composition, for example at least 2 vol%, at least 3 vol%, or at least 5 vol%.
Furthermore, the redox active organic component is present in the electrode precursor composition in a smaller volume fraction than the electronically insulating polymer. Accordingly, in some embodiments, the redox active organic component is present in the electrode precursor composition in an amount of up to 20 vol%, based on the total volume of the electrode precursor composition, for example up to 18 vol%, up to 15 vol%, up to 10 vol%, or up to 8 vol%.
Accordingly, in some embodiments, the redox active organic component is present in the electrode precursor composition in an amount of between 1 to 20 vol%, based on the total volume of the electrode precursor composition. Other combinations of the above values may be combined to form a suitable range, such as between 2 to 18 vol%, between 2 to 10 vol%, or between 5 to 8 vol%.
It is noted that the total vol% of all ingredients in the electrode precursor composition is 100 vol%.
Redox active organic components can undergo reversible oxidation and reduction processes. Accordingly, they represent a particularly useful class of component because they have the ability to store charge. Thus, the use of a redox active organic component achieves compensation or improvement of energy density of an electrode.
Figure 1 is used to show schematically the way the energy density of an electrode can be increased compared to a corresponding electrode without redox active organic component. In Figure 1, (a) shows a close to ideal electrode with near perfect packing of electrochemically active particles.
Theoretically, this has a >73% solids packing (close to ideal) with -68% volume electrochemically active material (black circles) and the intervening space filled with gel (white). This can result in an active material capacity of around 210 mAhg-1, and an electrode capacity of around 183 mAhg-1. The same electrode as (a) is shown in (b) but with a redox active conductive component (grey) included in the gel in the pores, which may be represented e.g. by PhenQ (1,10-phenanthroline-5,6-dione, a cationic type of molecule which is discussed further herein). While the other values remain the same, the electrode capacity may be increased to 196 mAhg-1.
A similar trend can be seen for a lower packing efficiency scenario. Figure 1(c) shows a non-ideal electrode, such as of the kind which may more typically be achieved through an extrusion process. This electrode has an imperfect packing of <73% solids packing and -63% volume of electrochemically active particles (black circles) and the intervening space filled with gel (white). This can result in an active material capacity of around 210 mAhg-1, and electrode capacity of 177 mAhg1. The same electrode as (c) is shown in (d) but with a redox active conductive component such as 1,8 PhenQ (grey) included in the gel in the pores. While the other values remain the same, the electrode capacity may be increased to 196 mAhg-1. Thus, it can be seen that replacing some of the gel polymer with a redox active organic component can compensate somewhat for loss of volumetric capacities and increase the electrode capacity. Thus, higher energies may be achieved. This is particularly important for the non-ideal example, since this already has lower energy density.
In each of (a) to (d), the other components such as conductive additive and electronically insulating polymer are not shown.
In cathodes, the charge is stored through anionic insertion. That is, the compensation of energy density is achieved by an anionic doping reaction. The skilled person will be familiar with electrochemical storage mechanisms using redox-active organics; in this regard we further refer to Figure 9 and Table 1 of Poizot et al. (Chem. Rev. 2020, 120, 14, 6490-6557). Figure 9a of Poizot et al. shows an example of anionic compensation of a p-type system in which a polymer (shown as R) and comprising a conjugated double bond can be reversibly doped with anion A. This process is shown for a two-fold reversible doping step (n=2). Each doping step involves loss of one electron from the polymer.
Accordingly, in embodiments using a redox active component, such as a redox active polymer, which undergoes an anionic doping reaction, the gel electrode can comprise up to 8 vol% of the redox active polymer, such as up to 7 vol%, up to 6 vol% or up to 5 vol% of the redox active polymer, to avoid effective depletion of anions and thus maintain cell performance.
Many redox active organic molecules, both small molecules and polymers, will be known to the skilled person. They may be used in the present invention alone or in combination. Purely by way of example and not limitation, redox active organic molecules suitable for use in the invention include one or more of poly(3,4-theylenedioxythiophene) (PEDOT), polyaniline (PANI), polypyrrole (PPy), as well as derivatives and doped derivatives thereof, such as poly(3,4-theylenedioxythiophene)-polystyrene sulfonate (PEDOT-PSS). Further examples include polyacetylene, coronene, polydopamine, 4,5-PhenQ, and others set out in Table 2 of Poizot et al. (Chem. Rev. 2020, 120, 14, 6490-6557) which is herein incorporated by reference in its entirety.
In some embodiments, the redox active organic molecules for use in the invention have a minimum redox activity of about 100 mAhg-1 with an average voltage about 2.5V. In some embodiments, the redox activity is higher, such as about 150 mAhg-lor about 200 mAhg-1. No particular upper limit is envisaged, as higher redox activity is generally desirable.
Redox activity can be measured using suitable means known in the art.
The electrode precursor composition of the present invention also comprises an electronically insulating polymer. These polymers are not intrinsically conducting polymers, and do not conduct electricity or conduct electricity to a negligible degree.
Typically, these polymers are substantially free of conjugated double bonds which allow the flow of electrons across the polymer backbone.
The electronically insulating polymer(s) for use in the present electrode precursor compositions are polymers typically used in the preparation of gel electrodes. They are generally swellable. They may be used in the present invention alone or in combination.
Many will be known to the skilled person. Purely by way of example and not limitation, electronically insulating polymers suitable for use in the present invention include one or more of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), polymethylmethacrylate (PMMA) and polyacrylonitrile.
In some embodiments, the electronically insulating polymer is present in the electrode precursor composition in an amount of at least 5 vol%, based on the total volume of the electrode precursor composition, such as at least 7 vol%, at least 10 vol% or at least 15 vol%.
In some embodiments, the electronically insulating polymer is present in the electrode precursor composition in an amount of up to 30 vol%, based on the total volume of the electrode precursor composition, such as up to 28 vol%, up to 25 vol%, or up to 20 vol%.
Accordingly, in some embodiments, the electronically insulating polymer is present in the electrode precursor composition in an amount of between 5 to 30 vol%, based on the total volume of the electrode precursor composition. Other combinations of the above values may be combined to form a suitable range, such as between 5 to 28 vol%, between 7 to 25 vol%, or between 10 to 20 vol%.
The electrode precursor composition of the present invention comprises at least one alkali metal salt.
The alkali metal of the at least one alkali metal salt may be any suitable alkali metal (Group I of the periodic table). Typically, it may be lithium, sodium and potassium. In some embodiments, the at least one alkali metal of the alkali metal salt is lithium, and this may be preferred in all embodiments of the invention.
The anion of the at least one alkali metal salt may be any suitable anion. Typical anions are known to the skilled person and may be chosen based on the nature of the alkali metal. In some embodiments, when the at least one alkali metal is lithium, the anion of the or each alkali metal salt is independently selected from: a lithium borate salt, a lithium imide salt, and a lithium imidazolide salt, or comprises a halogen such as fluorine. Examples include BF4-, PF6-, TESL FSI-and TDI-.
Accordingly, in some embodiments, the at least one alkali metal salt comprises one or more of lithium bis(oxalato)borate, lithium tetrafluoroborate, lithium difluoro(oxalate)borate (LiDFOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFS1), lithium bis(fluorosulfonyl) imide (LiFS1), lithium 2-trifluoromethy1-4,5-dicyanoimidaxolide (LiTDI) and lithium hexafluorophosphate (LiPF6).
In some embodiments, the at least one alkali metal salt comprises one or more of LiFSI, LiDFOB and LiTDI In some particularly useful embodiments, the at least one alkali metal salt comprises one or more of LiBF4, LiPF6, LiTFSI, LiFSI and LiTDI.
One or more kinds of alkali metal salt may be used in accordance with the present invention. Typically, but not exclusively, when more than one kind of alkali metal salt is used, they share a common alkali metal cation. Typically, but not exclusively, when more than one salt is present, they are each a lithium salt.
The organic solvent used in the present invention is an organic solvent which is typically used in the manufacture of electrodes for alkali metal secondary cells. The organic solvent should suitably be capable of being blended with, e.g. to form a solution with the polymer and redox active organic component of the electrode precursor composition.
In some embodiments, the organic solvent is non-aqueous. In some embodiments, the solvent comprises one or more cyclic or linear carbonate, ether or nitrile compounds In some embodiments the solvent comprises one or more cyclic or linear carbonate compounds.
In some embodiments the one or more linear or cyclic carbonate compound comprises one or more cyclic carbonate compounds. In some embodiments the solvent comprises one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate and y-butyrolactone.
In some embodiments, the alkali metal salt and organic solvent together is present in an amount of at least 1 vol%, based on the total volume of the electrode precursor composition, such as at least 5 vol%, at least 10 vol% or at least 15 vol%.
In some embodiments, the alkali metal salt and organic solvent is present in an amount of up to 50 vol%, based on the total volume of the electrode precursor composition, such as up to 45 vol%, up to 35 vol% or up to 25 vol%.
Accordingly, in some embodiments, the alkali metal salt and organic solvent is present in an amount of between 1 to 50 vol%, based on the total volume of the electrode precursor composition. Other combinations of the above values may be combined to form a suitable range, such as between 5 to 45 vol%, between 5 to 35 vol%, or between 10 to 25 vork.
The skilled person will be aware of a large number of possible electrochemically active materials, including cathode active materials (also called positive active materials) and anode active materials (also called negative active materials), which may be used in the present invention.
The electrochemically active material is a particulate material, i.e. a material made up of a plurality of discrete particles. The particles may comprise primary particles and/or secondary particles formed from the agglomeration of a plurality of primary particles.
In some embodiments, the electrochemically active material is a positive active material. That is, the electrode functions as a cathode.
In some embodiments, the positive active material is a lithium transition metal oxide material. In some embodiments, the positive active material is a lithium transition metal oxide material, or a lithium transition metal phosphate material, or a lithium transition metal sulfide material. These comprise, respectively, a mixed metal oxide, phosphate or sulfide of lithium and one or more transition metals, optionally further comprising one or more additional non-transition metals. In some embodiments, the positive active material is a lithium transition metal oxide, phosphate or sulfide material comprising lithium and one or more transition metals selected from nickel, cobalt and manganese.
In some embodiments, the positive active material is a lithium transition metal oxide material comprising a mixed metal oxide of lithium and one or more transition metals, optionally further comprising one or more additional non-transition metals. In some embodiments, the positive active material is selected from one or more of lithium cobalt oxide ([GO), lithium manganese oxide ([MO), lithium nickel cobalt oxide (NCO), aluminium-doped lithium nickel cobalt oxide (NCA), lithium nickel manganese cobalt oxide (NMC), lithium nickel oxide ([NO), lithium nickel manganese oxide (LNMO), lithium iron phosphate ([FP), lithium manganese iron phosphate ([FP) and lithium nickel vanadate ([NV). In some embodiments, the positive active material is lithium nickel manganese cobalt oxide (NMC), optionally doped with another metal such as aluminium.
Such electrochemically active materials are commercially available or may be manufactured by methods known to the skilled person, for example through the precipitation of mixed metal hydroxide intermediates from a reaction mixture containing different precursor metal salts, followed by calcination to form a mixed metal oxide and optionally lithiation to incorporate lithium into the oxide.
The electrochemically active materials may be undoped or uncoated or may contain one or more dopants and/or a coating. For example, the electrochemically active material may be doped with small amounts of one or more metal elements. The electrochemically active material may comprise a carbon coating on the surface of the particles of the material.
In some embodiments, the electrochemically active material is present in an amount of at least 55 vol%, based on the total volume of the electrode precursor composition, such as at least 56 vol%, at least 57 vol%, at least 58 vol%, at least 59 vol%, at least 60 vol%, at least 61 vol%, or at least 62 vol%.
In some embodiments, the electrochemically active material is present in an amount of up to 75 vol%, based on the total volume of the electrode precursor composition, such as up to 74 vol%, up to 73 vol%, up to 72 vol%, up to 71 vol%, up to 70 vol%, up to 69 vol % or up to 68 vol%.
In some embodiments the electrochemically active material is present in an amount of from 55 to 75 vol%, based on the total volume of the electrode precursor composition.
Other combinations of the above values may be combined to form a suitable range, such as from 55 to 70 vol%, from 55 to 69 vol%, from 55 to 68 vol%, from 58 to 68 vol%, or from 60 to 68 vol%.
In some embodiments the electrochemically active material makes up from 62 to 75 vol% of the electrode precursor composition, for example from 62 to 70 vol%, from 62 to 69 vol%, from 62 to 68 vol% or from 62 to 69 vol%.
In some embodiments the electrochemically active material is present in an amount of between 62 to 75 vol% of the electrode precursor composition, such as from 60 to 75 vol%, from 60 to 72 vol%, from 60 to 70 vol% or from 60 to 68 vol%.
In some embodiments, the electrode precursor composition further comprises a conductive additive, preferably which includes a conductive carbon. The conductive additive may be particulate.
In some embodiments, the conductive additive comprises or consists of one or more of carbon black, carbon nanotubes, graphene and graphite. In some embodiments, the conductive additive comprises or consists of carbon black or graphite, preferably carbon black. Examples of commercially available carbon black include Ketjen Black and Super 065.
In some embodiments, the conductive additive is present in an amount of at least 1 vol%, based on the total volume of the precursor composition, such as at least 2 vol%, at least 3 vol%, or at least 4 vol% In some embodiments, the conductive additive is present in an amount of up to 10 vol%, based on the total volume of the electrode precursor composition, such as up to 9 vol%, up to 8 vol%, or up to 7 vol%.
Accordingly, in some embodiments, the conductive additive is present in an amount of between 1 to 10 vol%, based on the total volume of the electrode precursor composition. Other combinations of the above values may be combined to form a suitable range, such as between 1 to 9 vol%, between 1 to 8 vol%, between 2 to 8 vol% or between 3 to 7 vol%.
In embodiments where a composition contains redox active organic component On an amount of q vol%), electronically insulating polymer (in an amount of z vol%), alkali metal salt, organic solvent and electrochemically active material (together in an amount totalling x vol%), and conductive additive On an amount of y vol%), then x+y+z+q= vol%.
In some such embodiments, typically (x+y) > (q+z).
In some such embodiments, q/(q+z) is typically at least 0.25, such as at least 0.27 or at least 0.30. In further examples, q/(q+z) may be at least 0.32, at least 0.35 or at least 0.40. In some such embodiments, q/(q+z) is typically less than 0.5, such as up to 0.49, up to 0.47, up to 0.45 or up to 0.40. Accordingly, in some such embodiments, when x+y > 70 vol% then q/(q+z) is typically between 0.25 and less than 0.50. Other combinations of the above values may be combined to form a suitable range, such as between 0.27 and less than 0.50, between 0.27 and 0.49, or between 0.30 and 0.45.
Also provided herein is a method of making an electrode precursor composition as described herein. In general, the method comprises blending the redox active organic component, the electronically insulating polymer, the alkali metal salt, and the organic solvent. Typically, this blend will form a gel. Without wishing to be bound by theory, it is considered that cooling provides the gel with sufficient mechanical strength. The ingredients can be blended simultaneously or in any appropriate order, for any suitable time, in any suitable way. For example, the appropriate amounts of each may be simultaneously added and mixed.
Subsequently, the blend of organic solvent, alkali metal salt, electronically insulating polymer, and redox active organic component, is combined with the electrochemically active material and the conductive additive, and optionally any further components. The electrochemically active material and the conductive additive can be combined with the blend simultaneously or in any appropriate order, for any suitable time, in any suitable way.
Typically the components will be mixed together using a variety of standard mixing equipment such as planetary mixing to ensure a good dispersion of components. The mixture will then be passed through a twin-screw extruder at elevated temperatures (>110 °C) which will may combine the polymers and liquids into a viscous gel. Alternatively, the components maybe fed individually into the extruder via individual feeders and the mixing occurs inside the extruder. The material can then either be extruded directly through a die head into a thin sheet or can be extruded roughly before being calendared into a film. This film can then be adhered to a metal foil which can be assembled into a battery.
Any suitable equipment for preparing electrode precursor compositions may be used to prepare the electrode precursor compositions herein, for example standard mixing equipment.
The electrode precursor composition may subsequently be processed into an electrode as described herein.
Also provided herein is a method of preparing an electrode for an alkali metal ion secondary cell. In general, the method includes a providing step, comprising providing an electrode precursor composition as described herein, and a processing step, comprising processing the electrode precursor composition to form an electrode. Thus, it will be understood that electrode precursor compositions as described herein are used for preparing electrodes according to the invention. Accordingly, steps described elsewhere herein for preparing the electrode precursor compositions apply equally to the providing step of the method of preparing an electrode.
In some embodiments, the processing step comprises one or more of extrusion and thermal processing In some embodiments, the processing step comprises at least thermal processing. That is, the processing step comprises a step of applying high temperature in a fluid state formation process.
In some embodiments the thermal processing comprises passing the electrode precursor composition through a roller assembly at a temperature of at least 50 °C, for example at least 60 °C, at least 70 °C, at least 80 °C, at least 90 °C or at least 100 °C. In some embodiments the thermal processing comprises passing the electrode precursor composition through rollers at a temperature of up to 150 °C, for example up to 140 °C or up to 130 °C. In some embodiments the thermal processing comprises passing the electrode precursor composition through rollers at a temperature of from 50 °C to 150 °C, for example from 60°C to 150 °C, from 70°C to 150 °C, from 80 °C to 150 °C, from 80°C to 140 °C, from 90°C to 140 °C, from 100°C to 140°C or from 110°C to 130 °C.
The roller assembly may comprise two rollers separated by a small distance such that the electrode precursor composition is pressed into a thin film when passed through the rollers.
In some embodiments the processing step comprises at least extruding the electrode, or extrusion. In some embodiments the processing step comprises extruding the electrode using an extrusion apparatus comprising one or more screw feeding sections and an extrusion die. In some embodiments, extrusion is achieved using a twin screw extruder.
In some embodiments in which both extrusion and thermal processing are used in the processing step, the temperature of the die is at least 50 °C, for example at least 60 °C, at least 70 °C, at least 8000, at least 9000 or at least 100 °C. In some embodiments the temperature of the die is up to 150 °C, for example up to 140 °C or up to 130 °C. In some embodiments the temperature of the die is from 50 °C to 150 °C, for example from °C to 150 °C, from 70°C to 150 °C, from 8000 to 15000 from 8000 to 140°C from 90°C to 140 °C, from 100°C to 140°C or from 110 °C to 130 °C.
In some embodiments the electrode has a thickness of less than 150 pm, for example less than 100 pm, less than 90 pm, less than 80 pm or less than 70 pm. In some embodiments the electrode has a thickness of from 40 to 150 pm, for example from 40 to 100 pm, from 40 to 90 pm, from 40 to 80 pm, from 40 to 70 pm or from 50 to 70 pm. In particular embodiments, the electrode has a thickness of from 40 to 100 pm.
In some embodiments the electrode has a thickness of from 40 to 150 pm, for example from 40 to 100 pm, from 40 to 90 pm, from 40 to 80 pm, from 40 to 70 pm or from 50 to pm, and comprises the electrochemically active material in an amount of from 60 to 75 vol% of the electrode precursor composition, for example from 60 to 70 vol%, from 60 to 69 vol%, from 60 to 68 vol% or from 62 to 69 vol%.
In some cases, the extruded electrode may form part of an extruded monolith which includes one or more further layers which are present in an electrochemical battery. For instance, the monolith may include a separator layer, and/or may include the other electrode (i.e. the extruded monolith may include both a cathode and anode). The different layers may be coextruded and have different compositions from one another.
In some embodiments, the method of the invention further comprises shaping and/or cutting the electrode to form an electrode of predetermined dimensions.
In some embodiments, the electrode film has a thickness of from 500 to 700 pm. In some embodiments, the method of the invention further comprises performing a second thermal processing step on a cut film to reduce the thickness of the film to within a range of 50 to 70 pm.
In some embodiments, the temperature during that thermal processing step is from 100 to 140 °C.
Also provided herein as an aspect of the invention is an electrode prepared by a method of the invention or from an electrode precursor composition of the invention. Typically, the electrode which results from the method of the invention is a gel electrode.
In some embodiments, the electrode which is prepared by the method of the invention has less than 10% porosity, such as less than 8% porosity, less than 5% porosity, less than 3% porosity or less than 1% porosity. In some embodiments, the electrode which is prepared by the method of the invention has 0% porosity.
The electrode porosity may be determined for example by comparison of theoretical density with observed density. That is, a skilled person can calculate the theoretical density of the electrode, and then measure the actual electrode density, using suitable means. Subsequently, the actual density is subtracted from the theoretical density to provide the porosity.
Without wishing to be bound by theory, the inventors consider that a lower porosity is generally advantageous because it reduces the tortuosity for the ions (e.g. lithium ions) to move through the gel of the electrode. Thus, the initial rate capability of the electrode is expected to be higher compared with an electrode having higher porosity. For similar reasons, it is expected that the electronic conductivity might be impacted in a similar way. Thus, the inventors expect the energy density is related to the porosity.
Also provided as an aspect of the invention is an electrochemical secondary cell comprising such electrode. The cell may be an alkali metal ion secondary cell, for example a sodium-ion secondary cell or a lithium-ion secondary cell. In some embodiments, the cell is a lithium-ion secondary cell.
In some embodiments the electrochemical secondary cell comprises a first electrode according to the invention, wherein the first electrode is a cathode, and an anode. In some embodiments, the electrochemical secondary cell comprises a second electrode according to the invention, wherein the second electrode is an anode, and a cathode. In some embodiments, the electrochemical secondary cell comprises a first and a second electrode according to the invention, wherein the first electrode is a cathode, and the second electrode is an anode. In each of these embodiments, the electrochemical secondary cell also comprises an electrolyte between the cathode and the anode. In some embodiments, the electrolyte is a liquid electrolyte. In some embodiments, the liquid electrolyte comprises or is a solution comprising an alkali metal salt as described herein.
In some embodiments the electrochemical secondary cell comprises an electrode according to the invention laminated with a current collector, for example a metallic foil.
Also provided herein as an aspect of the invention is an electrochemical energy storage device comprising an electrochemical secondary cell of the invention. In some embodiments, the electrochemical energy storage device is a battery. In some embodiments, the electrochemical energy storage device is a lithium-ion battery.
Also provided herein as an aspect of the invention is the use of a redox active organic component in a method of preparing an electrode for an alkali metal ion secondary cell using at least one of a thermal processing step or an extrusion step. The redox active organic component of this aspect is preferably a redox active organic component as described herein for use in the first aspect. The method of preparing an electrode of this aspect is preferably a method of the second aspect as described herein.
In some embodiments, such use provides the electrode with an increased energy density compared to a corresponding electrode without the redox active organic component.
Examples
The following is an exemplary electrode precursor composition for use in the present invention: Ingredient Vol% of Specific Example 1 Specific Example 2 Composition Redox active organic component 1-20 5 10 Electronically insulating polymer (e.g. one or more of PVDF, PEO or PAN) 5-30 5 10 Alkali metal salt (e.g. one or more of LiFSI, LiTFSI, or L1BF4); and organic solvent (e.g. one or more of ethylene carbonate, propylene carbonate, vinylidene carbonate, fluoroethylene carbonate, and ybutyrolactone) 1-50 15 20 Electrochemically active material (e.g. one or more of LiCo02, NMC, or LiMn204) up to 75, preferably 70 55 at least 45 Conductive carbon 1-10 5 10
Claims (24)
- Claims 1. An electrode precursor composition suitable for preparing a gel electrode, the composition comprising an organic solvent, an alkali metal salt, an electronically insulating polymer, and a redox active organic component, wherein the redox active organic component is present in a smaller volume fraction than the electronically insulating polymer.
- 2. An electrode precursor composition according to claim 1, wherein the redox active organic component is present in the electrode precursor composition in an amount of between 1 to 20 vol%, based on the total volume of the electrode precursor composition.
- 3. An electrode precursor composition according to claim 2, wherein the redox active organic component is present in the electrode precursor composition in an amount of up to 8 vol%, based on the total volume of the electrode precursor composition.
- 4. An electrode precursor composition according to any one of the preceding claims, wherein the redox active organic component is a redox active polymer.
- 5. An electrode precursor composition according to claim 4, wherein the redox active polymer comprises one or more selected from poly(3,4-theylenedioxythiophene), polyaniline, polypyrrole, and doped derivatives thereof, such as poly(3,4-theylenedioxythiophene)-polystyrene sulfonate.
- 6. An electrode precursor composition according to any one of the preceding claims, wherein the electronically insulating polymer comprises one or more selected from polyvinylidene fluoride, polyethylene oxide, polymethylmethacrylate and polyacrylonitrile.
- 7. An electrode precursor composition according to claim 6, wherein the electronically insulating polymer is present in the electrode precursor composition in an amount of between 5 to 30 vol%, based on the total volume of the electrode precursor composition.
- 8. An electrode precursor composition according to any one of the preceding claims, wherein the alkali metal salt comprises a lithium salt.
- 9. An electrode precursor composition according to claim 8, wherein the lithium salt comprises one or more of LiBF4, LiPF6, LiTFSI, LiFSI or LiTDI.
- 10. An electrode precursor composition according to any one of the preceding claims, wherein the organic solvent comprises one or more of a carbonate, an ether, or a nitrile.
- 11. An electrode precursor composition according to any one of the preceding claims, further comprising an electrochemically active material.
- 12. An electrode precursor composition according to claim 10, wherein the electrochemically active material comprises a positive active material.
- 13. An electrode precursor composition according to claim 11 or claim 12, wherein the electrochemically active material is present in the electrode precursor composition in an amount of at least 60 vol%, based on the total volume of the electrode precursor composition.
- 14. An electrode precursor composition according to any one of the preceding claims, further comprising an additive which includes a conductive carbon.
- 15. An electrode precursor composition according to claim 14, wherein the conductive carbon comprises one or more of carbon black, carbon nanotubes, graphene and graphite.
- 16. An electrode precursor composition according to claim 14 or claim 15, wherein the conductive carbon is present in the electrode precursor composition in an amount of between 1 to 10 vol%, based on the volume of the electrode precursor composition. 30
- 17. A method of preparing an electrode for an alkali metal ion secondary cell, the method comprising a providing step, comprising providing an electrode precursor composition according to any one of claims 1 to 16; and a processing step, comprising processing the electrode precursor composition to form an electrode.
- 18. A method according to claim 17, wherein the processing step comprises one or more of extrusion and thermal processing.
- 19. A method according to claim 17 or claim 18, wherein the providing step comprises providing an electrode precursor composition according to any one of claims 1 to 10, subsequently combining the electrode precursor composition with an electrochemically active material and conductive carbon.
- 20. A method according to any one of claims 16 to 19, wherein the electrode is a gel electrode
- 21. An electrode for an alkali metal ion secondary cell prepared from an electrode precursor composition according to any one of claims 1 to 16 or prepared by a method according to any one of claims 17 to 20.
- 22. An electrochemical secondary cell comprising an electrode according to claim 21.
- 23. An electrochemical energy storage device comprising an electrochemical cell according to claim 22.
- 24. Use of a redox active organic component in a method of preparing an electrode for an alkali metal ion secondary cell using a high temperature processing step.
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Citations (3)
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US5814420A (en) * | 1994-11-23 | 1998-09-29 | Polyplus Battery Company, Inc. | Rechargeable positive electrodes |
JP2011100594A (en) * | 2009-11-05 | 2011-05-19 | Tayca Corp | Conduction aid composition for lithium ion battery, method of manufacturing the same, electrode mixture composition for lithium ion battery, method of manufacturing the electrode mixture composition, and lithium ion battery |
CN112490405A (en) * | 2020-12-01 | 2021-03-12 | 西安建筑科技大学 | Gel-state positive electrode of lithium-sulfur battery and preparation method thereof |
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SE512579C2 (en) * | 1998-07-09 | 2000-04-03 | Forskarpatent I Linkoeping Ab | Polymer gel electrode, and process for its preparation |
JP4365572B2 (en) | 2002-11-06 | 2009-11-18 | 株式会社ニチリン | Positive electrode material composite containing poly (3,4-ethylenedioxythiophene) and lithium secondary battery having a positive electrode made of the composite |
KR101461424B1 (en) * | 2009-11-30 | 2014-11-13 | 나노스캐일 컴포넌츠, 인코포레이티드 | Methods for producing textured electrode based energy storage device |
DE102012022976A1 (en) | 2012-11-26 | 2014-05-28 | Ewe-Forschungszentrum Für Energietechnologie E. V. | Use of conductive polymers in battery electrodes |
CN110429279B (en) | 2019-07-12 | 2021-05-18 | 华中科技大学 | Organic anode material of lithium ion battery and application thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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US5814420A (en) * | 1994-11-23 | 1998-09-29 | Polyplus Battery Company, Inc. | Rechargeable positive electrodes |
JP2011100594A (en) * | 2009-11-05 | 2011-05-19 | Tayca Corp | Conduction aid composition for lithium ion battery, method of manufacturing the same, electrode mixture composition for lithium ion battery, method of manufacturing the electrode mixture composition, and lithium ion battery |
CN112490405A (en) * | 2020-12-01 | 2021-03-12 | 西安建筑科技大学 | Gel-state positive electrode of lithium-sulfur battery and preparation method thereof |
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