EP3445794A1 - Copolymer binder - Google Patents
Copolymer binderInfo
- Publication number
- EP3445794A1 EP3445794A1 EP17785216.7A EP17785216A EP3445794A1 EP 3445794 A1 EP3445794 A1 EP 3445794A1 EP 17785216 A EP17785216 A EP 17785216A EP 3445794 A1 EP3445794 A1 EP 3445794A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomer
- copolymer
- electrode
- suspension
- binder
- 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.)
- Withdrawn
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 112
- 239000011230 binding agent Substances 0.000 title claims description 55
- 239000000178 monomer Substances 0.000 claims abstract description 155
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 34
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 21
- 230000009477 glass transition Effects 0.000 claims abstract description 20
- -1 poly(ethylene oxide) Polymers 0.000 claims abstract 3
- 239000000725 suspension Substances 0.000 claims description 79
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 36
- 229910001416 lithium ion Inorganic materials 0.000 claims description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- 239000011149 active material Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 13
- 239000004917 carbon fiber Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical group COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical group CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- FUSJZTVOKYJFPI-UHFFFAOYSA-N cyclopentane;iron;5-methylcyclopenta-1,3-diene Chemical compound [Fe].[CH-]1[CH-][CH-][CH-][CH-]1.C[C-]1C=CC=C1 FUSJZTVOKYJFPI-UHFFFAOYSA-N 0.000 claims description 3
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical group CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 3
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical group CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 16
- 239000004615 ingredient Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910010689 LiFePC Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000013504 Triton X-100 Substances 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XGDRLCRGKUCBQL-UHFFFAOYSA-N 1h-imidazole-4,5-dicarbonitrile Chemical compound N#CC=1N=CNC=1C#N XGDRLCRGKUCBQL-UHFFFAOYSA-N 0.000 description 1
- ZOCKVPYUHQDWAU-UHFFFAOYSA-N 2-ethenyl-1h-imidazole-4,5-dicarbonitrile Chemical compound C=CC1=NC(C#N)=C(C#N)N1 ZOCKVPYUHQDWAU-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011244 liquid electrolyte Substances 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
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/04—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
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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
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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
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- 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
- the present invention relates to a copolymer useful as a binder for lithium-ion battery electrodes.
- Secondary lithium-ion batteries are used as power sources in laptops, cell phones, power tools and electronic and communication devices where they allow a reduction in size and weight. In recent years, secondary lithium-ion batteries have also been used for electric cars and hybrid cars. There is a strong demand for secondary lithium-ion batteries with high efficiency, high capacity, and long life for these latter applications.
- a negative electrode comprising a carbon material such as graphite as the active material
- an electrolyte solution an electrolyte typically comprising carbonates as a solvent.
- the positive electrode is typically obtained by applying a slurry composed of the active material and a binder to the surface of a positive electrode current collector such as aluminum foil, by drying the suspension. and then cutting the current collector into a suitable size.
- the negative electrode is obtained by applying a slurry composed of the active material and a binder on the surface of a negative electrode current collector such as a copper foil, drying the suspension, and then by cutting the current collector into a suitable size.
- the binders used for secondary lithium-ion battery electrodes are to bind the active materials to each other and to bind the active materials to the current collector to prevent the separation of active materials from the surface of the collector. current.
- Polymeric binders are widely used to help the cohesion and adhesion of active battery materials on the collector. These binders are typically electrochemically inactive, stable and chemically inert polymers. They contribute significantly to the mass and stability of the battery.
- the most commonly used polymer binder is poly (vinyl difluoride) (PVDF).
- PVDF poly (vinyl difluoride)
- NMP N-methyl pyrrolidone
- this polymer has significant problems in its industrial use, such as a high production cost and a large energy demand for evaporating the solvent during the manufacture of the electrodes.
- NMP N-methyl pyrrolidone
- its use in a battery with a liquid electrolyte induces the formation of LiF, which accelerates the chemical degradation of PVDF.
- Another factor that accelerates the degradation rate of the electrode is the lack of flexibility of the PVDF; the effects of contraction and expansion caused by cycling causing the formation of cracks in the electrode.
- Another polymer coating conventionally used consists of a mixture of styrene-butadiene rubber (SBR) and methylated cellulose (CMC).
- SBR styrene-butadiene rubber
- CMC methylated cellulose
- the SBR provides good adhesion to the collector while the CMC helps to thicken the dispersion and adhesion of the active materials to each other.
- the SBR has a negative impact on the conductivity of the electrode.
- this mixture is very effective in the case of LiFePC and LTO (Li isO ⁇ ), it is not very effective in the case of LCO (UC0O2) for example.
- PAN Poly (acrylonitrile)
- PAA poly (acrylic acid)
- PVA poly (vinyl alcohol)
- the present invention relates to:
- a copolymer comprising:
- the monomer A being a hydrophilic monomer comprising a pendant chain of poly (ethylene oxide) (POE) of low molecular weight
- monomer B being a hydrophobic monomer having a glass transition temperature (Tg) of about -30 ° C or less,
- monomer C being a monomer more hydrophobic than monomer B and having a glass transition temperature (Tg) of about 80 ° C or more,
- said monomers being organized in:
- the intermediate segment having an intermediate hydrophilicity between the hydrophilicity of the hydrophilic segment and the hydrophilicity of the hydrophobic segment
- the hydrophilic segment comprising the monomer A and a part of the monomer B
- the intermediate segment and the hydrophobic segment comprising the rest of the monomer B as well as the monomer C
- the intermediate segment being enriched in monomer B with respect to the hydrophobic segment
- the segment hydrophobic being enriched in monomer C with respect to the intermediate segment
- copolymer according to item 1 wherein the copolymer further comprises a monomer D, which is a chemically crosslinkable monomer in water, in a molar ratio d ranging from about 0 to about 0.10.
- copolymer according to item 1 or 2 wherein the copolymer has the following formula: which :
- A, B, C and D respectively represent said monomers A, B, C and D and
- a, b, c and d respectively represent said molar ratios a, b, c, and d.
- copolymer according to any one of items 1 to 3 wherein the molar mass of the POE pendant chain ranges from about 300 to about 2000 g / mol, preferably from about 300 to 1000 g / mol, and more preferably from about 300 to and about 500 g / mol.
- copolymer according to any one of items 1 to 4 wherein the monomer A is polyethylene glycol methyl acrylate or polyethylene glycol methyl methacrylate.
- R is a hydrogen atom or a methyl group and x represents a POE repeating unit number such that the molar mass of the POE chain is as defined in item 4.
- another acrylate or methacrylate having a Tg of about -30 ° C or less, particularly an alkyl acrylate or methacrylate, the alkyl being unsubstituted or substituted, preferably end-chain, with one or more hydroxy groups and / or alkoxy, the alkoxy being non substituted or substituted, preferably at the end of the chain, with one or more hydroxy and / or alkoxy groups, preferably with an alkoxy group;
- copolymer according to item 10 wherein monomer B is n-butyl acrylate, iso-decyl acrylate, n-decyl methacrylate, n-dodecyl methacrylate, 2-ethylhexyl acrylate, acrylate 2- (2-ethoxyethoxy) ethyl, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, n-propyl acrylate, ethylene glycol methyl ether acrylate, vinyl butyl ether, or a mixture thereof.
- vinazene TM an imidazole derivative, more particularly 2-vinyl-4,5 -dicyanoimidazole
- methyl methacrylate tert-butyl methacrylate
- acryloyl morpholine phenyl methacrylate
- ferrocene vinyl methyl ferrocene methacrylate or a mixture thereof.
- copolymer according to any one of items 1 to 16 comprising diacetone acrylamide as monomer D.
- copolymer according to any one of items 1 to 17 wherein the monomer A is polyethylene glycol methyl acrylate or polyethylene glycol methyl methacrylate, monomer B is n-butyl acrylate and monomer C is styrene, preferably the copolymer has the following formula:
- R and x are as defined in item 6 and a, b and c are as defined in item 1.
- copolymer according to any one of items 1 to 18 wherein the copolymer further comprises diacetone acrylamide as monomer D, preferably the copolymer is of the following formula:
- R and x are as defined in item 6, a, b and c are as defined in item 1 and d is as defined in item 2.
- Tg glass transition temperature
- copolymer as defined according to any one of items 1 to 21 as a binder for a lithium-ion battery electrode.
- a binder for lithium-ion battery electrode comprising a copolymer as defined in any one of items 1 to 21.
- a binder suspension comprising a copolymer as defined according to any of items 1 to 21 suspended in water.
- the binder suspension according to item 24 comprising about 10% and about 20%, and preferably about 10% to about 13%, by weight percent, of the copolymer based on the total mass of the slurry.
- the binder suspension according to item 24 or 25 further comprising a surfactant.
- the binder suspension according to item 26 comprising from about 3% to about 7% by weight percent of the surfactant based on the total mass of the slurry.
- a binder for a lithium ion battery electrode comprising a binder suspension as defined in any of items 24 to 28.
- binder suspension as defined in any of items 24 to 28 as a lithium ion battery electrode binder.
- a method of manufacturing an electrode for a lithium-ion battery comprising the steps of:
- step a) comprises crosslinking the copolymer via the D monomer.
- step a) uses a dihydrazine or dihydrazide compound as a crosslinking agent for the crosslinking of the D monomer.
- step a) uses adipic acid dihydrazide as a crosslinking agent.
- An electrode suspension comprising a binder suspension as defined in any of items 24 to 28 and further comprising an active material for lithium-ion battery electrode.
- the electrode suspension according to item 36 comprising from about 80% to about 95%, preferably from about 90% to about 95% or from about 80% to about 90%, by weight percent, of the active material based on the total mass. dryer of the electrode suspension.
- the electrode suspension according to item 36 or 37 further comprising carbon black.
- the electrode suspension according to item 38 comprises between about 1% and about 5%, preferably about 3%, by weight percent, of carbon black based on the total dry mass of the electrode suspension.
- the electrode suspension according to any one of items 36 to 38 further comprising carbon fibers.
- the electrode suspension according to item 40 comprises between about 1% and about 5%, preferably about 3%, by weight percent, of carbon fibers based on the total dry mass of the electrode suspension.
- the electrode suspension according to any of items 36 to 41 comprising from about 2% to about 15%, preferably from about 3% to about 10%, and more preferably from about 5% to about 10%, by weight percent, of the copolymer based on the total dry mass of the electrode suspension.
- a lithium-ion battery electrode comprising an electrode current collector having on at least a portion, preferably all of its surface, a membrane formed of a mixture of the copolymer as defined in any of the items 1 at 21 and at least one active material.
- a lithium-ion battery comprising a positive electrode, a negative electrode and an electrolytic solution in contact with the positive electrode and the negative electrode; the positive electrode and / or the negative electrode being an electrode according to the invention as defined according to item 38.
- Figure 1 shows the polymerization kinetics of the polymer of the half-cell 3 as followed by proton NMR.
- Figures 2 and 3 A) and B) are SEM images of the surface of an electrode according to an embodiment of the invention at different magnifications.
- Figures 4 A) and B) are SEM images of a cross section of an electrode according to an embodiment of the invention at different magnifications.
- Figure 5 is an EDX image of a cross section of an electrode according to an embodiment of the invention.
- Figure 6 shows the capacity of half-cells A) 1a, 1b, 2a and 2b and B) 3, 4 and 5 during 200 cycles of charging / discharging.
- Figure 7 shows the capacity of the half batteries A) 1b and 2b and B) 3, 4 and 5 depending on the charge rate.
- Figure 8 shows the capacity of the half batteries 1 b, 2b and reference (PVDF) during 100 cycles of charging / discharging at different discharge rate (+ C / 4 -1C; + C / 4 -3C - + C / 4 -4 C and + C / 4 -1 C).
- the present invention therefore relates to a copolymer comprising
- the monomer A being a hydrophilic monomer comprising a pendant chain of poly (ethylene oxide) (POE) of low molecular weight
- the monomer B being a hydrophobic monomer having a a glass transition temperature (Tg) of about -30 ° C or lower
- the C monomer being a more hydrophobic monomer than the B monomer and having a glass transition temperature (Tg) of about 80 ° C or higher
- said monomers being organized in:
- the hydrophilic segment comprising the monomer A and a part of the monomer B
- the intermediate segment and the hydrophobic segment comprising the rest of the monomer B as well as the monomer C
- the intermediate segment being enriched in monomer B with respect to the hydrophobic segment
- the segment hydrophobic being enriched in monomer C with respect to the intermediate segment
- the copolymer thus has a hydrophilicity gradient from the hydrophilic segment to the hydrophobic segment through the intermediate segment.
- the copolymer further comprises a monomer D, which is a monomer chemically crosslinkable in water, in a molar ratio d ranging from about 0 to about 0.10, preferably from about 0.01 to about 0.10. Since the monomer D is hydrophilic and water-soluble, it is found in the hydrophilic segment of the copolymer.
- a monomer D which is a monomer chemically crosslinkable in water, in a molar ratio d ranging from about 0 to about 0.10, preferably from about 0.01 to about 0.10. Since the monomer D is hydrophilic and water-soluble, it is found in the hydrophilic segment of the copolymer.
- the copolymer is of the following formula:
- A, B, C and D respectively represent said monomers A, B, C and D and
- A, b, c and d respectively represent said molar ratios a, b, c, and d.
- the copolymer of the invention comprises segments of different hydrophilicities.
- the copolymer is amphiphilic.
- the sum of total number of monomers in the copolymer these molar ratios, (a + b + c) or, if the monomer D is present (a + b + c + d), is necessarily equal to 1.
- d varies between about 0 and about 0.10. When d is 0, monomer D is absent.
- the monomer A is a POE derivative of low molecular weight, the latter feature to prevent the crystallization of the pendant chains of POE.
- the molar mass of the POE pendant chain ranges from about 300 to about 2000 g / mol, preferably from about 300 to 1000 g / mol, and more preferably from about 300 to about 500 g / mol. .
- the monomer A is, for example, a polyethylene glycol methyl acrylate or a polyethylene glycol methyl methacrylate.
- the monomer A is of formula:
- Formula 2 wherein R is a hydrogen atom or a methyl group and x represents a POE repeating unit number such that the molar mass of the POE chain is as defined above.
- the monomer B has, for example, a Tg between about -30 ° C and about -60 ° C. In embodiments, monomer B has a Tg of -40 ° C or less, for example a Tg between about -40 ° C and about -60 ° C.
- the monomer B may be, for example:
- any other acrylate or methacrylate having a suitable Tg in particular an alkyl acrylate or methacrylate, the alkyl being unsubstituted or substituted, preferably at the end of the chain, with one or more hydroxyl and / or alkoxy groups, alkoxy being unsubstituted or substituted, preferably at the end of the chain, with one or more hydroxy groups and / or alkoxy, preferably with an alkoxy group; such as iso-decyl acrylate, n-decyl methacrylate, n-dodecyl methacrylate, 2-ethylhexyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2-hydroxyethyl, 2-methoxyethyl acrylate, n-propyl acrylate, ethylene glycol methyl ether acrylate, etc.,
- monomer B is n-butyl acrylate or vinyl butyl ether, preferably n-butyl acrylate.
- alkyl and “alkoxy” (i.e. -O-alkyl) denotes, in preferred embodiments, groups comprising from 1 to 20, preferably from 1 to 12 carbon atoms.
- the monomer C is, for example, styrene and its derivatives, acrylonitrile, vinazene TM (an imidazole derivative, more particularly 2-vinyl-4,5). dicyanoimidazole), methyl methacrylate, tert-butyl methacrylate, acryloyl morpholine, phenyl methacrylate, ferrocene vinyl, methyl ferrocene methacrylate or a mixture thereof.
- the monomer C is styrene or acrylonitrile, preferably styrene.
- the monomer D is absent.
- the monomer D is present.
- the monomer D is, for example, diacetone acrylamide.
- the copolymer is not crosslinked. In other embodiments, the copolymer is crosslinked via monomer D.
- the copolymer comprises polyethylene glycol methyl acrylate or polyethylene glycol methyl methacrylate as monomer A, n-butyl acrylate (Tg ⁇ -49 ° C) as monomer B and styrene (Tg ⁇ 90 ° C) as monomer C.
- the copolymer has the following formula:
- this copolymer furthermore comprises diacetone acrylamide as monomer D and is therefore of the following formula:
- R is a hydrogen atom or a methyl group and x, a, b, c and d are as defined above.
- the glass transition temperature (Tg) of the copolymer is between about 0 ° C and about 20 ° C and preferably between about 5 ° C and about 10 ° C.
- the molar mass (M n ) of the copolymer is between about 100,000 g / mol and about 300,000 g / mol and preferably between about 150,000 g / mol and about 200,000 g / mol. mol.
- the copolymer described above can be manufactured by emulsion polymerization in water. To do this, the monomers are added to water. Depending on their solubility in water, the monomers will be in solution in water (monomer A and, if appropriate, monomer D), in hydrophobic droplets immiscible in water (monomer C) or in water. both media (monomer B), which produces an emulsion which serves as a reaction medium.
- a water-soluble radical polymerization initiator is used. The initiator may be, for example, potassium persulfate or any other water-soluble initiator.
- a nonionic surfactant, such as Triton X-100, is used to stabilize the emulsion.
- the various monomers are in water and / or in hydrophobic droplets while the initiator is solubilized in water.
- the polymerization begins with the solubilized monomers in water (i.e., the monomer A, a small portion of the monomer B and optionally, the monomer D), thereby creating the hydrophilic segment of the copolymer.
- the reaction is continued by the polymerization of the monomers in the droplets (most of the monomer B and the monomer C), starting mainly with the monomer B, thus creating the intermediate segment, and ending mainly with the monomer C, finally creating the hydrophobic segment.
- the present invention also relates to the use of the copolymer described above as a binder for a lithium-ion battery electrode and therefore a binder for a lithium-ion battery electrode comprising said copolymer.
- the present invention also relates to a binder suspension.
- the binder suspension comprises the copolymer described above suspended in water.
- this binder suspension will sometimes be referred to as a "latex".
- This suspension can be used as a binder for a lithium-ion battery electrode and the invention therefore relates to a binder for lithium-ion battery electrode comprising said binder suspension.
- this binder suspension comprises from about 10% to about 20% and preferably from about 10% to about 13%, by weight percent, of the copolymer based on the total weight of the slurry.
- this binder suspension further comprises a surfactant for the purpose of stabilizing the suspension.
- this binder suspension comprises from about 3% to about 7%, by weight percent, of the surfactant based on the total mass of the slurry.
- the present invention also relates to a binder suspension as described above in which the copolymer is crosslinked.
- the binder suspension consists of the reaction mixture in which the copolymer has been manufactured. It is indeed possible to reuse this mixture directly, diluting it with water if necessary.
- the present invention also relates to a method of manufacturing an electrode for lithium-ion battery. This method includes the following steps:
- the stage a) comprises the crosslinking of the copolymer via the monomer D.
- a dihydrazine or dihydrazide compound such as adipic acid dihydrazide.
- the reaction is carried out at room temperature in a few minutes.
- this method further comprises, after step d), the step of cutting the electrode current collector into a suitable size.
- the present invention also relates to an electrode suspension comprising a binder suspension as described above and, in addition, an active material for lithium-ion battery electrode.
- this electrode suspension comprises from about 80% to about 95%, preferably from about 90% to about 95%, or from about 80% to about 90%, by weight percent, of the active material based on the total mass. dryer of the electrode suspension.
- Said suspension may also comprise other ingredients typically used in lithium-ion battery electrodes, for example carbon black and / or carbon fibers.
- carbon black is the carbon black Denka TM Black AB HS-100.
- carbon fibers are VGCF TM -H carbon fibers.
- the electrode slurry comprises between about 1% and about 5%, preferably about 3%, by weight percent, of carbon black based on the total dry mass of the electrode slurry.
- the electrode suspension comprises between about 1% and about 5%, preferably about 3%, by mass percentage, of carbon fibers based on the total dry mass of the electrode suspension.
- the electrode suspension (comprising the active material, the copolymer and, where appropriate, the other ingredients) comprises between about 2% and about 15%, preferably between about 3% and about 10%, and more preferably between about 5% and about 10%, by weight percent, of the copolymer based on the total dry mass of the slurry.
- the present invention also relates to a lithium-ion battery electrode comprising an electrode current collector having at the point a part, preferably on the whole, of its surface a membrane formed of a mixture of the copolymer described hereinabove. and at least one active material and optionally said other ingredients, such as carbon black and carbon fibers.
- the electrode current collector, the active materials and the other ingredients are current collectors.
- electrode, active materials and conventionally used ingredients in the electrodes for lithium-ion batteries are well known to those skilled in the art.
- the present invention also relates to a lithium-ion battery comprising a positive electrode, a negative electrode and an electrolytic solution in contact with the positive electrode and the negative electrode; the positive electrode and / or the negative electrode being an electrode according to the invention as described above.
- the electrolytic solution is an electrolytic solution conventionally used in lithium-ion batteries. Such solutions are well known to those skilled in the art.
- the solvent used for both the polymerization and the suspension for the manufacture of electrode is water: an environmentally friendly solvent and inexpensive.
- the low boiling point of water compared to NMP
- the suspension may not require thickening agent (CMC).
- CMC thickening agent
- the copolymer may contribute to the ionic conductivity of the electrode.
- the binder would no longer be an inactive mass in the lithium-ion battery.
- the hydrophilic portion comprising poly (ethylene oxide) makes it possible to increase the flexibility, the adhesion as well as the ionic conductivity of the membrane on the electrode.
- POE is useful for dispersing inorganic particles and for stabilizing the suspension where it stabilizes the polymer droplets. If the membrane is more flexible, the durability of the electrode increases because the crack formation in the electrodes during their use is limited.
- the hydrophobic part is, among others, consisting of a monomer having a high glass transition temperature, which makes it possible to modulate the overall glass transition temperature of the copolymer as a function of the material specific flexibility and adhesion requirements. electrode.
- this monomer e.g. styrene
- this monomer comprises an aromatic ring
- the latter allows better carbon dispersion by stacking effect n.
- the stability of the electrode during the cycling as well as the adhesion can be improved thanks to the crosslinking of the copolymer via the monomer D.
- PEGMA 300 Poly (ethylene glycol) methacrylate, PEGMA 500 monomer 500 300 g / mol and 500 g / mol
- the polymers were prepared in a 250 ml flask in which was added 80 ml of water with PEGMA 300 or 500 and 0.5 g of triton X-100. The reaction mixture was stirred until dissolved. Styrene and nBA were added to the flask, and then the solution was stirred for 30 minutes at 750 rpm to create an emulsion. The emulsion was degassed under N 2 for 30 min, then 100 mg of KPS was added. The emulsion was heated at 80 ° C. with stirring for 8 hours under nitrogen.
- suspensions for electrodes were prepared. To do this, the reaction mixture resulting from the manufacture of the copolymers was first homogenized in a roll mill for 72 hours. A Thinky TM centrifugal planetary mixer was then used to incorporate the other ingredients (6 times 5 minutes of mixing). Finally, the viscosity of the The suspension was adjusted by adding water to the mixture as needed and stirring for 5 minutes with the Thinky TM blender.
- the suspensions for the different half-cells contained the following ingredients and showed the following viscosities and percentages of crosslinking:
- Positive electrodes were produced by depositing suspensions on aluminum collectors using the Dr. Blade technique. Then, the electrodes were dried for 1 h at 80DC and then 1 h at 120DC. For comparison, electrodes were produced by replacing the polymers of the invention with polyvinyl difluoride (PVDF) or styrene-butadiene rubber (SBR) with methylated cellulose (CMC) (SBR). / CMC).
- PVDF polyvinyl difluoride
- SBR styrene-butadiene rubber
- CMC methylated cellulose
- the conductivity of the electrodes was measured in S / cm by a conductivity meter.
- the adhesion of the polymeric coating to the collector was measured in N / m by an Instron TM T-Peel. The results obtained are shown below.
- the polymeric coatings containing the polymers of the invention have excellent adhesion.
- the PVDF and the SBR / CMC have an adhesion of 13 N / m and 10 N / m, respectively, as measured in our installations.
- the invention makes it possible to have an adhesion of 21 N / m without crosslinking agent.
- this value can be increased when crosslinking is used (compare entries 3 and 4).
- the electrodes were examined by scanning electron microscopy (SEM, Figures 2 to 4).
- Figures 2 and 3 show the surface of the electrode while Figure 4 shows a cross section.
- the images in these figures show that the (dark) polymer makes it possible to homogeneously disperse the particles of active material (lighter) and that each of the particles is coated with polymer.
- Electrodes were studied by energy dispersive analysis (EDX) of carbon.
- Figure 5 shows the image obtained from a cross section of an electrode. Again, there is good dispersion and homogeneity of the material constituting the electrode.
- the electrodes had the following thicknesses, densities and charges:
- Half-cells were made from the above electrodes, a lithium anode of 200 ⁇ and an electrolyte (LIPF6 in a mixture of ethylene carbonate and diethyl carbonate (EC-). DEC) containing 2% of vinyl carbonate (VC)).
- LIPF6 electrolyte in a mixture of ethylene carbonate and diethyl carbonate (EC-).
- DEC ethylene carbonate and diethyl carbonate
- VC vinyl carbonate
- the half-cells were studied at a potential of 2.0 - 4.0 V and at a temperature of 25 ° C.
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Abstract
Description
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CA2928121A CA2928121A1 (en) | 2016-04-22 | 2016-04-22 | Copolymeric binder |
CA2928216A CA2928216A1 (en) | 2016-04-26 | 2016-04-26 | Copolymeric binder |
PCT/CA2017/050505 WO2017181294A1 (en) | 2016-04-22 | 2017-04-24 | Copolymer binder |
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JP6109525B2 (en) | 2011-10-24 | 2017-04-05 | 東洋インキScホールディングス株式会社 | Emulsion binder for forming nickel-metal hydride secondary battery electrode and composite ink for forming nickel-hydrogen secondary battery electrode |
CN103682433A (en) | 2012-09-26 | 2014-03-26 | 中国科学院研究生院 | Multi-arm star-shaped block polymer based electrolyte and preparation method thereof |
CN103524687B (en) * | 2013-09-11 | 2015-11-25 | 江南大学 | A kind of surface topography and the controlled Photosensitive degradable comb-like copolymer film of performance |
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2017
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- 2017-04-24 US US16/094,687 patent/US10964948B2/en active Active
- 2017-04-24 CN CN201780024620.0A patent/CN109071739B/en active Active
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WO2017181294A1 (en) | 2017-10-26 |
US20210159504A1 (en) | 2021-05-27 |
JP2019513869A (en) | 2019-05-30 |
US10964948B2 (en) | 2021-03-30 |
US20190386310A1 (en) | 2019-12-19 |
JP7145759B2 (en) | 2022-10-03 |
US11652209B2 (en) | 2023-05-16 |
KR102335809B1 (en) | 2021-12-08 |
KR20180136997A (en) | 2018-12-26 |
CA3020192A1 (en) | 2017-10-26 |
EP3445794A4 (en) | 2019-09-11 |
CN109071739A (en) | 2018-12-21 |
CN109071739B (en) | 2021-08-13 |
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