CN114437358A - Polymer resin with polyethylene glycol side chain, preparation method thereof and power storage electrode - Google Patents
Polymer resin with polyethylene glycol side chain, preparation method thereof and power storage electrode Download PDFInfo
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- CN114437358A CN114437358A CN202210086613.6A CN202210086613A CN114437358A CN 114437358 A CN114437358 A CN 114437358A CN 202210086613 A CN202210086613 A CN 202210086613A CN 114437358 A CN114437358 A CN 114437358A
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- electrode
- polymer
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- dry
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- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 22
- 125000003827 glycol group Chemical group 0.000 title claims abstract description 20
- 239000002952 polymeric resin Substances 0.000 title claims description 16
- 229920003002 synthetic resin Polymers 0.000 title claims description 16
- 238000003860 storage Methods 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 87
- 239000011230 binding agent Substances 0.000 claims description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 34
- 229910052744 lithium Inorganic materials 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 29
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- 239000006258 conductive agent Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000013543 active substance Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- -1 carboxyl bisphenol Chemical compound 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011889 copper foil Substances 0.000 claims description 11
- 239000011267 electrode slurry Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 229930185605 Bisphenol Natural products 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000002931 mesocarbon microbead Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 125000000468 ketone group Chemical group 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000011366 tin-based material Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 229920006260 polyaryletherketone Polymers 0.000 abstract description 8
- 150000003457 sulfones Chemical class 0.000 abstract description 6
- 239000004695 Polyether sulfone Substances 0.000 abstract description 2
- 229920001643 poly(ether ketone) Polymers 0.000 abstract description 2
- 229920006393 polyether sulfone Polymers 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 238000003825 pressing Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- OGTSHGYHILFRHD-UHFFFAOYSA-N (4-fluorophenyl)-phenylmethanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1 OGTSHGYHILFRHD-UHFFFAOYSA-N 0.000 description 1
- NDTOCQNXMGILGR-UHFFFAOYSA-N 1-(4-fluorophenyl)sulfonyl-4-[4-(4-fluorophenyl)sulfonylphenyl]benzene Chemical group C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(C=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(F)=CC=2)C=C1 NDTOCQNXMGILGR-UHFFFAOYSA-N 0.000 description 1
- MONGUDQJUIVFPI-UHFFFAOYSA-N 1-(benzenesulfonyl)-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=CC=C1 MONGUDQJUIVFPI-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- QSUWIYOOMLCSPE-UHFFFAOYSA-N 1-fluoro-4-[4-(4-fluorophenyl)sulfonylphenyl]sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(S(=O)(=O)C=2C=CC(F)=CC=2)C=C1 QSUWIYOOMLCSPE-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block 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
- H01M4/13—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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a polyethylene glycol side chain-containing polyaryletherketone/sulfone polymer material, which aims at the problem that unmodified pure polyethersulfone or polyetherketone polymers limit the conductivity between an electrode active material and a conductive medium and a current collector. In addition, the polymer with the polyethylene glycol side chain has enough adhesive force and adhesive strength as an adhesive, an electrode film can be prepared by adopting a wet method or a melt extrusion drying method, and an electrode active material and a conductive medium are adhered on a current collector, so that the electrode film is not easy to crack and fall off, and an electrochemical device has enough capacity and cycle performance and excellent rate performance.
Description
Technical Field
The invention belongs to the technical field of energy sources, and particularly relates to a polymer resin with a polyethylene glycol side chain, a preparation method and a power storage electrode.
Background
The electrode is a core component of an electric energy storage device such as a power battery and a capacitor, and is also the largest part of the cost of the electric energy storage device such as the battery and the capacitor. The conductive paste mainly comprises four parts, namely an active substance, a conductive agent, a binder and a current collector. The conventional electrode preparation method is to uniformly disperse active substances, conductive agents and binders in a solvent and then coat the active substances, the conductive agents and the binders on a current collector to prepare a pole piece. In addition, the active substance, the conductive agent and the binder can be mechanically manufactured into a film and then adhered to a current collector to manufacture the pole piece. In the whole preparation process of the electrode, although the dosage of the binder is small, the binder is an additional material with higher technical content in the electrode material.
The polyaryletherketone and polyaryletherketone materials with good heat-resistant stability and chemical stability are applied to the field of power batteries and mainly applied to the field of battery diaphragms due to good heat-resistant stability, chemical stability and electrochemical stability. In recent years, with the rapid development of lithium batteries, materials such as polyarylethersulfones and polyaryletherketones are beginning to be applied to solid electrolytes and electrode binders. Due to the large number of aromatic ring structures, the material has excellent mechanical properties such as high tensile strength and elastic recovery capability, so that the material can effectively limit the thickness change of the electrode in the lithium intercalation process. The lithium ion battery can also show better recovery capability in the lithium removal process, and can effectively maintain the stability of the electrode in the lithium removal and insertion process. However, due to its insulating properties, unmodified pure polyethersulfone or polyetherketone-based polymeric materials are electrically resistive to electrons and lithium ions, limiting to some extent the electrical conductivity between the electrode active material and the conductive media and current collectors. Therefore, if a novel binder capable of enhancing the conductivity of the electrode can be developed, the binder is very important for the fields of silicon-carbon negative electrodes and lithium-air electrodes, and is bound to become an important means for preparing batteries with high cycle stability and high rate characteristics.
Disclosure of Invention
The invention aims to solve the problems of the existing polyarylethersulfone and polyaryletherketone materials, provides a polyarylethersulfone and polyaryletherketone polymer resin with polyethylene glycol side chains, further provides a preparation method of the polymer resin and provides a power storage electrode.
The purpose of the invention is realized by the following technical scheme:
firstly, in the aspect of structural design of materials, a large-branched polyethylene glycol chain segment with low polymerization degree is adopted as a side chain of an aryl ether ketone or a polyarylethersulfone material, so that lithium ions can be effectively conducted through the chain segment, the transmission speed of the lithium ions in a battery is improved, and the difficult problem that the side chain of polyethylene glycol is easy to crystallize is solved due to the characteristics of a large-branched structure and low polymerization degree, and the problems that the chain segment is slow in movement and low in ionic conductivity due to the fact that the polyethylene glycol chain segment is easy to highly crystallize at room temperature are solved; then, the electrode film and the corresponding electrode preparation method provided by the invention are adopted to produce a finished electrode.
In order to solve the problems, the invention provides a polymer resin with a polyethylene glycol side chain structure, which is characterized in that: is a polymer of type (I) and comprises a structural chain segment of formula (I);
wherein n and m are positive integers representing the degree of polymerization;
a is one of structures shown in formulas (A1) to (A6):
formula (A3), (A6) wherein, X is 1,2 or 3;
b is one of structures shown in formulas (B1) to (B3):
formulas (B1) - (B3) are shown in the specification, wherein y is an integer of 1-100;
e is one of the structures shown in formulas (E1) to (E4):
a preparation method of polymer resin with a polyethylene glycol side chain structure comprises the following steps:
A. stirring and heating a difluoride monomer containing a sulfone group or a ketone group, a bisphenol monomer, a side-chain carboxyl bisphenol monomer, a catalyst, a solvent and toluene as a water-carrying agent in a nitrogen environment to 140-150 ℃ to reflux the toluene for 3h, discharging the toluene and water by using an oil-water separator after the toluene and the water are fully carried out, heating to 160-190 ℃ for continuous reaction for 3-8h, discharging the obtained product into an aqueous solution of hydrochloric acid to obtain a white blocky solid, crushing the solid, boiling and washing, and drying to obtain an intermediate polymer (i);
B. mixing the obtained polymer (I) with polyvinyl alcohol B-OH, N' -Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) with linear or branched structures of different chain segment lengths and tetrahydrofuran solution, stirring overnight at room temperature under nitrogen, filtering to remove impurities after the reaction is finished, discharging in ethanol to obtain a polymer crude product, and heating and drying to obtain the (I) type polymer.
Further, in the step A, the catalyst is at least one of potassium carbonate and sodium bicarbonate; the solvent is at least two of N, N' -dimethylformamide, N-dimethylacetamide, sulfolane and N-methylpyrrolidone.
A power storage electrode, characterized by: the invention also provides a method for preparing the polymer (I) by using the polymer (I) as a binder through a dry method or a wet method.
Further, the dry method specifically comprises the following steps: preliminarily premixing the ground and dried conductive agent, active substance and fine binder powder particles; then adding a double screw for further composite dispersion and melt extrusion; a self-supporting dry film of the electrode, namely a dry electrode film, is prepared by extruding a sheet die orifice, and the dry electrode film is adhered on a current collector after anhydrous drying to prepare the electrode.
Further, the dry electrode film is adhered to a current collector by heating and rolling to form an electrode, or is adhered to the current collector by a conductive adhesive and then rolled to form an electrode.
Further, the wet method specifically comprises the following steps: dissolving a binder in a solvent, adding a conductive agent and an active substance in batches, and fully mixing and dispersing in the solvent to obtain stable electrode slurry; then coating the solution on a current collector; and heating and drying to prepare the electrode, wherein the dosage of the solvent is 1-60 times of the total mass of the electrode active material, the conductive agent and the binder.
Furthermore, the active substance accounts for 50 to 99 percent, the conductive medium accounts for 0.5 to 25 percent and the binder accounts for 0.5 to 20 percent by weight percentage.
Still further, the active material includes a positive active material, a negative active material and other non-carbon negative materials, wherein the positive active material includes lithium cobaltate, lithium nickel cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt ferrate, lithium nickelate, ternary materials and the like, the negative active material includes natural graphite, artificial graphite, mesocarbon microbeads (MCMB), soft carbon (such as coke), hard carbon, carbon nanotubes, graphene, carbon fibers, microphone (MXene) and the like, and the other non-carbon negative materials are mainly classified into silicon-based and composite materials thereof, nitride negative electrodes, tin-based materials, lithium titanate, alloy materials and the like, but not limited to particle size, specific surface area, crystal form, hardness, and combination manner; the conductive substance comprises traditional conductive agents such as carbon black, conductive graphite, carbon fiber and the like, and novel conductive agents such as carbon nano tubes, graphene, microphone, conductive polymers and the like, but is not limited to particle size, specific surface area, crystal form and hardness.
Furthermore, the current collector is one or more of metal foils such as copper foil, aluminum foil, carbon-coated aluminum foil and carbon-coated copper foil, metal meshes such as nickel mesh, copper mesh, aluminum mesh and stainless steel mesh, foam metals such as metal sheet layer, porous metal foil and foam nickel, carbon cloth, graphite plate, graphene layer and carbon nanotube layer, and can be used in a single layer or in a layer structure.
Compared with the prior art, the invention has the beneficial effects that:
1. the electrode binder is a polymer resin material with a side chain containing polyethylene glycol and a main chain of a polyaryletherketone/sulfone structure, and the main chain and the side chain structure in the polymer have good thermal stability, chemical stability and electrochemical stability, so that the requirements of the electrode on the binder are met;
2. the rigidity of the main chain structure is beneficial to maintaining the film forming stability of the self-supporting film, and in addition, the resin material with the polyaryletherketone/sulfone structure has strong adhesion to a metal current collector, which is far higher than that of the conventional polytetrafluoroethylene and polyvinylidene fluoride, and is beneficial to the stability of electrodes;
3. the flexible polyvinyl alcohol chain segment structure of the side chain is beneficial to regulating and controlling the processing performance of the polymer resin; on one hand, the lithium ion battery can bring a good wetting effect between an electrolyte and an electrode, for example, lithium ions can be rapidly transmitted back and forth between an electrode active material and the electrolyte, so that the lithium battery which can stably run under the rapid charging and discharging condition is obtained; on the other hand, a self-aggregation phase can be formed, and the effects of weakening and buffering the contraction and expansion problem of the electrode volume are achieved in the working process of the electrode;
4. the proper combination of the hard-soft segment makes the adhesive have the easy processing characteristic of preparing the electrode by a dry method, has good solubility and can complete the processing technology of preparing the electrode by a conventional wet method in various solvents.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an IR spectrum of a polymer P14-P17 provided in example 1 of the present invention;
FIG. 2 shows the NMR spectra of polymers P14-P17 provided in example 1 of the present invention;
FIG. 3 is a graph of glass transition temperatures of polymers P1, P14-P17 provided in example 1 of the present invention;
FIG. 4 is a schematic diagram of a positive electrode preparation flow of example 4 of the present invention;
FIG. 5 is a schematic view of a negative electrode preparation process of example 5 of the present invention;
FIG. 6 is a cross-sectional scanning electron microscope image of a sample of a lithium battery positive electrode prepared by a wet process in example 8 of the present invention and exemplified by polymer P4;
FIG. 7 is a reaction scheme for the preparation of polymer resins with polyethylene glycol side chains according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polymer resin with the polyethylene glycol side chain structure comprises a structural chain segment shown in a formula (I):
wherein n and m are positive integers representing the degree of polymerization;
a is one of structures shown in formulas (A1) to (A6):
in the formulae (A3) and (A6), X is 1,2 or 3;
b is one of structures shown in formulas (B1) to (B3):
in the formulae (B1) to (B3), y is an integer of 1 to 100.
E is one of the structures shown in formulas (E1) to (E4):
in an embodiment provided by the present invention, the structure may be specifically a P1-P41 structure:
the preparation method of the polymer resin with the polyethylene glycol side chain structure comprises the following steps:
1. putting a diphenylsulfone or diphenylketone monomer containing a double-halogen structure and a bisphenol structure monomer, a bisphenol monomer containing a carboxyl side chain, a catalyst (potassium carbonate, sodium bicarbonate or any combination of the potassium carbonate and the sodium bicarbonate), a solvent (N, N' -dimethylformamide, N-dimethylacetamide, sulfolane, N-methylpyrrolidone or any combination of two or more of the two), and a water-carrying agent (toluene) into a multi-neck flask provided with an oil-water separator and a mechanical stirring device, stirring and heating to 140-150 ℃ under the protection of inert gas (nitrogen or argon) to reflux the toluene for 3h, discharging the toluene and water by using an oil-water separator after fully carrying water, then increasing the temperature to 160-190 ℃ to stir and react for 3-8h, and discharging the mixture into a hydrochloric acid aqueous solution to obtain a white blocky solid. And (3) crushing the solid, boiling, washing and drying to obtain an intermediate polymer (i), and directly putting the intermediate polymer (i) into the next reaction, wherein the reaction formula is shown in figure 7.
Wherein n and m are positive integers representing the degree of polymerization;
a is one of the structures A1-A6:
in the formulas (A3) and (A6), X is 1,2 or 3;
e is one of structures shown as E1-E4:
2. mixing the polymer intermediate (I) with polyvinyl alcohol B-OH, N' -Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) with linear or branched structures of different chain segment lengths and tetrahydrofuran solution, stirring overnight at room temperature under nitrogen, filtering to remove impurities after the reaction is finished, discharging in ethanol to obtain a polymer crude product, and heating and drying to obtain the (I) type polymer.
Wherein n and m are positive integers representing the degree of polymerization;
a is one of the structures A1-A6:
in the formulas (A3) and (A6), X is 1,2 or 3;
b is one of the structures B1-B3:
in the formulae (B1) to (B3), y is an integer of 1 to 10000.
E is one of structures shown as E1-E4:
wherein, the corresponding molecular structure is obtained by changing different bifluoride monomers containing sulfuryl/keto and bisphenol monomers. The selected difluoride monomer (A1) containing sulfonyl is 4,4' -difluoro diphenyl sulfone; (A2) the formula is 4,4' -bis (4-fluoro-diphenylsulfone) ether; (A3) the formula is 1, 4-di (4-fluorobenzene sulfonyl) benzene or 4,4 '-di (4-fluorobenzene sulfonyl) biphenyl or 4,4' -di (4-fluorobenzene sulfonyl) terphenyl. The selected bifluoride monomer (A4) containing keto is 4,4' -difluorobenzophenone; (A5) formula (I) is 4,4' -bis (4-fluorobenzophenone-based) ether; (A6) the formula is 1, 4-bis (4-fluorophenonyl) benzene or 4,4 '-bis (4-fluorophenonyl) biphenyl or 4,4' -bis (4-fluorophenonyl) terphenyl. The selected monomer (E1) containing bisphenol is 4,4' -dihydroxy diphenylmethane; (E2) 2, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol a); (E3) 4,4' - (hexafluoroisopropylidene) diphenol; (E4)4,4' -dihydroxydiphenyl ether.
In the preparation process of the present invention, the catalyst and the reactants are first charged into the reaction apparatus. Wherein the reactant comprises a side chain carboxyl bisphenol monomer and a difluoride monomer. When the copolymer is prepared according to the present invention, the reactants further comprise bisphenol monomer E. The catalyst is preferably potassium carbonate, sodium bicarbonate or any combination of the potassium carbonate and the sodium bicarbonate, and the dosage of the catalyst is preferably 1.05-1.5 times of the molar weight of the sulfuryl-containing difluoride monomer. And then adding a solvent and toluene as a water-carrying agent into the reaction device, wherein the solvent can be N, N' -dimethylformamide, N-dimethylacetamide, sulfolane, N-methylpyrrolidone or any combination of two or more than three of the solvents. And after the catalyst, the reactant, the solvent and the water-carrying agent are added, the reaction is carried out. Wherein, the reaction is preferably carried out under the condition of removing water by toluene as a water-carrying agent; the water carrying temperature of the reaction is 140-150 ℃, toluene and water are discharged from the oil-water separator after the water is carried, the reaction temperature is increased to 160-190 ℃, and the reaction time is 3-8 h. After the reaction reaches a certain time, the viscosity of the system rises rapidly, and the reactant is poured into the hydrochloric acid removed aqueous solution to terminate the reaction. And finally, crushing, washing and drying the solid obtained by the reaction to obtain a polymer intermediate as shown in the formula (i).
And mixing the polymer intermediate (I) with polyvinyl alcohol B-OH, N' -Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) with different chain segment lengths and a tetrahydrofuran solution, stirring overnight at room temperature under nitrogen, filtering to remove impurities after the reaction is finished, discharging in ethanol to obtain a polymer crude product, and heating and drying to obtain the (I) type polymer binder with the polyethylene glycol side chain structure.
The power storage electrode is prepared by using the type (I) polymer as a binder through a dry method or a wet method. The binder may be any one type (I) polymer, or any combination of a plurality of types (I) polymers.
The dry method specifically comprises the following steps:
1. compounding superfine polyethylene glycol side chain-containing type (I) polymer powder particles with a conductive agent by a ball mill or a high-speed stirrer, adding an active material, and continuously performing compound processing by the ball mill or the high-speed stirrer to finally form a premixed dry material; according to weight percentage, the active substance is 50 to 99 percent, the conductive medium is 0.5 to 25 percent, and the binder is 0.5 to 20 percent; the dosage of the solvent is 1-60 times of the total mass of the electrode active material, the conductive agent and the binder.
2. Adding the premixed dry material into a double-screw extruder, extruding the premixed dry material from a sheet die orifice through four temperature control areas of 170 ℃, 185 ℃, 195 ℃ and 190 ℃, and cooling and drying the premixed dry material in a waterless area to obtain a self-supporting electrode dry film taking the type (I) polymer as a binder to form a dry electrode film; the dry electrode film has a thickness of 20-260 microns; the method is suitable for preparing the anode and the cathode.
3. Adhering the dry electrode film on a current collector through conductive adhesive, and rolling at 280 ℃ to prepare a positive electrode/a negative electrode; or directly hot-pressing with a metal current collector at 280 ℃ to obtain the electrode. The electrode film has a thickness of 20-260 microns; the method is suitable for preparing the anode and the cathode.
In step 3, the dry electrode film and the current collector can be adhered to the current collector through the conductive adhesive and the rolling operation, and the current collector can be adhered to the dry electrode film on one side of the dry electrode film in the modes of evaporation, electroplating, spraying, deposition, 3d printing and the like, and can be used independently or combined by multiple methods.
The wet method specifically comprises the following steps:
1. dissolving type (I) polymer fine powder particles containing polyethylene glycol side chains in an organic solvent, sequentially adding a conductive agent and an active material, and mechanically stirring the mixture for a long time to obtain a viscous liquid mixed with the type (I) polymer fine powder particles and the active material; according to weight percentage, the active substance is 50-99%, the conductive medium is 0.5-25%, and the binder is 0.5-20%.
2. Then coating the solution on a current collector;
3. heating and drying to obtain the electrode.
In the dry and wet electrode preparation processes, the active material comprises: the positive active materials include lithium cobaltate, lithium nickel cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt ferrite, lithium nickelate, ternary materials and the like; and negative active materials such as natural graphite, artificial graphite, mesocarbon microbeads (MCMB), soft carbon (e.g., coke), hard carbon, carbon nanotubes, graphene, carbon fibers, graphene (MXene), and the like, and other non-carbon negative materials mainly include silicon-based and composite materials thereof, nitride negative electrodes, tin-based materials, lithium titanate, alloy materials, and the like, but are not limited to particle size, specific surface area, crystal form, hardness, and combination manner; the conductive substance includes: traditional conductive agents such as carbon black, conductive graphite and carbon fiber, and novel conductive agents such as carbon nanotubes, graphene, microphone and conductive polymers, but not limited to particle size, specific surface area, crystal form and hardness.
The current collector is one or more of metal foils such as copper foil, aluminum foil, carbon-coated copper foil and the like, metal meshes such as nickel mesh, copper mesh, aluminum mesh, stainless steel mesh and the like, foam metals such as metal sheet layer, porous metal foil, foam nickel and the like, carbon cloth, graphite plate, graphene layer and carbon nanotube layer, and can be used in a single layer or a layer structure;
the binder, the continuous electrode film and the electrode product are characterized in that the binder, the continuous electrode film and the electrode product are applied to various chemical power sources; the plurality of chemical sources of electrical energy include: lithium batteries, supercapacitors, fuel cells, metal-air batteries, nickel-metal hydride batteries, and the like; the electrolyte may be a solid electrolyte or a liquid electrolyte.
Example 1: preparation of Binder P1
Step 1: 4,4 '-dihydroxydiphenyl-n-pentanoic acid (0.20mol), 4' -difluorodiphenyl sulfone (0.20mol), 1.2 equivalents of catalyst potassium carbonate (0.24mol), 260mL of NMP (solid content 25%), 100mL of toluene as a water-carrying agent were put into a 50mL three-necked flask equipped with a nitrogen port, an oil-water separator, and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene refluxed for 3 hours, and after being sufficiently hydrated, toluene and water were discharged with the oil-water separator. The temperature is raised to 170 ℃ and the reaction is stirred for 8 h. After the reaction, the solution was poured into 500mL of an aqueous hydrochloric acid solution with stirring. Pulverizing into powder with tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times 1000mL) and ethanol (3 times 500mL), filtering, collecting, standing in oven, and drying at 80 deg.C for 10 hr. A white polymer intermediate was obtained (yield 90%).
Step 2: the polymer intermediate (0.10mol) was directly dissolved in 300mL of dry tetrahydrofuran, and then N, N' -dicyclohexylcarbodiimide (DCC, 0.15mol), 4-dimethylaminopyridine (DMAP, 0.015mol), 2,5,8,11,15,18,21, 24-octaoxopentacosan-13-ol (0.50mol) were added to the solution in this order, and the mixture was stirred at room temperature for 48 hours under nitrogen protection. After the reaction is finished, filtering and repeatedly discharging the materials into ethanol. A white polymer was obtained. Vacuum drying at 110 ℃ for 24 hours gave white polymeric binder P1 (93% yield).
Example 2: preparation of Binder P4
The present embodiment differs from embodiment 1 in that: the pre-polymerized double-halogenated monomer adopted in the step one is 4,4' -difluorobenzophenone. Stirring and heating the mixture in a nitrogen atmosphere until toluene refluxes for 2 hours to finish the water carrying process, and then discharging the toluene and water by using an oil-water separator. The temperature was then raised to 175 ℃ and the reaction stirred for 9 hours. Other steps are the same as in the embodiment. A white polymeric binder P1 was obtained (yield 90%).
Example 3: preparation of Binder P10
Step 1: 4,4 '-dihydroxydiphenyl-n-pentanoic acid (0.20mol), 4' -difluorodiphenyl sulfone (0.20mol), 1.2 equivalents of catalyst potassium carbonate (0.24mol), 260mL of NMP (solid content 25%), 100mL of toluene as a water-carrying agent were put into a 50mL three-necked flask equipped with a nitrogen port, an oil-water separator, and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene refluxed for 3 hours, and after being sufficiently hydrated, toluene and water were discharged with the oil-water separator. The temperature is raised to 170 ℃ and the reaction is stirred for 8 h. After the reaction, the solution was poured into 500mL of an aqueous hydrochloric acid solution with stirring. Pulverizing into powder with tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times 1000mL) and ethanol (3 times 500mL), filtering, collecting, standing in oven, and drying at 80 deg.C for 10 hr. A white polymer intermediate was obtained (91% yield).
Step 2: the above polymer intermediate (0.10mol) was directly dissolved in 300mL of dry tetrahydrofuran, and then N, N' -dicyclohexylcarbodiimide (DCC, 0.15mol), 4-dimethylaminopyridine (DMAP, 0.015mol), (3,4, 5-tris (2- (2- (2-methoxyethoxy) ethoxy) phenyl) methanol (0.50mol) were sequentially added to the solution, and stirred at room temperature for 48 hours under nitrogen. After the reaction is finished, filtering and repeatedly discharging the materials into ethanol. A white polymer was obtained. Vacuum drying at 110 ℃ for 24 hours gave white polymeric binder P10 (87% yield).
Example 4: preparation of Binder P18
The present embodiment differs from embodiment 3 in that: the pre-polymerized double-halogenated monomer adopted in the step one is 4,4' -difluorobenzophenone. Stirring and heating the mixture in a nitrogen atmosphere until toluene reflows for 2.5 hours, finishing the water carrying process, and then discharging the toluene and water by using an oil-water separator. Then the temperature is raised to 170 ℃, 175 ℃ and 180 ℃ and the mixture is stirred and reacted for 2 hours, 2 hours and 3 hours respectively. Other steps are the same as in the embodiment. This gave a white polymeric binder P18 (yield 84%).
Example 5: preparation of Binder P28
Step 1: 4,4 '-dihydroxydiphenyl-n-pentanoic acid (0.10mol), 4' -difluorodiphenyl sulfone (0.20mol), bisphenol A ((0.10mol))1.2 equivalents of catalyst potassium carbonate (0.24mol), 260mL of NMP (solid content 25%), 100mL of water-carrying agent toluene were put into a 50mL three-necked flask equipped with a nitrogen port, an oil-water separator, and mechanical stirring, heated under stirring in a nitrogen atmosphere until toluene refluxed for 3 hours, and after sufficient water-carrying, toluene and water were discharged with the oil-water separator. The temperature is raised to 170 ℃ and the reaction is stirred for 8 h. After the reaction, the solution was poured into 500mL of an aqueous hydrochloric acid solution with stirring. Pulverizing into powder with tissue pulverizer, filtering under reduced pressure, collecting solid precipitate, boiling with hot water (5 times 1000mL) and ethanol (3 times 500mL), filtering, collecting, standing in oven, and drying at 80 deg.C for 10 hr. A white polymer intermediate was obtained (yield 87%).
Step 2: the above polymer intermediate (0.10mol) was directly dissolved in 300mL of dry tetrahydrofuran, and then N, N' -dicyclohexylcarbodiimide (DCC, 0.15mol), 4-dimethylaminopyridine (DMAP, 0.015mol), (3,4, 5-tris (2- (2- (2-methoxyethoxy) ethoxy) phenyl) methanol (0.30mol) were sequentially added to the solution, and stirred at room temperature for 48 hours under nitrogen. After the reaction is finished, filtering and repeatedly discharging the materials into ethanol. A white polymer was obtained. Vacuum drying at 110 ℃ for 24 hours gave white polymeric binder P28 (83% yield).
Example 6: preparation of Binder P31
The present embodiment differs from embodiment 5 in that: the pre-polymerized double-halogenated monomer adopted in the step one is 4,4' -difluorobenzophenone. Stirring and heating the mixture in a nitrogen atmosphere until toluene reflows for 2.5 hours, finishing the water carrying process, and then discharging the toluene and water by using an oil-water separator. Then the temperature is increased to 160 ℃, 165 ℃ and 170 ℃ and the reaction is stirred for 2 hours, 2 hours and 1 hour respectively. Other steps are the same as in the embodiment. This gave a white polymeric binder P31 (yield 86%).
Example 7: wet preparation of lithium battery positive electrode by taking polymer P1 as example
(1) Adopting dry nickel cobalt lithium ferrite powder as an active substance, carbon black powder as a conductive agent and polymer P1 as a powder binder, and uniformly mixing the three powders by a high-speed mixer according to a mass ratio of 83:5:12 at dry room temperature for 5 minutes each time and 3 times in total to obtain a dry mixture;
(2) dispersing and dissolving the mixture obtained in the step (1) in anhydrous methyltetrahydrofuran, wherein the mass ratio of the solvent to the binder P1 is 15: 1, stirring at a high speed for 1 hour until the corresponding electrode slurry is uniformly coated;
(3) and (3) uniformly coating the electrode slurry prepared in the step (2) on two sides of an aluminum foil with the thickness of 14 microns, transferring the aluminum foil to an oven for drying, starting gradient temperature rise from 60 ℃, rising to 120 ℃ at a speed of 10 ℃ per 1 hour, then carrying out vacuum drying at the temperature for 6 hours, recovering the room temperature, taking out, and finally forming a finished electrode through three processes of mechanical cold pressing, strip separation and tab welding to obtain the positive electrode piece with the thickness of about 80 microns and capable of being used for the lithium battery.
Example 8: wet preparation of lithium battery positive electrode by taking polymer P4 as example
The present embodiment differs from embodiment 7 in that: the solution used for preparing the electrode slurry in the step (2) is N-methylpyrrolidone (NMP), and the mass ratio of the agent to the binder P4 is 10: 1. and in the step (3), the temperature rise process of the oven drying is carried out by starting from 80 ℃ and carrying out gradient temperature rise, wherein the temperature rise speed is 20 ℃ per 1 hour to 150 ℃, then the drying is carried out for 8 hours in vacuum at the temperature, and the drying is carried out after the room temperature is recovered. Other steps are the same as in the embodiment.
Example 9: dry preparation of lithium battery positive electrode by taking polymer P14 as example
(1) After 30 minutes, the binder P14 ultrafine powder particles are compounded with a conductive agent by a ball mill or a high-speed stirrer, then an active material lithium cobaltate is added, and the ball mill compounding processing is continued for 1 hour, so as to finally form a black premixed dry material;
(2) adding the premixed dry material into a double-screw extruder, extruding the premixed dry material from a sheet die orifice through four temperature control areas of 150 ℃, 160 ℃, 165 ℃ and 170 ℃, and cooling and drying the premixed dry material in a waterless area to obtain a self-supporting electrode dry film taking the type (I) polymer as a binder to form a dry electrode film;
(3) the dry electrode film is adhered to a current collector through conductive adhesive, and a positive electrode is manufactured through 220-roll pressing. And then, taking out the electrode after the room temperature is recovered, and finally forming a finished electrode through three processes of mechanical cold pressing, splitting and tab welding to obtain the positive pole piece which is about 110 microns thick and can be used for the lithium battery.
Example 10: preparation of lithium battery positive electrode by taking polymer P4 as an example
(1) Adopting dry nickel cobalt lithium ferrite powder as an active substance, carbon black powder as a conductive agent and polymer P1 as a powder binder, and uniformly mixing the three powders by a high-speed mixer according to a mass ratio of 83:5:12 at dry room temperature for 5 minutes each time and 3 times in total to obtain a dry mixture;
(2) dispersing and dissolving the mixture obtained in the step (1) in anhydrous methyltetrahydrofuran, wherein the mass ratio of the solvent to the binder P1 is 15: 1, stirring at a high speed for 1 hour until the corresponding electrode slurry is uniformly coated;
(3) and (3) uniformly coating the electrode slurry prepared in the step (2) on two sides of an aluminum foil with the thickness of 14 microns, transferring the aluminum foil to an oven for drying, starting gradient temperature rise from 60 ℃, rising to 120 ℃ at a speed of 10 ℃ per 1 hour, then carrying out vacuum drying at the temperature for 6 hours, recovering the room temperature, taking out, and finally forming a finished electrode through three processes of mechanical cold pressing, strip separation and tab welding to obtain the positive electrode piece with the thickness of about 80 microns and capable of being used for the lithium battery.
Example 11: wet preparation of lithium battery negative electrode by taking polymer P1 as example
(1) Uniformly mixing three kinds of powder in a mass ratio of 85:7:8 by using a dry negative electrode silicon-carbon active material (consisting of 35% by mass of fine silica powder and 65% by mass of fine graphite powder) as an active substance, carbon black powder as a conductive agent and polymer P1 powder as a binder by using a high-speed mixer at dry room temperature, wherein the mixing time is 5 minutes each time and 3 times in total, so as to obtain a dry mixture;
(2) dispersing and dissolving the mixture obtained in the step (1) in anhydrous methyltetrahydrofuran, wherein the mass ratio of the solvent to the binder P1 is 15: 1, stirring at a high speed for 1 hour until the corresponding cathode electrode slurry is uniformly coated;
(3) and (3) uniformly coating the electrode slurry prepared in the step (2) on two sides of a copper foil with the thickness of 12 microns, transferring the copper foil to an oven for drying, starting gradient temperature rise from 60 ℃, rising to 120 ℃ at a speed of 10 ℃ per 1 hour, then carrying out vacuum drying at the temperature for 6 hours, recovering the room temperature, taking out, and finally forming a finished electrode through three processes of mechanical cold pressing, strip splitting and tab welding to obtain the negative pole piece which is about 300 microns and can be used for the lithium battery.
Example 12: wet preparation of lithium battery negative electrode by taking polymer P15 as example
(1) Uniformly mixing the three kinds of powder in a mass ratio of 87:6:7 by using dry lithium titanate as an active substance, carbon black powder as a conductive agent and polymer P1 fine powder as a binder through a high-speed mixer at dry room temperature, wherein the mixing time is 15 minutes each time and 3 times in total, so as to obtain a dry mixture;
(2) dispersing and dissolving the mixture obtained in the step (1) in anhydrous N-methylpyrrolidone (NMP), wherein the mass ratio of the solvent to the binder P16 is 10: 1, stirring at a high speed for 1 hour until the corresponding cathode electrode slurry is uniformly coated;
(3) and (3) uniformly coating the electrode slurry prepared in the step (2) on two sides of a copper foil with the thickness of 12 microns, transferring the copper foil to an oven for drying, starting gradient temperature rise from 60 ℃, rising to 150 ℃ at the speed of 20 ℃ per 1 hour, then carrying out vacuum drying at the temperature for 6 hours, recovering the temperature to room temperature, taking out, and finally forming a finished electrode through three processes of mechanical cold pressing, strip splitting and tab welding to obtain the negative pole piece which is about 120 microns and can be used for the lithium battery.
Example 13: dry preparation of negative electrode of lithium battery by taking polymer P16 as example
(1) After 30 minutes, the binder P16 ultrafine powder particles are compounded with a conductive agent by a ball mill or a high-speed stirrer, then an active material lithium titanate material is added, and the ball mill compounding processing is continued for 1 hour, and finally a black premixed dry material is formed;
(2) adding the premixed dry material into a double-screw extruder, extruding the premixed dry material from a sheet die orifice through four temperature control areas of 130 ℃, 140 ℃, 150 ℃ and 160 ℃, and cooling and drying the premixed dry material in a waterless area to obtain a self-supporting electrode dry film taking the type (I) polymer as a binder to form a dry electrode film;
(3) and adhering the dry electrode film on a copper foil through conductive adhesive, and rolling 220 to prepare a negative electrode current collector. And then, taking out the electrode after the room temperature is recovered, and finally forming a finished electrode through three processes of mechanical cold pressing, splitting and tab welding to obtain the negative pole piece which is about 100 microns thick and can be used for the lithium battery.
Example 14: preparation of lithium battery with polymer P1 as binder
Sequentially stacking the positive and negative electrode plates prepared in the embodiment 4, the commercial polypropylene film type diaphragm and the negative electrode plate prepared in the embodiment 5 according to a sequence to ensure that the isolating film is positioned between the positive and negative electrode plates, and then mechanically winding to prepare a bare cell; under the inert anhydrous condition, the bare cell is placed in a metal circular battery packaging shell, and the preparation of the lithium battery can be completed through the working procedures of liquid injection, formation, standing and the like.
While embodiments of the invention have been disclosed above, it is not intended to be limited to the uses set forth in the specification and examples. It can be applied to all kinds of fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. It is therefore intended that the invention not be limited to the exact details and illustrations described and illustrated herein, but fall within the scope of the appended claims and equivalents thereof.
Claims (10)
1. A polymer resin with a polyethylene glycol side chain structure is characterized in that: is a polymer of type (I) and comprises a structural chain segment of formula (I);
wherein n and m are positive integers representing the degree of polymerization;
a is one of structures shown in formulas (A1) to (A6):
wherein X is 1,2 or 3;
b is one of structures shown in formulas (B1) to (B3):
wherein y is an integer of 1-100;
e is one of the structures shown in formulas (E1) to (E4):
2. the method for preparing the polymer resin with the polyethylene glycol side chain structure according to claim 1, comprising the following steps:
A. stirring and heating a difluoride monomer containing a sulfone group or a ketone group, a bisphenol monomer, a side-chain carboxyl bisphenol monomer, a catalyst, a solvent and toluene as a water-carrying agent in a nitrogen environment to 140-150 ℃ to reflux the toluene for 3h, discharging the toluene and water by using an oil-water separator after the toluene and the water are fully carried out, heating to 160-190 ℃ for continuous reaction for 3-8h, discharging the obtained product into an aqueous solution of hydrochloric acid to obtain a white blocky solid, crushing the solid, boiling and washing, and drying to obtain an intermediate polymer (i);
B. mixing the obtained polymer (I) with polyvinyl alcohol B-OH, N' -Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) with linear or branched structures of different chain segment lengths and tetrahydrofuran solution, stirring overnight at room temperature under nitrogen, filtering to remove impurities after the reaction is finished, discharging in ethanol to obtain a polymer crude product, and heating and drying to obtain the (I) type polymer.
3. The method for preparing the polymer resin with the polyethylene glycol side chain structure according to claim 2, wherein in the step A, the catalyst is at least one of potassium carbonate and sodium bicarbonate; the solvent is at least two of N, N' -dimethylformamide, N-dimethylacetamide, sulfolane and N-methylpyrrolidone.
4. An electric power storage electrode using a polymer resin having a polyethylene glycol side chain structure according to claim 1, characterized in that: the polymer of the type (I) is used as a binder and is prepared by a dry method or a wet method.
5. A power storage electrode according to claim 4, characterized in that said dry method comprises in particular the steps of: preliminarily premixing the ground and dried conductive agent, active substance and fine binder powder particles; then adding a double screw for further composite dispersion and melt extrusion; a self-supporting dry film of the electrode, namely a dry electrode film, is prepared by extruding a sheet die orifice, and the dry electrode film is adhered on a current collector after anhydrous drying to prepare the electrode.
6. A power storage electrode according to claim 5, wherein the dry electrode film is adhered to a current collector by heat rolling to form an electrode, or by a conductive adhesive to a current collector and then rolling to form an electrode.
7. A power storage electrode according to claim 4, characterized in that the wet method comprises in particular the steps of: dissolving a binder in a solvent, adding a conductive agent and an active substance in batches, and fully mixing and dispersing in the solvent to obtain stable electrode slurry; then coating the solution on a current collector; and heating and drying to prepare the electrode, wherein the dosage of the solvent is 1-60 times of the total mass of the electrode active material, the conductive agent and the binder.
8. A power storage electrode according to any one of claims 5 to 7, wherein the active material is 50% to 99%, the conductive medium is 0.5% to 25%, and the binder is 0.5% to 20% by weight.
9. The power storage electrode of any of claims 5 to 7, wherein the active material comprises a positive active material, a negative active material, and other non-carbon negative materials, wherein the positive active material comprises lithium cobaltate, lithium nickel cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt ferrite, lithium nickelate, and ternary materials,
the negative active material comprises natural graphite, artificial graphite, mesocarbon microbeads, soft carbon, hard carbon, carbon nanotubes, graphene, carbon fibers and microphone, and other non-carbon negative materials are mainly silicon-based and composite materials thereof, nitride negative electrodes, tin-based materials, lithium titanate and alloy materials; the conductive substance comprises carbon black, conductive graphite, carbon fiber, carbon nano tube, graphene, microphone and conductive polymer.
10. A power storage electrode according to any of claims 5 to 7, wherein: the current collector is one or more of a copper foil, an aluminum foil, a carbon-coated copper foil, a nickel net, a copper net, an aluminum net, a stainless steel net, a metal sheet layer, a porous metal foil, foamed nickel, carbon cloth, a graphite plate, a graphene layer and a carbon nanotube layer, and can be used in a single-layer mode or a layer structure mode.
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