CN117736668A - Adhesive, negative plate comprising adhesive and battery - Google Patents
Adhesive, negative plate comprising adhesive and battery Download PDFInfo
- Publication number
- CN117736668A CN117736668A CN202311762753.1A CN202311762753A CN117736668A CN 117736668 A CN117736668 A CN 117736668A CN 202311762753 A CN202311762753 A CN 202311762753A CN 117736668 A CN117736668 A CN 117736668A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- binder
- acrylate
- battery
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 65
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 65
- 239000011230 binding agent Substances 0.000 claims abstract description 111
- 239000000178 monomer Substances 0.000 claims abstract description 84
- 229920001577 copolymer Polymers 0.000 claims abstract description 57
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 229910021385 hard carbon Inorganic materials 0.000 claims description 37
- 229910001415 sodium ion Inorganic materials 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 26
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- -1 N-dimethylacrylamide Chemical compound 0.000 claims description 21
- 239000007773 negative electrode material Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000011888 foil Substances 0.000 claims description 14
- 239000006183 anode active material Substances 0.000 claims description 13
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- TUWWOIIMFKLZJJ-UHFFFAOYSA-N C(C=C)(=O)OCC.[Na] Chemical compound C(C=C)(=O)OCC.[Na] TUWWOIIMFKLZJJ-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000011366 tin-based material Substances 0.000 claims description 2
- AUCNMQYOQYTGPE-UHFFFAOYSA-N n-(hydroxymethyl)-n-methylprop-2-enamide Chemical compound OCN(C)C(=O)C=C AUCNMQYOQYTGPE-UHFFFAOYSA-N 0.000 claims 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 16
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- 230000009286 beneficial effect Effects 0.000 abstract description 10
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- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 56
- 238000002360 preparation method Methods 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 25
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 description 22
- 229910019142 PO4 Inorganic materials 0.000 description 22
- 239000010452 phosphate Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 19
- 229920003048 styrene butadiene rubber Polymers 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
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- 230000009477 glass transition Effects 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 7
- 238000005056 compaction Methods 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 230000010261 cell growth Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- AOOOGDNZPXWIMU-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate phosphoric acid Chemical compound P(=O)(O)(O)O.C(C(=C)C)(=O)OCCCO AOOOGDNZPXWIMU-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
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- 239000007774 positive electrode material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 239000002998 adhesive polymer Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- UMAFYWRLCSIUBO-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate phosphoric acid Chemical compound P(=O)(O)(O)O.C(C(=C)C)(=O)OCCCCO UMAFYWRLCSIUBO-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
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- NVJCKICOBXMJIJ-UHFFFAOYSA-M potassium;1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [K+].C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O NVJCKICOBXMJIJ-UHFFFAOYSA-M 0.000 description 2
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
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- 230000001627 detrimental effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a binder, a negative electrode plate and a battery comprising the binder, wherein the binder comprises a copolymer, and a comonomer of the copolymer comprises a matrix monomer and a monomer shown in a formula (1);in the formula (1), R 1 、R 2 、R 3 、R 4 、R 5 The same or different are independently selected from H or alkyl, and n is an integer between 1 and 3. The binder provided by the invention can improve the infiltration effect between the aqueous slurry and the metal current collector, is convenient for coating and processing the aqueous slurry, and is beneficial to promoting the green development of batteries. The adhesive provided by the invention can strengthen the bonding capability of the pole piece through the phosphorization bonding action between the adhesive and the metal current collector, improve the cycle performance of the battery, inhibit the expansion of the battery and prolong the service life.
Description
Technical Field
The invention relates to an adhesive, a negative plate comprising the adhesive and a battery, and belongs to the technical field of adhesives for batteries.
Background
The battery technology is used as an important component of sustainable energy, so that the sustainable development of society and the convenience and intellectualization of human life are greatly promoted. The lithium ion battery has the advantages of high energy density, long cycle life and the like, and is widely applied to the fields of mobile phones, notebook computers, electric tools, new energy automobiles, energy storage and the like. Sodium ion batteries are recognized as a beneficial supplement to lithium ion batteries by virtue of their extremely competitive cost advantages and abundant sodium resource reserves. The polymeric binder in the battery acts as one of the important components of the battery, binding the active material particles, as well as the active material and current collector together. At present, most emulsion-type binders are used in the industry, namely SBR emulsion formed by copolymer of styrene and butadiene and styrene-acrylic emulsion formed by copolymerization of styrene and acrylic ester, but only van der Waals acting force exists among particles in the emulsion, an effective three-dimensional bonding network cannot be formed inside a pole piece, and finally, the battery is damaged and fails due to the pole piece structure in the circulating process of the battery. In addition, various application scenarios of the battery place higher and higher demands on the capacity of the battery cell, and accordingly, demands on the negative electrode sheet with high areal density are becoming urgent. The preparation of the high-surface-density negative plate is matched with a binder with high binding power so as to ensure that the high-surface-density negative plate still has strong binding power under the condition of high active substance ratio. However, the conventional water-based adhesive only depends on van der Waals force to exert the adhesive effect, and is difficult to meet the requirements of the thick pole piece on the high active material ratio and the high adhesive force. In actual production, the high-surface-density negative electrode sheet is extremely easy to crack in the process of coating and baking, the prepared electrode sheet is poor in processability, powder is easy to fall off in the slicing or winding process, micro short circuit inside a battery is caused, and the problem of poor battery cycle performance exists. Therefore, there is an urgent need to develop a functional adhesive that can form a strong adhesive network in the electrode sheet to improve the processability and electrochemical properties of the battery.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a binder, a negative electrode sheet and a battery comprising the binder, and the cycle performance of the battery comprising the binder is greatly improved.
The invention aims at realizing the following technical scheme:
a binder comprising a copolymer, the comonomer of which comprises a base monomer and a monomer represented by formula (1);
in the formula (1), R 1 、R 2 、R 3 、R 4 、R 5 The same or different are independently selected from H or alkyl, and n is an integer between 1 and 3.
The invention has the beneficial effects that:
(1) The adhesive provided by the invention can improve the infiltration effect between the water-based slurry and the metal current collector through the phosphorization bonding effect between the phosphate group and the metal current collector, and simultaneously enhance the adhesive force between the active substance coating and the metal current collector, thereby being convenient for coating and processing of the water-based slurry.
(2) The adhesive provided by the invention can strengthen the bonding capability of the pole piece through the phosphorization bonding action between the adhesive and the metal current collector, improve the cycle performance of the battery, inhibit the expansion of the battery and prolong the service life.
(3) The binder provided by the invention can reduce the consumption of the binder while ensuring the binding force in the use process, and is beneficial to the performance of the negative electrode sheet and the improvement of the energy density of the battery.
(4) The binder provided by the invention can meet the processing requirement of the high-surface-density negative electrode, and can obtain a high-capacity battery.
Drawings
FIG. 1 is the infrared spectrum test results of the binders of example 1 and comparative example 1 of the present invention.
Fig. 2 shows the mechanism of action of the adhesive of the present invention.
Detailed Description
< binder >
As described above, the present invention provides a binder comprising a copolymer, the comonomer of which comprises a base monomer and a monomer represented by formula (1);
in the formula (1), R 1 、R 2 、R 3 、R 4 、R 5 The same or different are independently selected from H or alkyl, and n is an integer between 1 and 3.
According to the embodiment of the invention, the phosphate groups in the molecular chain of the binder polymer can form a bonding effect with the metal current collector, meanwhile, the alkyl chain segments in the molecular chain of the binder polymer can be connected with the anode active material, and the binder polymer can form a good bonding network in the paste coating layer through the combined action of the phosphate groups and the alkyl chain segments on the same molecular chain of the binder polymer, so that the bonding capability of the pole piece is enhanced, the cycle performance of the battery is improved, the expansion of the battery is inhibited, and the service life is prolonged; the binding agent has good binding effect, can effectively reduce the using amount of the binding agent, and is beneficial to the performance of the negative electrode sheet and the improvement of the energy density of the battery. The adhesive can also improve the infiltration effect between the water-based slurry and the metal current collector, and is beneficial to the coating processing of the water-based slurry.
According to an embodiment of the invention, R 1 、R 2 、R 3 、R 4 、R 5 Identical or different, independently of one another, from H or C 1-6 An alkyl group; preferably, R 1 、R 2 、R 3 、R 4 、R 5 Identical or different, independently of one another, from H or C 1-3 An alkyl group; also preferably, R 1 、R 2 、R 3 、R 4 、R 5 The same or different, independently of one another, from H, methyl, ethyl or propyl.
According to an embodiment of the invention, n is 1, 2 or 3. By adjusting the size of n, the molecular weight of the monomer represented by formula (1) can be adjusted, and the mass ratio of the phosphate groups in the copolymer can be further adjusted.
According to an embodiment of the invention, the comonomer of the copolymer further comprises a functional monomer.
According to an embodiment of the present invention, the functional monomer includes at least one of acrylonitrile, (meth) acrylamide, (meth) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-methylol (meth) acrylamide, N-dimethylacrylamide, sodium p-styrenesulfonate, sodium vinylsulfonate, sodium allylsulfonate, sodium 2-methylallylsulfonate, sodium ethylacrylate sulfonate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate. The introduction of the functional monomer is beneficial to improving the performance of the copolymer, such as improving the dispersion stability of the copolymer in water; the adhesive force to the metal current collector and the negative electrode active substance is enhanced, a good bonding network is formed, and the bonding effect of the pole piece is enhanced; the transmission of sodium ions in the cathode is quickened, and the dynamic performance of the battery is improved.
According to an embodiment of the present invention, the base monomer includes butadiene and styrene; the copolymer at this time is, for example, a copolymer of a monomer represented by the formula (1), butadiene and styrene, or a copolymer of a monomer represented by the formula (1), butadiene, styrene and a functional monomer.
According to an embodiment of the invention, the matrix monomer comprises styrene and at least one of the following compounds: alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates; in this case, the copolymer is, for example, at least one of an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate, a copolymer of a monomer represented by the formula (1) and styrene, or a copolymer of at least one of an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate, a monomer represented by the formula (1), and a styrene and a functional monomer.
According to an embodiment of the present invention, the base monomer includes at least one of an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate. In this case, the copolymer is, for example, a copolymer of a monomer represented by the formula (1) and at least one of an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate, or a copolymer of a monomer represented by the formula (1) and a functional monomer and at least one of an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate.
According to an embodiment of the invention, the choice of the matrix monomer affects the binding capacity and the kinetic properties of the binder; suitable matrix monomers can be selected according to the actual requirements of the binder. Illustratively, when the matrix monomer includes at least one of an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate, the dynamic properties of the adhesive can be significantly improved; when the matrix monomer comprises styrene, the bonding capability of the adhesive can be remarkably improved.
According to an embodiment of the present invention, the alkyl (meth) acrylate includes at least one of butyl methacrylate, butyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-octyl methacrylate, n-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, dodecyl methacrylate. The hydroxyalkyl (meth) acrylate comprises at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate.
According to an embodiment of the present invention, the mass of the monomer represented by formula (1) is 0.1wt% to 10wt% of the total mass of the copolymer. Preferably, the mass of the monomer represented by the formula (1) is 2wt% to 8wt% of the total mass of the copolymer. Illustratively, the monomer of formula (1) comprises 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt% of the total mass of the copolymer. When the mass of the monomer shown in the formula (1) accounts for the total mass of the copolymer in the range, the adhesive force to the anode active material and the metal current collector can be remarkably improved while the stability of the polymer adhesive emulsion is maintained; when the mass of the monomer shown in the formula (1) accounts for less than 0.1 weight percent of the total mass of the copolymer, the adhesive force of the adhesive is not obviously improved due to the too few phosphate groups in the copolymer; the mass of the monomer represented by the formula (1) is more than 10wt% based on the total mass of the copolymer, and the cohesive force of the copolymer is equivalent to that when the mass ratio of the monomer represented by the formula (1) is 10wt%, but too high the monomer represented by the formula (1) increases the polarity of the polymer, which is disadvantageous for emulsion stability.
According to an embodiment of the present invention, the mass of the matrix monomer is 90wt% to 99.9wt% of the total mass of the copolymer, preferably, the mass of the matrix monomer is 95wt% to 99wt% of the total mass of the copolymer, and illustratively, the mass of the matrix monomer is 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, 99.5wt%, 99.9wt% of the total mass of the copolymer. When the mass of the matrix monomer accounts for the total mass of the copolymer within the range, the adhesive force to the anode active material and the metal current collector can be obviously improved while the stability of the polymer adhesive emulsion is maintained; when the mass of the matrix monomer is less than 90wt% of the total mass of the copolymer, the dispersion stability of the polymer binder emulsion in water is poor, the mass of the matrix monomer is more than 99.9wt% of the total mass of the copolymer, the phosphate group with a modifying effect is too low, and the adhesive capability is not obviously improved.
According to an embodiment of the invention, the functional monomer is present in an amount of 0 to 10wt% based on the total mass of the copolymer. Preferably, the mass of the functional monomer accounts for 1wt% to 5wt% of the total mass of the copolymer. Illustratively, the functional monomer comprises 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt% of the total mass of the copolymer. When the monomers forming the copolymer include functional monomers, and the mass of the functional monomers is 10wt% or less of the total mass of the copolymer, properties of the copolymer, such as dispersion stability of an emulsion formed by the copolymer in water, adhesion to an active material, and ability to conduct active ions, can be improved; the functional monomer accounts for more than 10wt% of the total mass of the copolymer, which is disadvantageous in improving the properties of the copolymer, such as unstable dispersion of the copolymer emulsion in water, and reduced adhesion to the negative electrode active material and the metal current collector.
According to an embodiment of the invention, the binder comprises a copolymer, the comonomers of which include styrene, butadiene, acrylic acid and hydroxyethyl methacrylate phosphate.
According to an embodiment of the invention, the binder comprises a copolymer, the comonomers of which include styrene, butadiene, acrylic acid and hydroxypropyl methacrylate phosphate.
According to an embodiment of the invention, the binder comprises a copolymer, the comonomers of which include styrene, butyl acrylate, acrylonitrile and hydroxyethyl methacrylate phosphate.
According to an embodiment of the invention, the binder comprises a copolymer, the comonomers of which include styrene, butadiene, acrylic acid and hydroxybutyl methacrylate phosphate ester.
According to an embodiment of the invention, the glass transition temperature of the binder is between-20 ℃ and 80 ℃. When the glass transition temperature of the copolymer is in the range, the pole piece prepared by the adhesive has good flexibility, and is beneficial to the adaptation of the pole piece to various battery types such as square, cylinder, soft package (lamination/winding) and the like.
According to an embodiment of the invention, the binder is an emulsion type binder.
According to an embodiment of the invention, the particle size of the emulsion binder is 100-800nm, preferably 100-300nm, such as 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm or 800nm.
According to an embodiment of the invention, the emulsion binder has a PDI of not more than 0.3, preferably not more than 0.1. The viscosity of the emulsion type adhesive is 10-500 mPas, preferably 50-300 mPas. The emulsion type binder has a solid content of 1wt% to 70wt%, preferably 30wt% to 60wt%. It has been found that the binder having the above-mentioned solid content, viscosity and pH can be selected to better achieve the binding performance of the binder, for example, to be applicable to different anode active material materials, and also to have a certain help in thickening and dispersing the slurry.
< method for producing adhesive >
The invention also provides a preparation method of the adhesive, which comprises the following steps:
1) Preparation of monomer represented by formula (1):
mixing hydroxyl-containing acrylate monomer shown in formula a with P 2 O 5 Mixing, heating to 75-80 ℃, reacting at a temperature of 3-3.5h, adding water, heating to 90-95 ℃, and reacting at a temperature of 2-3h to obtain a monomer shown in a formula (1);
wherein the method comprises the steps of，R 1 、R 2 、R 3 、R 4 、R 5 And n is as defined above;
2) Preparation of the copolymer:
mixing a monomer shown in a formula (1), a matrix monomer and optionally a functional monomer, introducing inert gas, and reacting to prepare the copolymer;
3) Preparation of the adhesive:
the above copolymer is dispersed in a dispersion medium (e.g., water) to prepare the adhesive, preferably an emulsion adhesive.
According to an embodiment of the present invention, in step 1), the monomer represented by formula (1) is prepared from the following reaction formula:
according to the embodiment of the invention, in the step 1), the mass ratio of the hydroxyl-containing acrylate monomer shown in the formula a, phosphorus pentoxide and water is 40-80:10-55:2-5.
According to an embodiment of the present invention, in step 1), the hydroxyl-containing acrylate monomer represented by the formula a is one or a combination of several of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
According to an embodiment of the present invention, in step 2), the inert gas is one of high purity nitrogen and high purity argon.
According to an embodiment of the invention, in step 2), the temperature of the reaction is 30-120 ℃ and the time of the reaction is 5-24 hours.
According to an embodiment of the invention, in step 2), different auxiliaries may also be added during the reaction, depending on the base monomers and optionally the functional monomers. Illustratively, the adjuvant includes an initiator, a cross-linking agent, and may additionally include at least one of an emulsifying agent or a buffering agent.
According to an embodiment of the present invention, the initiator is at least one of potassium persulfate, ammonium persulfate, sodium persulfate, potassium permanganate, sodium persulfate/sodium bisulfite, ferrous sulfate/hydrogen peroxide, ammonium persulfate/tetramethyl ethylenediamine, ammonium persulfate/sodium sulfite. Wherein, sodium persulfate/sodium bisulfate, ferrous sulfate/hydrogen peroxide, ammonium persulfate/tetramethyl ethylenediamine, and ammonium persulfate/sodium sulfite respectively represent the initiators used in combination, and can be added sequentially at the time of use.
According to an embodiment of the present invention, the crosslinking agent includes at least one of divinylbenzene, N-methylenebisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate.
According to an embodiment of the present invention, the emulsifier is one or more of an anionic emulsifier, a cationic emulsifier, an amphoteric emulsifier and a nonionic emulsifier. Further, the emulsifier is one or more of SDS (sodium dodecyl sulfate), OP-10 (polyoxyethylene octyl phenol ether-10), dodecyl trimethyl ammonium bromide, sodium dodecyl sulfonate, SDBS (sodium dodecyl benzene sulfonate), dioctyl sodium succinate, polyoxyethylene monolaurate and disproportionated abietic acid potassium soap.
According to an embodiment of the invention, the buffer is sodium bicarbonate or sodium phosphate dodecahydrate (Na 3 PO 4 ·12H 2 O)。
< use of adhesive >
The invention also provides application of the adhesive in the negative plate.
The invention also provides application of the binder in a battery.
The invention also provides application of the adhesive in sodium ion batteries or lithium ion batteries.
According to the embodiment of the invention, hard carbon is found to be the most common negative electrode material of sodium ion batteries, and the following problems still exist in processing: 1) The anode slurry using the oil-based solvent (such as NMP) has good wettability to the aluminum foil current collector, is more convenient for the production of the pole piece, but the use of the organic solvent can increase the cost, has great environmental pollution and damages the health of human bodies. From the cost and environmental protection angleFor the sodium ion battery, deionized water is more preferable as a solvent for the negative electrode slurry, but the water-based slurry has poor wettability with the aluminum foil, and the slurry at the edge can shrink and gather under the action of surface tension during coating processing, so that active substances in the pole piece are unevenly distributed. 2) Specific surface area of hard carbon material (2-9 m 2 Per g) is about 5 times that of conventional graphite negative electrodes, and the smaller particle size of the hard carbon material (Dv 50 distribution 4-10 μm) is only 1/3 of that of conventional graphite, which means that the hard carbon negative electrode formulation requires the introduction of more binder to ensure sufficient binding capacity of the pole piece. However, the introduction of excessive binder may reduce the energy density of the battery to some extent, which is detrimental to the performance of the battery. 3) Various application scenarios of sodium ion batteries place increasing demands on the capacity of the cells and correspondingly, demands on hard carbon cathodes with high areal density are becoming more stringent. The preparation of the high-surface-density pole piece is matched with a binder with high binding power so as to ensure that the pole piece still has strong binding power under the condition of high active substance ratio. However, the conventional water-based adhesive only depends on van der Waals force to exert the adhesive effect, and is difficult to meet the requirements of the thick pole piece on the high active material ratio and the high adhesive force. In actual production, the hard carbon negative plate with high surface density is easy to be cracked in the process of coating and baking, the prepared plate has poor processing property, powder is easy to be dropped in the process of slicing or winding, micro short circuit in the battery is caused, and the problem of poor battery cycle performance exists. Thus, the need for a functional binder that can form a strong binding network within the pole piece is highly stringent for sodium ion batteries.
When the adhesive is used in a sodium ion battery, the phosphate groups in the molecular chains of the adhesive polymer can form more sufficient bonding action with aluminum foil, meanwhile, the alkyl chain segments in the molecular chains of the adhesive polymer can be tightly connected with hard carbon, and the adhesive polymer can form a better bonding network in a paste coating layer through the combined action of the phosphate groups and the alkyl chain segments on the same polymer molecular chain, so that the bonding capability of a pole piece is enhanced, the cycle performance of the sodium ion battery can be improved more remarkably, the expansion of the battery is inhibited, and the service life is prolonged.
< negative plate >
As described above, the present invention also provides a negative electrode sheet including the above binder.
According to an embodiment of the present invention, the anode sheet includes an anode current collector and an anode active material layer on at least one side surface of the anode current collector, the anode active material layer including the above-described binder, and the mass of the binder is 0.5 to 20wt%, such as 0.6 to 10wt%, such as 1 to 5wt%, of the total mass of the anode active material layer.
According to an embodiment of the present invention, the mass of the binder accounts for 0.5wt%, 0.8wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt% or 20wt% of the total mass of the anode active material layer.
According to an embodiment of the present invention, the negative electrode current collector includes a single-sided copper foil, a double-sided copper foil, a porous copper foil, a single-sided aluminum foil, a double-sided aluminum foil, or a porous aluminum foil.
According to an embodiment of the present invention, the negative electrode sheet further includes a negative electrode active material and a conductive agent.
According to an embodiment of the present invention, the conductive agent includes at least one of conductive carbon black (SP), ketjen black, acetylene black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene, and reduced graphene oxide.
According to an embodiment of the present invention, the negative electrode active material includes at least one of natural graphite, artificial graphite, mesophase carbon microspheres, soft carbon, hard carbon, silicon-based material, tin-based material, and the like.
According to an embodiment of the present invention, the adhesion between the anode active material layer and the anode current collector is not less than 5N/m, for example, 5 to 20N/m. The adhesive is proved to have the advantages that in the coating process, the phosphate group with strong polarity can improve the wettability of the aqueous slurry and the metal current collector through the phosphorization bonding action between the phosphate group and the metal current collector, strengthen the adhesive force between the anode active material layer and the metal current collector, and greatly improve the peeling strength of the pole piece.
According to an embodiment of the present invention, the negative electrode sheet has a single-sided surface density of 3 to 18mg/cm 2 For example 5mg/cm 2 、8mg/cm 2 、10mg/cm 2 、12mg/cm 2 Or 15mg/cm 2 . The energy density of the battery can be adjusted by adjusting the single-sided surface density of the negative plate, more importantly, the adhesive can be suitable for the negative plate with high surface density, in actual production, the negative plate with high surface density is free from paste coating cracking in coating baking, powder falling easily occurs in slicing or winding processes, and the like, so that the processability of the negative plate is remarkably improved, the improvement of the cycle performance of the battery is facilitated, and the adhesive is suitable for more application scenes.
According to an embodiment of the present invention, the negative electrode sheet has a compacted density of 0.8 to 1.7g/cm 3 For example 0.8g/cm 3 、0.85g/cm 3 、0.9g/cm 3 、0.95g/cm 3 、1g/cm 3 、1.1g/cm 3 、1.2g/cm 3 、1.3g/cm 3 、1.4g/cm 3 、1.5g/cm 3 Or 1.7g/cm 3 . And the improvement of the compaction density of the negative plate is beneficial to improving the energy density of the battery.
< preparation method of negative electrode sheet >
The invention also provides a preparation method of the negative plate, which comprises the following steps:
mixing the binder, the negative electrode active material, the conductive agent and deionized water to prepare slurry, coating the slurry on the surface of the negative electrode current collector, and drying.
< Battery >
As described above, the present invention provides a battery including the above-described binder and/or the above-described negative electrode sheet.
According to an embodiment of the invention, the battery is a sodium ion battery or a lithium ion battery.
According to the embodiment of the invention, the negative current collector in the negative plate in the lithium ion battery comprises at least one of a single-smooth-surface copper foil, a double-smooth-surface copper foil and a porous copper foil.
According to the embodiment of the invention, the negative electrode current collector in the negative electrode plate in the sodium ion battery comprises at least one of a single-smooth aluminum foil, a double-smooth aluminum foil or a porous aluminum foil.
According to the embodiment of the invention, the ratio of the thickness of the battery cell of the sodium ion battery, which is tested for 300 times at the temperature of 45 ℃ in a 2C cycle, to the thickness of the battery cell of the first discharge is less than 10%; the ratio of the thickness of the battery core of the lithium ion battery, which is tested for 500 times in a 1C cycle at 45 ℃ to the thickness of the battery core of the lithium ion battery which is discharged for the first time, is less than 10%; this shows that the phosphate group with strong polarity can improve the wettability of the aqueous slurry and the metal current collector through the phosphorization bonding action between the phosphate group and the metal current collector in the coating process of the binder, strengthen the adhesive force between the anode active material layer and the current collector, and greatly improve the peeling strength of the pole piece. Thanks to the improvement of the binding force of the pole piece, when the binding agent is applied to the sodium ion battery, the cycle performance of the sodium ion battery is obviously improved; compared with the SBR binder, the sodium ion battery using the binder has higher cycle capacity retention rate and lower expansion rate during the cycle.
According to an embodiment of the invention, the battery is a cylindrical battery, a prismatic battery or a pouch battery.
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The following examples 1-10 and comparative examples 1-5 are illustrative of the binders of the present invention.
Example 1
1) Preparation of hydroxyethyl methacrylate phosphate:
62 parts by mass of hydroxyethyl methacrylate (as described below) were added to a reactor, followed by 34 parts of P 2 O 5 Added in portions under high speed stirringAfter the addition of the water is completed within 1.5h, the temperature is quickly raised to 75 ℃, the reaction is carried out for 3.5h while keeping the temperature, then 4 parts of water is added, the temperature is quickly raised to 90 ℃, the reaction is carried out for 2h while keeping the temperature, and the hydroxyethyl methacrylate phosphate (formula I) is obtained after discharging.
2) Preparation of hydroxyethyl methacrylate phosphate modified styrene-butadiene rubber emulsion binder
Sequentially adding 30 parts of styrene, 70 parts of butadiene, 0.4 part of acrylic acid, 4 parts of hydroxyethyl methacrylate phosphate prepared by the above method, 4.5 parts of disproportionated potassium abietate soap, 160 parts of deionized water and 0.5 part of NaHCO into a reaction kettle 3 0.1 part of divinylbenzene and 0.5 part of tert-dodecyl mercaptan serving as a molecular weight regulator, nitrogen is introduced for protection, stirring is carried out at 300rpm, and the temperature is raised to 65 ℃. After stirring for 30 minutes, adding 0.3 part of sodium persulfate, preserving heat at 60 ℃, condensing, stirring at 300rpm continuously, reacting for 9 hours, adjusting the pH value by ammonia water after the reaction is finished, and filtering by a 200-mesh gauze to obtain the hydroxyethyl methacrylate phosphate modified styrene-butadiene rubber emulsion type binder. The emulsion adhesive has a glass transition temperature of 6deg.C, an average particle diameter of 180nm, a PDI of 0.06, a viscosity of 20-60 mPa.s, a solid content of 39-41wt%, and a pH=6-8.
Example 2
1) Preparation of hydroxypropyl methacrylate phosphate:
into a reaction vessel, 64 parts of hydroxypropyl methacrylate was added to obtain 32 parts of P 2 O 5 The mixture is added in portions under high-speed stirring, the mixture is added in 1.5 hours, then the temperature is quickly raised to 75 ℃, the reaction is carried out for 3.5 hours under heat preservation, then 4 parts of water is added, the temperature is quickly raised to 90 ℃, the reaction is carried out for 2 hours under heat preservation, and the hydroxypropyl methacrylate phosphate (formula II) is obtained after discharging.
2) Preparation of hydroxypropyl methacrylate phosphate modified styrene-butadiene rubber emulsion binder
Sequentially adding 30 parts of styrene, 70 parts of butadiene, 0.4 part of acrylic acid, 4 parts of hydroxypropyl methacrylate phosphate prepared by the above method, 4.5 parts of disproportionated potassium abietate soap, 160 parts of deionized water and 0.5 part of NaHCO into a reaction kettle 3 0.1 part of divinylbenzene and 0.5 part of tert-dodecyl mercaptan as a molecular weight regulator, nitrogen is introduced for protection, stirring is carried out at 300rpm, and the temperature is raised to 60 ℃. After stirring for 30 minutes, adding 0.3 part of sodium persulfate, preserving heat at 65 ℃, condensing, stirring at 300rpm continuously, reacting for 9 hours, adjusting the pH value by ammonia water after the reaction is finished, and filtering by a 200-mesh gauze to obtain the hydroxyethyl methacrylate phosphate modified styrene-butadiene rubber emulsion type binder. The emulsion adhesive has a glass transition temperature of 6deg.C, an average particle diameter of 183nm, a PDI of 0.06, a viscosity of 20-60 mPa.s, a solid content of 39-41wt%, and a pH=6-8.
Example 3
1) Preparation of hydroxyethyl methacrylate phosphate:
62 parts by mass of hydroxyethyl methacrylate (as described below) were added to a reactor, followed by 34 parts of P 2 O 5 Adding the mixture in batches under high-speed stirring, finishing the addition within 1.5h, then quickly heating to 75 ℃, preserving heat for 3.5h, then adding 4 parts of water, quickly heating to 90 ℃, preserving heat for 2h, discharging, and obtaining the hydroxyethyl methacrylate phosphate (formula I).
2) Preparation of hydroxyethyl methacrylate phosphate modified styrene-acrylic emulsion binder
The preparation method comprises the steps of sequentially adding a compound of octyl phenol polyoxyethylene ether (OP-10) and Sodium Dodecyl Sulfate (SDS) into a reaction kettle as an emulsifier, wherein the mass ratio is 2/1, 4 parts of styrene, 60 parts of butyl acrylate, 1 part of acrylonitrile, 0.1 part of N, N-methylene bisacrylamide, 4 parts of hydroxyethyl methacrylate phosphate prepared by the method and 200 parts of water. Nitrogen was introduced for protection, stirred at 300rpm and warmed to 75 ℃. After stirring for 30 minutes, adding 0.35 part of sodium persulfate, preserving heat at 80 ℃, condensing, stirring at 300rpm continuously, reacting for 8 hours, cooling to 40 ℃ after the reaction is finished, adjusting the pH by sodium hydroxide, and filtering by a 200-mesh gauze to obtain the hydroxyethyl methacrylate phosphate modified styrene-acrylic emulsion type binder. The emulsion adhesive has a glass transition temperature of 8deg.C, an average particle diameter of 190nm, a PDI of 0.05, a viscosity of 20-60 mPa.s, a solid content of 39-41wt%, and a pH=7-8.
Example 4
1) Preparation of hydroxybutyl methacrylate phosphate:
66 parts by mass of hydroxybutyl methacrylate (as described below) are added to a reaction vessel, and 30 parts by mass of P 2 O 5 Adding the mixture in batches under high-speed stirring, finishing the addition within 1.5h, then quickly heating to 75 ℃, preserving heat for 3.5h, then adding 4 parts of water, quickly heating to 90 ℃, preserving heat for 2h, discharging to obtain the hydroxybutyl methacrylate phosphate (formula III).
2) Preparation of hydroxybutyl methacrylate phosphate ester modified styrene butadiene rubber emulsion binder
Sequentially adding 30 parts of styrene, 70 parts of butadiene, 0.4 part of acrylic acid, 4 parts of the prepared hydroxybutyl methacrylate phosphate ester, 4.5 parts of disproportionated abietic acid potassium soap, 160 parts of deionized water and 0.5 part of NaHCO into a reaction kettle 3 0.1 part of divinylbenzene and 0.5 part of tert-dodecyl mercaptan serving as a molecular weight regulator, nitrogen is introduced for protection, stirring is carried out at 300rpm, and the temperature is raised to 65 ℃. After stirring for 30 minutes, adding 0.3 part of sodium persulfate, preserving heat at 60 ℃, condensing, stirring at 300rpm continuously, reacting for 9 hours, adjusting the pH value by ammonia water after the reaction is finished, and filtering by a 200-mesh gauze to obtain the hydroxyethyl methacrylate phosphate modified styrene-butadiene rubber emulsion type binder. The emulsion adhesive has a glass transition temperature of 6deg.C, an average particle diameter of 185nm, a PDI of 0.06, a viscosity of 20-70 mPa.s, a solid content of 39-41wt%, and a pH=6-8.
Example 5
Referring to example 1, except that acrylic acid was not added in the preparation of the styrene-butadiene rubber emulsion binder.
Example 6
1) Preparation of hydroxyethyl methacrylate phosphate:
62 parts by mass of hydroxyethyl methacrylate (as described below) were added to a reactor, followed by 34 parts of P 2 O 5 Adding the mixture in batches under high-speed stirring, finishing the addition within 1.5h, then quickly heating to 75 ℃, preserving heat for 3.5h, then adding 4 parts of water, quickly heating to 90 ℃, preserving heat for 2h, discharging, and obtaining the hydroxyethyl methacrylate phosphate (formula I).
2) Preparation of hydroxyethyl methacrylate phosphate modified acrylate emulsion type adhesive
The preparation method comprises the steps of taking a compound of octyl phenol polyoxyethylene ether (OP-10) and Sodium Dodecyl Sulfate (SDS) as an emulsifier, wherein the mass ratio is 1/1.5, 4 parts, 2 parts of methacrylic acid, 33 parts of methyl methacrylate, 60 parts of butyl acrylate, 4 parts of hydroxyethyl methacrylate phosphate prepared by the preparation method and 200 parts of water. Adding an emulsifier (OP-10/SDS) and deionized water into a reaction container by adopting a semi-continuous method, stirring for 1h, uniformly mixing and emulsifying; then heating to 80 ℃ and simultaneously introducing N 2 Adding 1/5 part of mixed monomer and 1/3 part of initiator, and reacting for 1h at 85 ℃; then respectively and simultaneously dripping the rest mixed monomers and the initiator into the system for about 3 hours, and after the dripping is completed, preserving heat and reacting for 2 hours; cooling to 25 ℃, and regulating the pH to 7.0-8.0 by ammonia water to obtain the target hydroxyethyl methacrylate phosphate modified acrylate emulsion adhesive. The glass transition temperature of the emulsion type adhesive is 20 ℃, the average particle diameter of the emulsion type adhesive is 150nm, the PDI is 0.04, the viscosity is 10-70 mPa.s, and the solid content is 38-40wt%.
Example 7
Referring to example 1, except that 1 part of hydroxyethyl methacrylate phosphate was added in the preparation of the styrene-butadiene rubber emulsion binder.
Example 8
Referring to example 1, except that 8 parts of hydroxyethyl methacrylate phosphate was added in the preparation of the styrene-butadiene rubber emulsion binder.
Example 9
Referring to example 1, except that 10 parts of hydroxyethyl methacrylate phosphate was added in the preparation of the styrene-butadiene rubber emulsion binder.
Example 10
Referring to example 1, except that 12 parts of hydroxyethyl methacrylate phosphate was added in the preparation of the styrene-butadiene rubber emulsion binder.
Comparative example 1
Referring to example 1, except that hydroxyethyl methacrylate phosphate was not added in the preparation of the styrene-butadiene rubber emulsion binder.
Comparative example 2
Referring to example 3, except that hydroxyethyl methacrylate phosphate was not added in the preparation of the styrene-acrylic emulsion binder.
Comparative example 3
Referring to example 6, except that hydroxyethyl methacrylate phosphate was not added in the preparation of the acrylate emulsion type binder.
Comparative example 4
Styrene-butadiene rubber emulsion binders are commercially available, specifically GD1331L styrene-butadiene emulsion from Shanghai, inc.
Comparative example 5
Referring to example 1, except that in the preparation of the styrene-butadiene rubber emulsion binder, hydroxyethyl methacrylate phosphate was added in an amount of 4% by mass of styrene-butadiene rubber in a physical mixing manner, instead of copolymerizing hydroxyethyl methacrylate phosphate with butadiene and styrene.
Emulsion colloidal particle size and PDI data for the above example and comparative binders were obtained by laser particle sizer (Mastersizer 3000) testing.
The viscosities of the above examples and comparative examples were measured using a viscometer (mountain intelligent NDJ-5S).
The glass transition temperatures of the above example and comparative binders were measured by differential scanning calorimeter (Shimadzu DSC-60A Plus).
The infrared spectra of the above examples and comparative adhesives were obtained using FTIR spectrometer (zemoer Nicolet iS 5) testing.
The gel fraction test method of the emulsion of the above example is as follows: the emulsion was filtered through a 100 mesh screen, and the resulting condensate was washed with distilled water several times and baked in an oven at 120℃for 1h, weighed, and calculated as follows:
gel fraction = (gel dry weight/emulsion total weight) ×100%
The chemical stability test method of the emulsion of the above example is as follows: 5mL of the emulsion was added to the tube, followed by 5mL of 0.5wt% CaCl 2 The solution was stirred uniformly, allowed to stand for 24 hours, and observed for the presence or absence of aggregation and delamination.
FIG. 1 is an infrared spectrum of the adhesive of example 1 and comparative example 1, from which it can be seen that the infrared spectrum of example 1 has a wave number of 1030cm -1 1174cm -1 The new two absorption peaks are added at the positions of (1) and can respectively correspond to the P-O-C stretching vibration and the P=O bond, which can indicate that the phosphate participates in the copolymerization reaction and is successfully introduced into emulsion colloidal particles. While the infrared spectrum of comparative example 1 had a wave number of 1030cm -1 1174cm -1 No absorption peak is located at the position of (2).
The following examples illustrate negative electrode sheets and sodium ion batteries using the phosphate modified binders of the present invention.
1. Preparation of positive electrode sheet
The positive electrode active material, the binder PVDF and the conductive carbon black are mixed and stirred at a high speed to obtain a uniformly dispersed mixture. In the mixture, the solid component contained 96wt%, 2wt% of binder PVDF and 2wt% of conductive carbon black. The mixture was prepared into a positive electrode active material slurry using N-methylpyrrolidone as a solvent, and the solid content in the slurry was 60wt%. And uniformly coating the slurry on two sides of an aluminum foil, and drying and compacting by a roller press to obtain the positive plate. In an embodiment, the positive electrode active material of the sodium ion battery is Na [ Ni ] 1/3 Fe 1/3 Mn 1/3 ]O 2 The positive active material of the lithium ion battery is LiFePO 4 。
2. Preparation of negative electrode sheet
The negative electrode active material, the binder, the thickener and the conductive carbon black are mixed, and the mixture containing the negative electrode active material is prepared by stirring at a high speed to obtain a uniformly dispersed mixture. Deionized water was used as a solvent to prepare a negative electrode active material slurry, the solid content in the slurry being 50wt%. The sizing agent is evenly coated on the two sides of the aluminum foil, and the negative plate is obtained after drying and rolling.
The solid components of the slurry of the negative electrode of the group A comprise 95 weight percent of hard carbon, 1 weight percent of sodium carboxymethyl cellulose, 2 weight percent of conductive carbon black and 2 weight percent of binder, and the single-sided area density of the negative electrode is 3.7mg/cm 2 A compaction density of 1g/cm 3 The particle diameter Dv50 of the hard carbon material was 5.11 μm, and the specific surface area was 5.88m 2 /g。
The slurry solid component of the negative electrode of the group B comprises 94 weight percent of hard carbon, 1 weight percent of sodium carboxymethyl cellulose, 2 weight percent of conductive carbon black and 3 weight percent of binder, and the single-sided area density of the negative electrode is 3.7mg/cm 2 A compaction density of 1g/cm 3 The particle diameter Dv50 of the hard carbon material was 5.11 μm, and the specific surface area was 5.88m 2 /g。
The solid components of the slurry of the negative electrode of the B' group comprise 94 weight percent of hard carbon, 1 weight percent of sodium carboxymethyl cellulose, 2 weight percent of conductive carbon black and 3 weight percent of binder, and the single-sided area density of the negative electrode is 3.7mg/cm 2 A compaction density of 1g/cm 3 The particle diameter Dv50 of the hard carbon material was 6.90 μm, and the specific surface area was 4.92m 2 /g。
The solid components of the slurry of the negative electrode of the group B' comprise 94 weight percent of hard carbon, 1 weight percent of sodium carboxymethyl cellulose, 2 weight percent of conductive carbon black and 3 weight percent of binder, and the single-sided area density of the negative electrode is 3.7mg/cm 2 A compaction density of 1g/cm 3 The particle diameter Dv50 of the hard carbon material was 9.82 μm, and the specific surface area was 2.10m 2 /g。
The solid component of the slurry of the negative electrode of the group C comprises 94 weight percent of hard carbon, 1 weight percent of sodium carboxymethyl cellulose, 2 weight percent of conductive carbon black and 3 weight percent of binder, and the single-sided area density of the negative electrode is 12mg/cm 2 A compaction density of 1g/cm 3 The particle diameter Dv50 of the hard carbon material was 5.11 μm, and the specific surface area was 5.88m 2 /g。
The solid components of the slurry of the negative electrode of the group D comprise 95 weight percent of graphite, 1 weight percent of sodium carboxymethyl cellulose, 2 weight percent of conductive carbon black and 2 weight percent of binder, and the single-sided area density of the negative electrode is 12mg/cm 2 A compaction density of 1.6g/cm 3 The particle diameter Dv50 of the graphite material is 15.36 mu m, and the specific surface area is 1.17m 2 /g。
3. Assembled battery
And after punching the negative plate and the positive plate, forming a bare cell by adopting a Z-shaped lamination, and respectively turning out the positive electrode and the negative electrode from the aluminum tab. Clamping the bare cell by using a glass clamp with the strength of 100MPa/m 2 And baking at 85 ℃ for 24 hours in vacuum, packaging with an aluminum plastic film, injecting liquid, and then performing formation and aging on the battery to obtain the soft package battery with the length and width of 75mm multiplied by 50mm multiplied by 5mm, wherein the design capacity of the battery core is 1000mAh. Wherein, the electrolyte of the sodium ion battery adopts 1mol/L NaPF 6 (EC/DEC+5% FEC), the electrolyte of the lithium ion battery adopts 1mol/L LiPF 6 (EC/DEC+5％FEC)。
The binders of examples 1-10 and comparative examples 1-5 were used to prepare hard carbon anodes according to the group a hard carbon anode slurry formulation and areal density, and the prepared anode sheets were designated as A1-a15, respectively; preparing a hard carbon negative electrode according to the formula and the surface density of the hard carbon negative electrode slurry of the group B, wherein prepared negative electrode sheets are respectively marked as B1-B15, and assembled sodium ion batteries are respectively marked as E1-E15; preparing a hard carbon negative electrode according to the formula and the surface density of the hard carbon negative electrode slurry of the group C, wherein the prepared negative electrode sheets are respectively marked as C1-C15; preparing graphite negative electrodes according to the formula and the surface density of the group D graphite negative electrode slurry, wherein prepared negative electrode sheets are respectively marked as D1-D15, and assembled lithium ion batteries are respectively marked as F1-F15;
preparing a hard carbon negative electrode according to the formula and the surface density of the hard carbon negative electrode slurry of the group B ' by adopting the binder of the embodiment 1, wherein the prepared negative electrode sheet is denoted as B '1, and the assembled sodium-ion batteries are respectively denoted as E '1; preparing a hard carbon negative electrode according to the formula and the surface density of the hard carbon negative electrode slurry of the group B ', wherein the prepared negative electrode sheet is denoted as B '1, and the assembled sodium ion batteries are respectively denoted as E '1;
The prepared negative electrode sheets A1-A15, B1-B15, B '1, B'1, C1-C15 and D1-D15 are respectively subjected to the following performance tests:
(1) Peel strength test: cutting the rolled negative plate into a sample with the size of 20 multiplied by 100mm for later use; the surface of the pole piece, which needs to be tested, is glued by double-sided adhesive, and compacted by a compression roller, so that the pole piece is completely attached to the pole piece; the other surface of the double faced adhesive tape of the sample is adhered to the surface of stainless steel, one end of the sample is reversely bent, and the bending angle is 180 degrees; and (3) testing by adopting a high-speed rail tensile machine, fixing one end of the stainless steel on a clamp below the tensile machine, fixing the bent tail end of the sample on the clamp above, adjusting the angle of the sample, ensuring that the upper end and the lower end are positioned at vertical positions, and then stretching the sample at the speed of 50mm/min until the negative electrode slurry is completely stripped from the substrate, recording the displacement and acting force in the process, and considering the force when the stress is balanced as the stripping strength of the pole piece.
(2) Appearance of the pole piece: whether obvious slurry shrinkage exists at the edge of the pole piece paste coating or not is visually detected, whether cracks exist on the surface of the pole piece paste coating or not is judged, and whether the pole piece is easy to fall off during cutting or not is judged.
And respectively carrying out the following performance tests on the prepared sodium ion batteries E1-E15, E '1 and E' 1:
(1) Multiplying power discharge: charging the battery to 4V at 25deg.C under constant current with 0.2C current, charging at constant voltage, cutting off the current by 0.02C, and standing for 5min; finally, discharging the 1C constant current to 1.5V, and standing for 5min, wherein the discharge capacity is C0; then charging to 4V by using 0.2C constant current and constant voltage, and cutting off 0.02C; standing for 5min; and finally, discharging the 30C constant current to 1.5V, wherein the discharge capacity is marked as C1, and C1/C0 is the 30C discharge capacity retention rate.
(2) Cyclic capacity retention rate and cell expansion rate: constant-current charging the battery to 3.95V at 45 ℃ by using 3C current, constant-voltage charging, cutting off the current by 0.05C, and then standing for 5min; finally, discharging the 3C constant current to 1.5V, and standing for 5min, thus circularly testing for 500 times. The ratio of 500 th discharge capacity to first discharge capacity is the capacity retention rate, and the ratio of the thickness of the battery cell after 500 times of charge and discharge to the thickness of the battery cell after the first time of discharge is the battery cell cyclic expansion rate.
The prepared lithium ion batteries F1-F15 are respectively subjected to the following performance tests:
(1) Multiplying power discharge: charging the battery to 3.65V at 25deg.C under constant current with 0.2C current, charging at constant voltage, cutting off the current by 0.02C, and standing for 5min; finally, discharging the 1C constant current to 2.5V, and standing for 5min, wherein the discharge capacity is C0; then charging to 3.65V by using 0.2C constant current and constant voltage, and cutting off 0.02C; standing for 5min; finally, 10C constant current discharge is carried out to 2.5V, the discharge capacity is marked as C1, and C1/C0 is the 10C discharge capacity retention rate.
(2) Cyclic capacity retention rate and cell expansion rate: constant-current charging the battery to 3.65V at 45 ℃ by using 1C current, constant-voltage charging, cutting off the current by 0.05C, and then standing for 5min; finally, discharging the 1C constant current to 2.5V, and standing for 5min, thus circularly testing for 500 times. The ratio of 500 th discharge capacity to first discharge capacity is the capacity retention rate, and the ratio of the thickness of the battery cell after 500 times of charge and discharge to the thickness of the battery cell after the first time of discharge is the battery cell cyclic expansion rate.
Table 1 results of performance test of negative electrode sheets prepared in examples and comparative examples
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From the results in table 1, it can be found that the negative electrode sheet using the phosphate modified binder has higher peeling force at the same amount of binder, and the powder falling off of the electrode sheet can be improved, so that edge shrinkage during coating of aqueous slurry is avoided. In addition, the phosphate modified binder can exert the same binding power as the conventional binder when the amount is small, which is beneficial to the improvement of the energy density of the battery. More importantly, the phosphate modified binder can assist the preparation of the high-surface-density negative electrode, and the surface density of the negative electrode is as high as 12mg/cm 2 When the phosphate modified binder is used, the negative plate still has excellent binding capacity and good appearance of the plate.
From the results of table 1, it was found that the physical mixing of the phosphate ester with the binder emulsion did not improve the binding effect of the binder; in contrast, the binder prepared by polymerizing the matrix monomer with the monomer represented by formula (1) may exhibit excellent binding ability because, after copolymerization, one end of the molecular chain of the binder polymer is a phosphate group which may be anchored to the metal current collector, and at the same time, the other end of the molecular chain of the polymer is an alkyl segment which may be connected to a negative electrode active material such as graphite, hard carbon, etc.; based on the synergistic effect of the metal current collector and the negative electrode active material, a good bonding network is formed between the metal current collector and the negative electrode active material. If the materials are simply and physically blended, no copolymerization reaction occurs between the materials, and the phosphate group and the alkyl chain segment of the binder are in mutually independent states, so that the negative electrode active material and the metal current collector cannot be connected like a bridge, and the binding force of the binder on the negative electrode active material and the metal current collector cannot be improved.
From the results of table 1, it can be seen that the peel force exhibited by the phosphate modified binder correlates with the ratio of phosphate functional monomers in the binder polymer. When the proportion is less than 8wt%, the binding capacity of the binder is obviously enhanced along with the increase of the proportion of phosphate; however, when the proportion exceeds 8wt%, the binding ability of the binder is substantially limited, and further improvement is difficult.
From the results of table 1, it can be found that, when the particle size of the hard carbon material is smaller and the specific surface area is larger, the bonding between the anode active material and the current collector is more difficult, the stripping force of the represented pole piece is relatively weaker, which just shows that the phosphate copolymerization modified binder in the invention has great application potential in improving the bonding force between the small-particle hard carbon and the metal current collector.
TABLE 2 ratio of phosphate monomers versus emulsion gel fraction and Ca 2+ Influence of stability
From the results of Table 2, it was found that the addition amount of the phosphate functional monomer had a certain effect on the gel fraction and chemical stability of the adhesive copolymer emulsion. As the proportion of the phosphate functional monomer increases, the gel rate first shows a tendency to decrease, because the phosphate functional monomer has good emulsifying property, and can enhance the stability of the emulsion polymerization system; meanwhile, the phosphate monomer also contains a longer carbon chain, so that the space obstruction of emulsion particle aggregation can be increased, and the gel rate can be reduced. As the phosphate functional monomer ratio was further increased to 8wt%, the pH of the emulsion polymerization system was lowered, causing partial demulsification, resulting in an increase in gel fraction. The phosphate functional monomer is an anionic surfactant and has good emulsification. Therefore, the introduction of the phosphate monomer effectively stabilizes the emulsion particles in the emulsion, and the calcium ion stability is remarkably improved. The proportion of the phosphate functional monomer is not more than 10wt% in consideration of the binding power and emulsion stability.
Table 3 table of sodium ion battery performance data
| Adhesive agent | Battery cell | 30C discharge capacity retention rate | Cycle capacity retention rate | Cell expansion rate |
| Example 1 | E1 | 86.7％ | 93.3％ | 3.3％ |
| Example 2 | E2 | 85.5％ | 93.0％ | 3.8％ |
| Example 3 | E3 | 88.5％ | 91.3％ | 4.6％ |
| Example 4 | E4 | 85.3％ | 92.5％ | 4.0％ |
| Example 5 | E5 | 86.2％ | 92.8％ | 3.8％ |
| Example 6 | E6 | 89.8％ | 89.0％ | 6.5％ |
| Example 7 | E7 | 83.5％ | 89.3％ | 6.6％ |
| Example 8 | E8 | 86.5％ | 93.5％ | 3.4％ |
| Example 9 | E9 | 86.3％ | 93.3％ | 3.2％ |
| Example 10 | E10 | 86.0％ | 93.0％ | 3.6％ |
| Comparative example 1 | E11 | 79.6％ | 75.2％ | 13.2％ |
| Comparative example 2 | E12 | 81.7％ | 73.6％ | 16.5％ |
| Comparative example 3 | E13 | 82.1％ | 70.0％ | 22.0％ |
| Comparative example 4 | E14 | 79.5％ | 75.5％ | 13.0％ |
| Comparative example 5 | E15 | 79.4％ | 75.0％ | 13.5％ |
| Example 1 | E’1 | 85.0％ | 93.6％ | 3.0％ |
| Example 1 | E”1 | 83.2％ | 93.8％ | 2.8％ |
Table 4 table for recording lithium ion battery performance data
| Adhesive agent | Battery cell | 10C discharge capacity retention rate | Cycle capacity retention rate | Cell expansion rate |
| Example 1 | F1 | 92.3％ | 92.6％ | 3.4％ |
| Example 2 | F2 | 91.5％ | 92.4％ | 3.7％ |
| Example 3 | F3 | 93.5％ | 91.8％ | 4.5％ |
| Example 4 | F4 | 90.8％ | 92.0％ | 3.9％ |
| Example 5 | F5 | 92.0％ | 92.3％ | 3.8％ |
| Example 6 | F6 | 94.3％ | 90.5％ | 5.5％ |
| Example 7 | F7 | 90.0％ | 90.5％ | 5.5％ |
| Example 8 | F8 | 92.5％ | 92.4％ | 3.5％ |
| Example 9 | F9 | 92.4％ | 92.4％ | 3.3％ |
| Example 10 | F10 | 92.3％ | 92.5％ | 3.3％ |
| Comparative example 1 | F11 | 85.6％ | 82.8％ | 8.2％ |
| Comparative example 2 | F12 | 86.7％ | 81.4％ | 9.3％ |
| Comparative example 3 | F13 | 87.6％ | 80.0％ | 10.4％ |
| Comparative example 4 | F14 | 85.8％ | 82.0％ | 8.0％ |
| Comparative example 5 | F15 | 85.4％ | 81.8％ | 8.2％ |
From the results of tables 3 and 4, it can be seen that the sodium ion battery and the lithium ion battery using the phosphate ester copolymerization modified binder of the present invention exhibit significant advantages in high-rate discharge, cycle capacity retention rate and cell expansion rate, which can be attributed to the strong bonding effect between the phosphate ester copolymerization modified binder and the current collector being able to effectively maintain the stable pole piece structure.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An adhesive, wherein the adhesive comprises a copolymer, and monomers of the copolymer comprise a matrix monomer and a monomer shown in a formula (1);
in the formula (1), R 1 、R 2 、R 3 、R 4 、R 5 The same or different are independently selected from H or alkyl, and n is an integer between 1 and 3.
2. The adhesive of claim 1 wherein R 1 、R 2 、R 3 、R 4 、R 5 Identical or different, independently of one another, from H or C 1-6 An alkyl group; preferably, R 1 、R 2 、R 3 、R 4 、R 5 Identical or different, independently of one another, from H or C 1-3 An alkyl group; also preferably, R 1 、R 2 、R 3 、R 4 、R 5 The same or different, independently of one another, from H, methyl, ethyl or propyl.
3. The adhesive according to claim 1 or 2, wherein the monomers forming the copolymer further comprise functional monomers;
the functional monomer comprises at least one of acrylonitrile, (methyl) acrylamide, (methyl) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-hydroxymethyl (methyl) acrylamide, N-dimethylacrylamide, sodium p-styrenesulfonate, sodium vinylsulfonate, sodium allylsulfonate, sodium 2-methylallylsulfonate, sodium ethylacrylate sulfonate, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
4. A binder as claimed in any one of claims 1 to 3, wherein the matrix monomer comprises butadiene and styrene; alternatively, the matrix monomer comprises styrene and at least one of the following compounds: alkyl (meth) acrylates and hydroxyalkyl (meth) acrylates; alternatively, the base monomer includes at least one of an alkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate.
Preferably, the alkyl (meth) acrylate includes at least one of butyl methacrylate, butyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-octyl methacrylate, n-octyl acrylate, isooctyl methacrylate, isooctyl acrylate, dodecyl methacrylate. The hydroxyalkyl (meth) acrylate comprises at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate.
5. The binder according to any one of claims 1 to 4, wherein the mass of the monomer represented by formula (1) is 0.1 to 10% by weight based on the total mass of the copolymer;
and/or, the mass of the matrix monomer accounts for 90-99.9 wt% of the total mass of the copolymer.
6. The binder of claim 3 or 4, wherein the functional monomer is 0-10wt% of the total mass of the copolymer.
7. A negative electrode sheet comprising the binder of any one of claims 1-6.
8. The negative electrode sheet according to claim 7, wherein the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer on at least one side surface of the negative electrode current collector, the negative electrode active material layer comprising the above binder, the mass of the binder accounting for 0.5 to 20wt% of the total mass of the negative electrode active material layer.
Preferably, the single-sided surface density of the negative electrode sheet is 3-18mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the negative plate has a compacted density of 0.8-1.7g/cm 3 。
Preferably, the adhesion between the anode active material layer and the anode current collector is 5 to 20N/m.
Preferably, the negative electrode sheet further includes a negative electrode active material including at least one of natural graphite, artificial graphite, mesophase carbon microspheres, soft carbon, hard carbon, a silicon-based material, and a tin-based material.
Preferably, the hard carbon has a specific surface area of 2-9m 2 And/or the hard carbon has a particle diameter Dv50 of 4 to 10 μm.
9. A battery comprising the binder of any one of claims 1-6 and/or the negative electrode sheet of claim 7 or 8.
10. The battery of claim 9, wherein the battery is a sodium ion battery or a lithium ion battery.
Preferably, the negative current collector in the negative plate in the lithium ion battery comprises at least one of a single-smooth-surface copper foil, a double-smooth-surface copper foil and a porous copper foil.
Preferably, the negative electrode current collector in the negative electrode sheet in the sodium ion battery comprises at least one of a single-smooth aluminum foil, a double-smooth aluminum foil or a porous aluminum foil.
Preferably, the negative electrode sheet in the sodium ion battery further includes a negative electrode active material including hard carbon.
Preferably, the hard carbon has a specific surface area of 2-9m 2 And/or the hard carbon has a particle diameter Dv50 of 4 to 10 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311762753.1A CN117736668A (en) | 2023-12-20 | 2023-12-20 | Adhesive, negative plate comprising adhesive and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311762753.1A CN117736668A (en) | 2023-12-20 | 2023-12-20 | Adhesive, negative plate comprising adhesive and battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117736668A true CN117736668A (en) | 2024-03-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311762753.1A Pending CN117736668A (en) | 2023-12-20 | 2023-12-20 | Adhesive, negative plate comprising adhesive and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117736668A (en) |
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2023
- 2023-12-20 CN CN202311762753.1A patent/CN117736668A/en active Pending
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