CN113773435A - Mussel bionic polymer, silicon-carbon negative electrode binder, silicon-carbon negative electrode material and application - Google Patents
Mussel bionic polymer, silicon-carbon negative electrode binder, silicon-carbon negative electrode material and application Download PDFInfo
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- CN113773435A CN113773435A CN202010522606.7A CN202010522606A CN113773435A CN 113773435 A CN113773435 A CN 113773435A CN 202010522606 A CN202010522606 A CN 202010522606A CN 113773435 A CN113773435 A CN 113773435A
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 118
- 229920000642 polymer Polymers 0.000 title claims abstract description 91
- 241000237536 Mytilus edulis Species 0.000 title claims abstract description 85
- 235000020638 mussel Nutrition 0.000 title claims abstract description 85
- 239000011883 electrode binding agent Substances 0.000 title claims abstract description 33
- 239000011664 nicotinic acid Substances 0.000 title abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims description 59
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical group NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 58
- 230000003592 biomimetic effect Effects 0.000 claims description 56
- 229920001577 copolymer Polymers 0.000 claims description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 30
- 229960003638 dopamine Drugs 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 23
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- 238000000034 method Methods 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
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- 238000007334 copolymerization reaction Methods 0.000 claims description 12
- 238000010526 radical polymerization reaction Methods 0.000 claims description 11
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
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- 238000002156 mixing Methods 0.000 claims description 6
- 239000011884 anode binding agent Substances 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-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
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims description 3
- 229960004502 levodopa Drugs 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 21
- 229920002125 Sokalan® Polymers 0.000 description 20
- 239000004584 polyacrylic acid Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 239000002002 slurry Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000006138 lithiation reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000006182 cathode active material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000003013 cathode binding agent Substances 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
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- 239000003999 initiator Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 239000002388 carbon-based active material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a mussel bionic polymer, a silicon-carbon negative electrode binder, a silicon-carbon negative electrode material and application thereof. The structural formula of the mussel bionic polymer is shown as a formula (I), wherein m is more than or equal to 5 and less than or equal to 500, n is more than or equal to 5 and less than or equal to 500, x is more than or equal to 5 and less than or equal to 200, and m, n and x are integers. The mussel bionic polymer has the advantages ofThe silicon-carbon negative electrode active material has strong hydrophobicity, and when the silicon-carbon negative electrode active material is used as a component of the silicon-carbon negative electrode binder, the interface bonding force with the silicon-carbon negative electrode active material which is hydrophobic is high, and the structure of the silicon-carbon negative electrode active material simultaneously has carboxyl and flexible structures, so that the bonding force with the silicon-carbon negative electrode material is improved, the volume expansion of the silicon-carbon negative electrode active material is restrained and relieved, the silicon-carbon negative electrode active material is prevented from being powdered, and the cycle performance of the obtained silicon-carbon negative electrode material, the negative electrode and the lithium ion battery is improved;
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a mussel bionic polymer, a silicon-carbon negative electrode binder, a silicon-carbon negative electrode material and application thereof.
Background
With the demand of new energy automobiles, communication and portable equipment and the like for high capacity and high endurance capacity of lithium ion batteries, the development of lithium ion batteries reaches a bottleneck. For the negative electrode, the currently widely used negative electrode materials are various carbon materials mainly comprising graphite, the theoretical capacity of the carbon materials is only 372mAh/g, and the carbon materials are close to the theoretical capacity in the practical application process, so that the higher capacity requirement is difficult to achieve. Therefore, research on the high-specific-capacity negative electrode active material is great, wherein the theoretical capacity of the silicon carbon material is far higher than that of the graphite carbon material, 4200mAh/g can be achieved, resources are relatively rich, and the silicon carbon material is a main choice of a next-generation novel negative electrode material. However, the silicon-carbon material is accompanied by huge volume change in the process of lithium intercalation and deintercalation, which causes pulverization of the silicon-carbon active material and cracking of a conductive network, and finally causes rapid capacity fading. At this time, a strong binder is required to maintain the stability of the composite electrode coating during charge and discharge. The silicon-carbon negative electrode binder is a substance for adhering particles such as a silicon-carbon composite material and a conductive agent to a current collector, and accounts for 2% -12% of the negative electrode slurry.
Polyacrylic acid is a water-soluble chain polymer, can form polyacrylate with a plurality of metal ions, such as sodium polyacrylate, and the sodium polyacrylate is easily soluble in water, has a thickening effect, and can be used as a thickener of lithium ion battery slurry. Molecular chains of polyacrylic acid and salts thereof also have a plurality of oxygen-containing groups (-COOH), which can form hydrogen bond action with the surface of the silicon-carbon active material, endow the active particles with stronger binding force with a current collector, simultaneously have the function of relieving the volume expansion of the silicon-based material, can improve the cycle performance of the battery, prolong the service life of the battery, and have been applied to silicon-carbon cathodes of lithium ion batteries. However, the adhesion of the polyacrylic acid binder used in commercial industry is mainly due to van der waals force and carboxyl, and since the surface group content of the silicon-carbon negative electrode material is limited and the polyacrylic acid is a rigid linear polymer chain as a whole, when the volume of the silicon-carbon negative electrode material expands to a certain extent, the adhesion effect of the polyacrylic acid binder is poor, and the silicon-carbon negative electrode material still suffers from chalking.
Disclosure of Invention
The invention aims to provide a mussel bionic polymer, a silicon-carbon negative electrode binder, a silicon-carbon negative electrode material and application thereof, and aims to solve the technical problems that the existing polyacrylic acid binder has poor binding effect on a silicon-carbon negative electrode active material and the silicon-carbon negative electrode active material is easy to be powdered.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a mussel biomimetic polymer, which has a structural formula shown as a formula (I):
wherein m is more than or equal to 5 and less than or equal to 500, n is more than or equal to 5 and less than or equal to 500, x is more than or equal to 5 and less than or equal to 200, and m, n and x are integers.
The invention also provides a preparation method of the mussel biomimetic polymer, which comprises the following steps:
providing an acrylic monomer, an acrylic ester soft monomer and a compound containing a dopamine structure;
carrying out free radical polymerization reaction on the acrylic acid monomer and the acrylate soft monomer to generate polyacrylic acid-acrylate copolymer;
carrying out copolymerization grafting reaction on the polyacrylic acid-acrylate copolymer and the compound containing the dopamine structure to obtain a mussel bionic polymer;
the structural formula of the mussel biomimetic polymer is shown as the formula (I):
the structural formula of the polyacrylic acid-acrylate copolymer is shown as the formula (II):
wherein m is more than or equal to 5 and less than or equal to 500, n is more than or equal to 5 and less than or equal to 500, x is more than or equal to 5 and less than or equal to 200, and m, n and x are integers.
In a preferred embodiment of the present invention, the acrylate soft monomer is at least one selected from butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate. In a preferred embodiment of the present invention, the compound containing a dopamine structure is selected from dopamine and/or levodopa.
In a preferred embodiment of the present invention, in the step of polymerizing the acrylic acid monomer and the soft acrylate monomer, a molar ratio of the soft acrylate monomer to the acrylic acid monomer is 0.35 to 2.76.
In a preferred embodiment of the present invention, in the step of grafting the compound containing a dopamine structure to the polyacrylic acid-acrylate copolymer, a molar ratio of the polyacrylic acid-acrylate copolymer to the compound containing a dopamine structure is (2-5): 714.
The invention also provides a silicon-carbon negative electrode binder which comprises the mussel biomimetic polymer or the mussel biomimetic polymer prepared by the preparation method of the mussel biomimetic polymer.
The invention further provides a silicon-carbon negative electrode material which comprises the silicon-carbon negative electrode binder.
In another aspect, the present invention provides a method for preparing a silicon-carbon negative electrode material, which comprises the following steps:
providing a silicon-carbon negative electrode active material, a silicon-carbon negative electrode binder, a conductive agent and a solvent;
mixing the silicon-carbon negative electrode binder with the solvent to obtain a glue solution;
mixing the glue solution with the silicon-carbon negative electrode active material and the conductive agent to obtain the silicon-carbon negative electrode material;
wherein, the silicon-carbon negative electrode binder comprises the mussel biomimetic polymer or the mussel biomimetic polymer prepared by the preparation method of the mussel biomimetic polymer.
The invention also provides a negative electrode which comprises the silicon-carbon negative electrode material or the silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material.
In a final aspect, the invention provides a lithium ion battery, which comprises the negative electrode.
The mussel bionic polymer has carboxyl in the chemical structure, and can react with silicon oxygen groups and silicon hydroxyl groups on the surface of a silicon-carbon negative active material to form hydrogen bonds and covalent ester bonds, so that the mussel bionic polymer has strong binding force with the silicon-carbon negative active material, and the formation of the covalent ester bonds also restrains and relieves the volume expansion of the silicon-carbon negative active material, so that the mussel bionic polymer can keep the electrical contact between silicon and carbon in the lithiation/delithiation process, and further improves the cycle performance and the conductivity of the silicon-carbon negative active material; secondly, the whole polyacrylic acid is a rigid linear macromolecular chain, and the mussel biomimetic polymer has high modulus and good flexibility by introducing a flexible structure, so that the silicon-carbon negative active material can be further prevented from being powdered; thirdly, the mussel biomimetic polymer has a catechol structure with wet adhesion resistance, and phenolic hydroxyl groups on the catechol structure can be in contact with silicon surfaces in the silicon-carbon negative electrode active material, so that the binding force is enhanced; finally, the silicon-carbon negative electrode material is subjected to high-temperature treatment, the surface of the silicon-carbon negative electrode material is hydrophobic, and the mussel biomimetic polymer also has certain hydrophobicity, so that the mussel biomimetic polymer is more compatible with the interface between the silicon-carbon negative electrode active materials, and the binding force between the silicon-carbon negative electrode active materials and the mussel biomimetic polymer can be further improved.
According to the preparation method of the mussel bionic polymer, free radical polymerization reaction is carried out on an acrylic acid monomer and an acrylate soft monomer to obtain a polyacrylic acid-acrylate copolymer with a carboxyl and flexible structure, then copolymerization grafting reaction is carried out on the polyacrylic acid-acrylate copolymer and a compound containing a dopamine structure, a catechol structure is introduced into a branched chain of the polyacrylic acid-acrylate copolymer, contact points can be increased, the length and flexibility of the branched chain are lengthened, the glass transition temperature of the polyacrylic acid-acrylate copolymer is further reduced, and the fluidity and wettability of the obtained silicon-carbon negative electrode adhesive are improved. The preparation method of the mussel biomimetic polymer is simple and easy to implement, the reaction process is easy to control, and the large-scale production is favorably realized.
The silicon-carbon negative electrode binder comprises the mussel bionic polymer or the mussel bionic polymer prepared by the preparation method of the mussel bionic polymer. The mussel bionic polymer has strong binding force with the silicon-carbon negative electrode active material, can restrict and relieve volume expansion of the silicon-carbon negative electrode active material, can keep electric contact between silicon and carbon in the lithiation/delithiation process, and prevents the silicon-carbon negative electrode active material from being powdered, so that the silicon-carbon negative electrode binder also has the effects, and can improve the cycle performance and the conductivity of the silicon-carbon active negative electrode material.
The silicon-carbon negative electrode material comprises the silicon-carbon negative electrode binder. The silicon-carbon cathode binder has good binding force with the silicon-carbon cathode active material, can restrict and relieve the volume expansion of the silicon-carbon cathode active material, can keep the electrical contact between silicon and carbon in the lithiation/delithiation process, and prevents the silicon-carbon cathode active material from being powdered, so the silicon-carbon cathode material has good cycle performance and conductivity.
According to the preparation method of the silicon-carbon negative electrode material, the glue solution containing the silicon-carbon negative electrode binder is prepared firstly, and then the glue solution, the silicon-carbon negative electrode active material and the conductive agent are mixed, so that the prepared silicon-carbon negative electrode material is good in dispersibility and high in solid content, and the preparation process is simple and easy to implement.
The negative electrode comprises the silicon-carbon negative electrode material or the silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material. The silicon-carbon negative electrode material has good cycle performance and conductivity, so the negative electrode of the invention also has good cycle performance and conductivity.
The lithium ion battery comprises the cathode. The negative electrode has good cycle performance and conductivity, so the lithium ion battery also has good cycle performance and conductivity.
Drawings
FIG. 1 is a nuclear magnetic spectrum of P (BA-co-AA) obtained in example 3 of the present invention;
FIG. 2 is an IR spectrum of dopamine, P (BA-co-AA) and P (BA-co-AA) -g-Dopa in example 2 of the present invention;
FIG. 3 is a DSC curve of P (BA-co-AA) obtained in examples 1-5 of the present invention;
FIG. 4 is a DSC curve of P (BA-co-AA) -g-Dopa obtained in examples 1-5 of the present invention;
FIG. 5 is a graph comparing the contact angle test results of Experimental example 6 of the present invention;
FIG. 6 shows the results of the peel force test of Experimental example 7 of the present invention;
FIG. 7 is a comparison of the morphology change of the electrode sheets obtained in example 9 of the present invention and the comparative example before and after 100 charge-discharge cycles;
FIG. 8 is a graph showing the cycle life of batteries fabricated from the electrode sheets obtained in example 9 of the present invention and comparative example.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as including the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a mussel bionic polymer, which has a structural formula shown as a formula (I):
wherein m is more than or equal to 5 and less than or equal to 500, n is more than or equal to 5 and less than or equal to 500, x is more than or equal to 5 and less than or equal to 200, and m, n and x are integers.
The mussel bionic polymer has carboxyl in the chemical structure, and can react with silicon oxygen groups and silicon hydroxyl groups on the surface of a silicon-carbon negative active material to form hydrogen bonds and covalent ester bonds, so that the mussel bionic polymer has strong binding force with the silicon-carbon negative active material, and the formation of the covalent ester bonds also restrains and relieves the volume expansion of the silicon-carbon negative active material, so that the mussel bionic polymer can keep the electrical contact between silicon and carbon in the lithiation/delithiation process, and further improves the cycle performance and the conductivity of the silicon-carbon negative active material; secondly, the polyacrylic acid is integrally a rigid linear polymer chain, and the silicon-carbon negative electrode binder has high modulus and good flexibility by introducing a flexible structure, so that the silicon-carbon negative electrode active material can be further prevented from being powdered; thirdly, the mussel biomimetic polymer has a catechol structure with wet adhesion resistance, and phenolic hydroxyl groups on the catechol structure can be in contact with silicon surfaces in the silicon-carbon negative electrode active material, so that the binding force is enhanced; finally, the silicon-carbon negative electrode material is subjected to high-temperature treatment, the surface of the silicon-carbon negative electrode material is hydrophobic, and the mussel biomimetic polymer also has strong hydrophobicity, so that the mussel biomimetic polymer is more compatible with the interface between the silicon-carbon negative electrode active materials, and the binding force between the silicon-carbon negative electrode active materials and the mussel biomimetic polymer can be further improved.
The embodiment of the invention also provides a preparation method of the mussel bionic polymer, which comprises the following steps:
s1, providing an acrylic monomer, an acrylate soft monomer and a compound containing a dopamine structure;
s2, carrying out free radical polymerization reaction on an acrylic acid monomer and an acrylate soft monomer to generate a polyacrylic acid-acrylate copolymer;
s3, carrying out copolymerization grafting reaction on a polyacrylic acid-acrylate copolymer and a compound containing a dopamine structure to obtain a mussel bionic polymer;
wherein, the structural formula of the mussel biomimetic polymer is shown as the formula (I):
the structural formula of the polyacrylic acid-acrylate copolymer is shown as the formula (II):
wherein m is more than or equal to 5 and less than or equal to 500, n is more than or equal to 5 and less than or equal to 500, x is more than or equal to 5 and less than or equal to 200, and m, n and x are integers.
According to the preparation method of the mussel bionic polymer, free radical polymerization reaction is carried out on an acrylic acid monomer and an acrylate soft monomer to obtain a polyacrylic acid-acrylate copolymer with a carboxyl and flexible structure, then copolymerization grafting reaction is carried out on the polyacrylic acid-acrylate copolymer and a compound containing a dopamine structure, a catechol structure is introduced into a branched chain of the polyacrylic acid-acrylate copolymer, contact points can be increased, the length and flexibility of the branched chain are lengthened, the glass transition temperature of the polyacrylic acid-acrylate copolymer is further reduced, and the fluidity and wettability of the obtained silicon-carbon negative electrode adhesive are improved. The preparation method of the mussel biomimetic polymer is simple and easy to implement, the reaction process is easy to control, and the large-scale production is favorably realized.
In S1, the acrylate soft monomer is selected as the raw material for synthesizing the mussel biomimetic polymer, so that a flexible structure can be provided for the obtained mussel biomimetic polymer, and the obtained mussel biomimetic polymer has high modulus and good flexibility, thereby preventing the silicon carbon negative electrode active material from being powdered. In some embodiments, the acrylate soft monomer is selected from at least one of butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, and these compounds have lower glass transition temperatures, which can improve the flexibility of the obtained mussel biomimetic polymer and make it have better elongation at break under high stress.
The acrylic monomer can enable the obtained mussel biomimetic polymer to have carboxyl, so that the mussel biomimetic polymer reacts with silicon oxygen groups and silicon hydroxyl groups on the surface of the silicon-carbon negative active material to form hydrogen bonds and covalent ester bonds, and meanwhile, the formation of the covalent ester bonds also restrains and relieves the volume expansion of the silicon-carbon negative active material, and the electric contact between silicon and carbon can be kept in the lithiation/delithiation process.
The compound containing dopamine is used as a raw material for synthesizing the mussel biomimetic polymer, and can provide a catechol structure for the obtained mussel biomimetic polymer so as to enhance the binding force between the mussel biomimetic polymer and the silicon-carbon negative electrode active material. In some embodiments, the dopamine-containing compound is selected from dopamine and/or levodopa for amidation with an acrylic monomer starting material.
S2 is polyacrylic acid-acrylic ester copolymer produced by free radical polymerization of acrylic acid monomer and acrylic ester soft monomer. By optimizing the molar ratio between the two monomers, the glass transition temperature of the resulting polyacrylic acid-acrylate copolymer can be adjusted. In some embodiments, the molar ratio of acrylate soft monomer to acrylic acid monomer is controlled to be 0.35 to 2.76 to improve the flow and wetting properties of the resulting polyacrylic acid-acrylate copolymer.
In some embodiments, the chain initiation reaction is the slowest since the free radical polymerization reaction is the process of chain initiation, chain growth, chain termination. By adding the initiator, molecules with high activation energy can be formed, and the chain initiation reaction is accelerated. Among them, Azobisisobutyronitrile (AIBN) is preferably used as an initiator for the free radical polymerization reaction of an acrylic monomer and an acrylic ester soft monomer, and has the advantages of stable decomposition reaction, generation of only one free radical and difficult induced decomposition. Correspondingly, as the decomposition temperature of the azobisisobutyronitrile, the temperature of the free radical polymerization reaction of the acrylic acid monomer and the acrylate soft monomer is adjusted to 50 ℃ to 70 ℃ (inclusive). Specifically, typical but not limiting reaction temperatures are 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃.
And S3 is to perform copolymerization grafting reaction on the polyacrylic acid-acrylate copolymer obtained in S2 and a compound containing a dopamine structure so as to introduce a catechol structure into a polyacrylic acid-acrylate copolymer system, increase contact points and change the mechanical strength, elasticity and viscosity of the mussel biomimetic polymer. The glass transition temperature of the obtained mussel biomimetic polymer can be further adjusted by optimizing the molar ratio between the polyacrylic acid-acrylate copolymer and the compound containing a dopamine structure. In some embodiments, the molar ratio of polyacrylic acid-acrylate copolymer to dopamine structure-containing compound is controlled at (2-5):714, such that the resulting mussel biomimetic polymer has the correct flowability and wettability for use as a binder.
Since the above copolymerization grafting reaction causes amidation reaction between acrylic acid and the dopamine structure-containing compound, in some embodiments, the dopamine structure-containing compound is grafted to the polyacrylic acid-acrylate copolymer using 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC · HCl) and 1-Hydroxybenzotriazole (HOBT) to obtain the mussel biomimetic polymer.
Correspondingly, the embodiment of the invention provides a silicon-carbon negative electrode binder, which comprises the mussel biomimetic polymer or the mussel biomimetic polymer prepared by the preparation method of the mussel biomimetic polymer.
The silicon-carbon negative electrode binder comprises the mussel bionic polymer or the mussel bionic polymer prepared by the preparation method of the mussel bionic polymer. The mussel bionic polymer has strong binding force with the silicon-carbon negative electrode active material, can restrict and relieve volume expansion of the silicon-carbon negative electrode active material, can keep electric contact between silicon and carbon in the lithiation/delithiation process, and prevents the silicon-carbon negative electrode active material from being powdered, so that the silicon-carbon negative electrode binder also has the effects, and can improve the cycle performance and the conductivity of the silicon-carbon active negative electrode material.
Correspondingly, the embodiment of the invention also provides a silicon-carbon anode material which comprises the silicon-carbon anode binder.
The silicon-carbon negative electrode material comprises the silicon-carbon negative electrode binder. The silicon-carbon cathode binder has good binding force with the silicon-carbon cathode active material, can restrict and relieve the volume expansion of the silicon-carbon cathode active material, can keep the electrical contact between silicon and carbon in the lithiation/delithiation process, and prevents the silicon-carbon cathode active material from being powdered, so the silicon-carbon cathode material has good cycle performance and conductivity.
It is to be understood that in some embodiments, the silicon carbon anode material may include, but is not limited to, a silicon carbon anode active material, a conductive agent, a solvent, and the like, in addition to the silicon carbon anode binder.
In some embodiments, the silicon carbon anode binder comprises 0.5% to 15% by weight of the silicon carbon anode material, based on 100% by weight of the total silicon carbon anode material.
Correspondingly, the embodiment of the invention also provides a preparation method of the silicon-carbon anode material, which comprises the following steps:
s4, providing a silicon-carbon negative electrode active material, a silicon-carbon negative electrode binder, a conductive agent and a solvent;
s5, mixing the silicon-carbon negative electrode binder with a solvent to obtain a glue solution;
s6, mixing the glue solution with a silicon-carbon negative electrode active material and a conductive agent to obtain a silicon-carbon negative electrode material;
wherein, the silicon-carbon negative electrode binder comprises the mussel biomimetic polymer or the mussel biomimetic polymer prepared by the preparation method of the mussel biomimetic polymer.
According to the preparation method of the silicon-carbon negative electrode material, the glue solution containing the silicon-carbon negative electrode binder is prepared firstly, and then the glue solution, the silicon-carbon negative electrode active material and the conductive agent are mixed, so that the prepared silicon-carbon negative electrode material is good in dispersibility and high in solid content, and the preparation process is simple and easy to implement.
It should be noted that, although the steps S4-S6 describe the preparation process of the silicon-carbon anode material in a specific order, it is not required that the steps are necessarily performed in the specific order, and the steps may be performed simultaneously or sequentially according to actual situations.
In S4, the embodiment of the present invention does not particularly require specific selection of the silicon-carbon negative electrode active material, and any silicon-carbon negative electrode active material having electrochemical properties may be used as a raw material for preparing the silicon-carbon negative electrode material of the embodiment of the present invention.
The conductive agent has good conductivity, and plays a role in collecting micro current, reducing the contact resistance of the electrode and improving the migration rate of lithium ions in the silicon-carbon negative electrode active material between the silicon-carbon negative electrode active material and the current collector. In some embodiments, a combination of Carbon Nanotubes (CNTs) and other conventional conductive agents is preferred as the conductive agent.
The embodiment of the present invention does not particularly require specific selection of a solvent as long as it can be used to dissolve the silicon carbon anode binder and/or the conductive agent.
In S5, the silicon-carbon cathode binder and the solvent are mixed to obtain a glue solution, so that the silicon-carbon cathode binder can be dispersed in the solvent, the obtained glue solution has good stability, and a certain viscosity is provided for the silicon-carbon cathode material.
In S6, the glue solution is mixed with the silicon-carbon negative electrode active material and the conductive agent, so that the silicon-carbon negative electrode binder can play a binding role in the silicon-carbon negative electrode material, and the volume expansion of the silicon-carbon negative electrode active material is relieved.
Because the carbon nano tube has the characteristic of being difficult to disperse, in some embodiments, the carbon nano tube is preferably mixed with the glue solution, and then other conductive agents and the silicon-carbon negative electrode active material are sequentially added, so that the carbon nano tube is uniformly dispersed in the silicon-carbon negative electrode material, and the conductivity of the obtained silicon-carbon negative electrode material is improved.
The solid content is related to the particle size, the flowability, the viscosity and the like of the silicon-carbon negative electrode material. Within a certain viscosity range, the stability of the silicon-carbon negative electrode material can be improved by optimizing the solid content of the silicon-carbon negative electrode material, and the subsequent coating is facilitated. In some embodiments, the solid content of the silicon-carbon negative electrode material is preferably adjusted to 50%, and the fineness is controlled to be below 30 μm.
Correspondingly, the embodiment of the invention also provides a negative electrode, which comprises the silicon-carbon negative electrode material or the silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material.
The negative electrode comprises the silicon-carbon negative electrode material or the silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material. The silicon-carbon negative electrode material has good cycle performance and conductivity, so the negative electrode of the invention also has good cycle performance and conductivity.
Correspondingly, the embodiment of the invention also provides a lithium ion battery which comprises the negative electrode.
The lithium ion battery comprises the cathode. The negative electrode has good cycle performance and conductivity, so the lithium ion battery also has good cycle performance and conductivity.
In order to clearly understand the details and operations of the above embodiments of the present invention by those skilled in the art, and to obviously show the advanced performance of the mussel biomimetic polymer, the silicon-carbon negative electrode material and the preparation method thereof, the silicon-carbon negative electrode binder, the negative electrode and the lithium ion battery according to the embodiments of the present invention, the above technical solutions are illustrated by a plurality of examples.
Example 1
A mussel biomimetic polymer, wherein the preparation method comprises the following steps:
(1) synthesis of P (BA-co-AA): selecting an acrylic monomer (AA) and a butyl acrylate monomer (BA), carrying out free radical polymerization to obtain a polyacrylic acid-acrylic ester copolymer, marking as P (BA-co-AA), adding an initiator AIBN in the reaction process, wherein the reaction temperature is 60 ℃, and the molar ratio of the butyl acrylate monomer to the acrylic acid monomer is shown in Table 1;
(2) copolymerization grafting: under the protection of nitrogen, dissolving P (BA-co-AA) and dopamine in a mixed solution of dichloromethane and N-methylpyrrolidone (1:1), adding EDC & HCl, HOBT and triethylamine, reacting at room temperature for 12h, repeatedly washing the obtained reaction solution with N-hexane after the reaction is finished, and then drying in vacuum at 50 ℃ for 24h to obtain the mussel biomimetic polymer, which is marked as P (BA-co-AA) -g-Dopa, wherein the reaction raw materials and the content are shown in Table 2.
Example 2
This example is substantially the same as example 1, except that the molar ratio of the butyl acrylate monomer to the acrylic acid monomer in step (1) and the reaction raw materials and contents in step (2) are as shown in tables 1 and 2.
Example 3
This example is substantially the same as example 1, except that the molar ratio of the butyl acrylate monomer to the acrylic acid monomer in step (1) and the reaction raw materials and contents in step (2) are as shown in tables 1 and 2.
Example 4
This example is substantially the same as example 1, except that the molar ratio of the butyl acrylate monomer to the acrylic acid monomer in step (1) and the reaction raw materials and contents in step (2) are as shown in tables 1 and 2.
Example 5
This example is substantially the same as example 1, except that the molar ratio of the butyl acrylate monomer to the acrylic acid monomer in step (1) and the reaction raw materials and contents in step (2) are as shown in tables 1 and 2.
TABLE 1 examples 1-5 molar ratio of butyl acrylate monomer to acrylic acid monomer in the Synthesis of P (BA-co-AA) step
TABLE 2 examples 1-5 Cografting Steps, reactants and amounts
In Table 2, the mixed solution is prepared from dichloromethane/NMP according to the mass ratio of 1: 1.
Example 6
(3) Preparing glue: 10g P (BA-co-AA) -g-Dopa prepared in example 1 was dissolved in 100g of NMP and stirred at 80 ℃ for 2h to obtain a uniform gum solution;
(4) preparing a silicon-carbon negative electrode material: adding the glue solution into a stirring kettle, adding 5% of CNTs slurry with dry powder proportion, and stirring for 1h at the rotating speed of 1000; then adding a conductive agent Sp with a dry powder ratio of 5%, and stirring for 30min at a rotating speed of 1000; adding the SiC450 with the proportion of the residual dry powder of 80g for 2 times; adding 50% of the dry powder for the first time, adding NMP to adjust the solid content of the slurry to 65%, stirring for 2h at 1200 rpm, and then testing the fineness of the slurry; adding the rest positive active substances, adding NMP to adjust the solid content of the slurry to 50%, and continuing stirring for 2 h; testing the solid content and the fineness, if the fineness is less than 30, vacuumizing and removing bubbles, and then temporarily storing for later coating; if the fineness of the slurry is higher than 30, continuously stirring for 30 min;
(5) coating: and (4) coating by using a small-sized laboratory coating machine to obtain the pole piece.
Example 7
This example is substantially the same as example 6 except that P (BA-co-AA) -g-Dopa prepared in example 2 was used in step (3).
Example 8
(3) Preparing glue: 10g P (BA-co-AA) -g-Dopa prepared in example 3 was dissolved in 100g of NMP and stirred at 80 ℃ for 3 hours to obtain a uniform gum solution;
(4) preparing a silicon-carbon negative electrode material: adding the glue solution into a stirring kettle, adding 2.5 percent of CNTs slurry with dry powder proportion at the rotating speed of 100Stirring for 1h at 0 ℃; then adding a conductive agent Sp with a dry powder ratio of 5%, and stirring for 30min at a rotating speed of 1000; SiO in a residual dry powder ratio of 80gX@ C450 was added in 2 portions; adding 50% of the dry powder for the first time, adding NMP to adjust the solid content of the slurry to 65%, stirring for 2h at 1200 rpm, and then testing the fineness of the slurry; adding the rest positive active substances, adding NMP to adjust the solid content of the slurry to 50%, and continuing stirring for 2 h; testing the solid content and the fineness, if the fineness is less than 30, vacuumizing and removing bubbles, and then temporarily storing for later coating; if the fineness of the slurry is higher than 30, continuously stirring for 30 min;
(5) coating: and (4) coating by using a small-sized laboratory coating machine to obtain the pole piece.
Example 9
This example is substantially the same as example 8 except that P (BA-co-AA) -g-Dopa prepared in example 4 was used in step (3).
Example 10
This example is substantially the same as example 8 except that P (BA-co-AA) -g-Dopa prepared in example 5 was used in step (3).
Comparative example
(i) Preparing glue: dissolving 10g of PAA in 100g of NMP, and stirring for 3 hours at the temperature of 50 ℃ to obtain uniform glue solution;
(ii) preparing a silicon-carbon negative electrode material: adding the glue solution into a stirring kettle according to the proportion of 2.5 percent of dry powder, adding 5 percent of CNTs slurry according to the proportion of the dry powder, and stirring for 1 hour at the rotating speed of 1000; then adding a conductive agent with a dry powder proportion of 5%, and stirring for 30 minutes at a rotating speed of 1000; adding SiOx @ C420 with the proportion of the remaining dry powder of 80g in 2 times; adding 50% of the dry powder for the first time, adding NMP to adjust the solid content of the slurry to 65%, stirring for 2h at 1200 turns, and then testing the fineness of the slurry. Adding the rest positive active substances, adding NMP to adjust the solid content of the slurry to 50%, and continuing stirring for 2 h; the solids content and fineness, e.g., fineness less than 30, are measured. After vacuumizing and removing bubbles, the slurry can be temporarily stored for coating. If the fineness of the slurry is higher than 30, stirring for 30 min.
(iii) Coating: and (4) coating by using a small-sized laboratory coating machine to obtain the pole piece.
The contents of each raw material and the solid contents of the obtained silicon carbon anode materials in examples 6 to 10 and comparative example are shown in table 3.
Table 3 contents of respective raw materials and solid contents of obtained silicon carbon negative electrode materials in examples 6 to 10 and comparative example
Experimental example 1
The nuclear magnetic resonance spectroscopy method detects the structure of the P (BA-co-AA) obtained in the example 3,1HNMR measurements were performed on a Bruker Avance III 400 NMR spectrometer with DMSO-d 6 as the solvent and Trimethylsilane (TMS) as the internal standard at a temperature of 20 ℃ and the results are shown in FIG. 1. As can be seen from fig. 1, a peak appearing around 2.0 to 2.4ppm is the last methyl group (1H, -CH-) on the backbone identified by a + c in P (BA/AA ═ 0.70); peaks around 1.4-1.6ppm for methylene (2H, -CH2-) on the backbone identified by b + d in P (BA-co-AA) (BA/AA ═ 0.70); peaks near 1.2-1.4ppm of the middle two methylene groups (2H, -CH2-) on the pendant butyl formate identified by f + g in P (BA/AA ═ 0.70); the peak at around 4.0ppm was found to be the methylene group (2H, -CH2-) ester-linked on the longer side group identified by e in P (BA-co-AA) (BA/AA ═ 0.70); appearing around 0.9ppm is the peak of methyl (3H, -CH3) at H in P (BA-co-AA) (BA/AA ═ 0.70); a peak of a carboxyl group (1H, -COOH) at i mark in P (BA-co-AA) (BA/AA ═ 0.70) appeared around 12.3 ppm; appearing around 2.5ppm is the DMSO solvent peak.
Experimental example 2
Taking example 2 as an example, the infrared spectra of the Dopa, the obtained P (BA-co-AA) and the obtained P (BA-co-AA) -g-Dopa used in example 2 are compared, and the detection method of the infrared spectra is as follows: paragon 1000 type infrared spectrometer (Perkin-Elmer company, USA), the polymer adopts solution coating method, the scanning range is 4000--1The results are shown in FIG. 2. As can be seen from fig. 2:
(a) infrared spectrum of Dopa at 1600cm-1，1500cm-1And 1450cm-1Characteristic peaks of benzene ring skeletons appear nearby; at 3400cm-1The characteristic peak of the stretching vibration of N-H appears; at 3200cm-1A strong absorption band is nearby and is a stretching vibration band of-OH; the bending vibration absorption peak of N-H appears at 1550cm-1Nearby; at 1740cm-1A strong absorption band is nearby, and is a C ═ O stretching vibration peak; at 2900cm-1And 1380cm-1The nearby absorption band indicates the existence of-CH3(ii) a At 1640cm-1A strong absorption peak appears nearby, namely C ═ C stretching vibration; at 2930cm-1Nearby absorption is-CH2-a stretching vibration peak; at 1230cm-1a-C-N-absorption peak appears nearby; at 1350cm-1An O-H in-plane bending vibration band with a phenolic hydroxyl group nearby; at 750-650 cm-1An O-H bond face of a phenolic hydroxyl group appears in the vicinity of the O-H bond face to form an external bending vibration absorption band.
(b) In the infrared spectrum of P (BA-co-AA) (BA/AA ═ 1.40), at 3400cm-1A wider absorption band is arranged nearby and is a-OH telescopic vibration band; at 1740cm-1A strong absorption band is nearby, and is a C ═ O stretching vibration peak; at 2900cm-1And 1380cm-1The nearby absorption band indicates the existence of-CH3(ii) a At 2930cm-1Is absorbed by the site and is-CH2-an absorption peak; at 1300-1000cm-1Two absorption bands appear in the interval, which are C-O-C asymmetric stretching vibration bands. The C-O stretching vibration and the O-H in-plane deformation vibration are 1440-1395 cm-1And 1320-1210cm-1The interval has two absorption bands.
(c) In the infrared spectrum of P (BA-co-AA) -g-Dopa (BA/AA ═ 1.40), at 1600cm-1，1500cm-1And 1450cm-1Characteristic peaks of benzene ring skeletons appear nearby; at 3300cm-1A strong and wide absorption band is arranged nearby and is a-OH telescopic vibration band; at 1740cm-1A strong absorption band is nearby, and is a C ═ O stretching vibration peak; at 2900cm-1And 1380cm-1The nearby absorption band indicates the existence of-CH3(ii) a At 1640cm-1A strong absorption peak appears nearby, namely C-C bond stretching vibration; at 2930cm-1Is absorbed by the site and is-CH2-an absorption peak; at 1230cm-1Nearby occurrence of-C-N-getteringCollecting peaks; at 1350cm-1An O-H in-plane bending vibration band with a phenolic hydroxyl group nearby; at 750-650 cm-1An O-H bond surface external bending vibration absorption band of phenolic hydroxyl appears nearby; at 1300--1Two absorption bands appear in the interval, which is C-O-C asymmetric stretching vibration.
In combination with the above analyses (a) to (c), by comparing the IR spectra before and after grafting, it was found that P (BA-co-AA) -g-Dopa (BA/AA ═ 1.40) after grafting was at 1600cm-1，1500cm-1And 1450cm-1Characteristic peaks of benzene ring skeletons appear nearby, and the successful grafting of Dopa to P (BA-co-AA) (BA/AA is 1.40) is proved.
Experimental example 3
The molecular weights and distribution data of P (BA-co-AA) and polyacrylic acid (PAA) obtained in example 4 were analyzed by a Series 200 gel permeation chromatograph (Perkin-Elmer Co., U.S.A.) with a mobile phase of DMF containing 0.01mol/L lithium bromide, a sample solution concentration of 2mg/ml, a test temperature of 20 ℃ and a PS standard, and the results are shown in Table 4.
TABLE 4 molecular weights and distribution results of P (BA-co-AA) and polyacrylic acid obtained in example 4
As can be seen from table 4, the molecular weight of P (BA-co-AA) synthesized by us is closer to that of the conventional PAA (BA/AA ═ 0.47).
Experimental example 4
The sample size was about 5mg, as measured by a differential scanning calorimeter model Q2000 (TA Instruments, USA). Heating to 150 deg.C under nitrogen atmosphere (flow rate of 50ml/min) to eliminate heat history, scanning from 150 deg.C to-80 deg.C at 20 deg.C/min, holding for 3 min, and heating from-80 deg.C to 150 deg.C at 10 deg.C/min. In examples 1 to 5, the DSC curves and Tg values of P (BA-co-AA) obtained by radical copolymerization of butyl acrylate monomers and acrylic acid monomers in different molar ratios were analyzed, and the results are shown in FIG. 3 and Table 5.
TABLE 5 Tg values of P (BA-co-AA) obtained in examples 1-5
As can be seen from FIG. 3 and Table 5, as the acrylic acid content is increased, the crystallinity is gradually increased, and the glass transition temperature of the resulting P (BA-co-AA) polymer is also increased.
Experimental example 5
The sample size was about 5mg, as measured by a differential scanning calorimeter model Q2000 (TA Instruments, USA). Heating to 150 deg.C under nitrogen atmosphere (flow rate of 50ml/min) to eliminate heat history, scanning from 150 deg.C to-80 deg.C at 20 deg.C/min, holding for 3 min, and heating from-80 deg.C to 150 deg.C at 10 deg.C/min. In examples 1-5, the DSC curves and Tg values of P (BA-co-AA) -g-Dopa were obtained before and after copolymerization grafting of P (BA-co-AA) obtained by different molar ratios of butyl acrylate monomer to acrylic acid monomer, and the results are shown in FIG. 4 and Table 6.
TABLE 6 Tg values of P (BA-co-AA) obtained in examples 1-5 before and after the copolymerization grafting
As can be seen from FIG. 4 and Table 6, the Tg of the resulting P (BA-co-AA) -g-Dopa was reduced after the Dopa graft modification, probably because the graft modification of Dopa to the pendant group of P (BA-co-AA) results in longer pendant chain length, increased flexibility and thus smaller Tg, which is beneficial for increasing the fluidity and wettability when used as a binder.
Experimental example 6
Contact angle test (CA) analysis: the glass slide is cleaned by ethanol and acetone, 1 piece of the glass slide is respectively immersed in 5mg/mL ethanol solution of P (BA-co-AA) and P (BA-co-AA) -g-Dopa obtained in example 1 for 1h, and then the glass slide is placed under vacuum for 72h, so that the P (BA-co-AA) and the P (BA-co-AA) -g-Dopa are completely dissolved in the ethanol solution, and the effect is that the polymer contact angle is not allowed to block the needle head, and the test result is prevented from being influenced. The analysis was carried out using a contact angle measuring apparatus of the type OCA20 from DataPhysics, Germany, all measurements being carried out at room temperature. The static contact angle was measured by the solid-drop method using a drop volume of 4.0. mu.L and a flow rate of 1.00. mu.L/s. The contact angle values given herein are the average of three measurements, all within ± 4 ° of standard deviation. The results are shown in FIG. 5.
As can be seen from fig. 5, the commercially available polyacrylic acid has a contact angle of 8 ° due to its extreme hydrophilicity; the contact angle of P (BA-co-AA) obtained in example 1 was 83 DEG due to the hydrophobic group containing butyl acrylate; after grafting the dopamine, due to the hydrophilicity of the catechol group of the dopamine, the contact angle of the grafted P (BA-co-AA) -g-Dopa is 67 degrees.
Experimental example 7
180 ° peel force test: the pole pieces coated with the silicon-carbon negative electrode materials obtained in examples 6 to 10 and comparative example were rolled for later use (the compaction density was 1.55 g/cm)3) Then, a 3M tape (6.5N) having a width of about 25.4mm was applied to the plate and a 180 ℃ peel test was carried out on a tensile machine at a speed of 10 mm/min. The test results are shown in fig. 6.
As can be seen from FIG. 6, examples 6 to 10 using P (BA-co-AA) -g-Dopa as the binder for the silicon-carbon negative electrode had bonding strengths of 0.445N/cm, 0.56N/cm, 0.655N/cm, 0.815N/cm and 0.54N/cm, respectively. While the comparative example used PAA as the binder and had an adhesive strength of 0.36N/cm. It can be seen that the pole piece bonding strength using P (BA-co-AA) -g-Dopa is significantly higher than that of PAA because the commercial PAA bonding effect is mainly due to van der waals force and carboxyl group, but since the silicon carbon surface group content is limited and the polyacrylic acid is rigid as a whole, powdering still occurs when the volume expands to a certain extent; due to the existence of catechol groups, the P (BA-co-AA) -g-Dopa has a better bonding effect with a silicon-carbon negative electrode active material and a metal current collector; meanwhile, the existence of partial carboxyl improves the bonding performance of silicon oxygen carbon/silicon carbon and the bonding agent; on the other hand, as the silicon-carbon negative active material is subjected to high-temperature treatment, the surface of the silicon-carbon negative active material is hydrophobic, and the PAA is hydrophilic, the interface of the P (BA-co-AA) -g-Dopa with the contact angle of 67 degrees and the silicon-carbon negative active material is more affinity and higher in binding force.
Experimental example 8
The pole pieces obtained in the above example 9 and comparative exampleAfter vacuum drying at 150 ℃ for 2h, the electrode is cut into small disks with the diameter of 12mm, and assembled into a CR 2016 type lithium metal cathode, Celgard 2400 is a diaphragm, and the CR 2016 type button cell is assembled for research. The electrolyte contains 1mol L-1Lithium hexafluorophosphate (LiPF)6) Dimethyl carbonate (DMC) and Ethylene Carbonate (EC) (v: v ═ 1:1) binary solvents and 10 wt.% fluoroethylene carbonate (FEC) additive (both battery grade purity, new aegium). The assembly process of all batteries was carried out in an Ar glove box (MB 10compact MBRAUN O)2The content of H is less than 0.5ppm2O content less than 0.5ppm), the results are shown in fig. 7 and 8.
In FIG. 7, (a) and (b) show photographs of the pole pieces obtained in comparative example and example 9, respectively, before recycling, and (c) and (d) show photographs of the pole pieces obtained in comparative example and example 9, respectively, after 100 cycles. The topographical evolution of the electrode surface during cycling can be seen in fig. 7. The micron silicon electrode using the PBA-PAA-g-Dopa binder maintains a flat surface and intact silicon particles in morphology even after 100 charge and discharge cycles, while the electrode using the PAA binder has a large number of cracks and severe pulverization of the micron silicon particles over the entire electrode surface. The occurrence of these cracks is a manifestation of a decrease in the stress release efficiency of the active material layer under a strong volume change and the reversible elasticity of the binder. The newly exposed surfaces in the cracks and the active material of the micro particles in the electrode are continuously pulverized to become smaller, and more electrolyte is consumed to form a new SEI film. The apparent change in thickness before and after electrode cycling is a combined result of silicon particle breakage, powdering, and repeated SEI film generation, ultimately leading to active species dispersion and loss of electrical contact. Gradual degradation of the electrode structure is the root cause of coulombic inefficiency, significant capacity fade, and ultimately cell failure. Thus, the comparative results shown in FIG. 7 demonstrate that the P (BA-co-AA) -g-Dopa binder obtained in the examples of the present invention is useful for alleviating the adverse effects caused by the volume effect of the silicon material during the circulation.
Fig. 8 is a graph showing cycle life of the battery prepared in example 9 and the battery prepared in comparative example. It can be seen from the figure that the capacity retention rates of the batteries prepared from PBA-PAA-g-Dopa and PAA are 98.06% and 95.18% respectively after 100 cycles, and the capacity fading curve of the battery prepared from example 9 is more gentle.
It can be seen from the above examples, comparative examples and experimental examples that the mussel biomimetic polymer of the invention obtains a polyacrylic acid-acrylic ester copolymer with a carboxyl and flexible structure by performing a free radical polymerization reaction on an acrylic acid monomer and an acrylic ester soft monomer, and then performs a copolymerization grafting reaction on the polyacrylic acid-acrylic ester copolymer and a compound containing a dopamine structure, so as to introduce a catechol structure into a branched chain of the polyacrylic acid-acrylic ester copolymer, reduce the glass transition temperature of the polyacrylic acid-acrylic ester copolymer, and improve the fluidity and wettability of the obtained silicon carbon negative electrode binder. When the mussel bionic polymer is used for preparing the silicon-carbon negative electrode binder, the mussel bionic polymer has strong binding property with a silicon-carbon negative electrode active material and a metal current collector, and can relieve volume expansion of the silicon-carbon negative electrode active material and prevent the silicon-carbon negative electrode active material from being powdered.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A mussel biomimetic polymer, which has a structural formula shown in formula (I):
wherein m is more than or equal to 5 and less than or equal to 500, n is more than or equal to 5 and less than or equal to 500, x is more than or equal to 5 and less than or equal to 200, and m, n and x are integers.
2. A preparation method of a mussel biomimetic polymer is characterized by comprising the following steps:
providing an acrylic monomer, an acrylic ester soft monomer and a compound containing a dopamine structure;
carrying out free radical polymerization reaction on the acrylic acid monomer and the acrylate soft monomer to generate polyacrylic acid-acrylate copolymer;
carrying out copolymerization grafting reaction on the polyacrylic acid-acrylate copolymer and the compound containing the dopamine structure to obtain the mussel biomimetic polymer;
the structural formula of the mussel biomimetic polymer is shown as the formula (I):
the structural formula of the polyacrylic acid-acrylate copolymer is shown as the formula (II):
wherein m is more than or equal to 5 and less than or equal to 500, n is more than or equal to 5 and less than or equal to 500, x is more than or equal to 5 and less than or equal to 200, and m, n and x are integers.
3. The method for preparing a mussel biomimetic polymer according to claim 2, wherein the acrylate soft monomer is at least one selected from butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
4. The method for preparing a mussel biomimetic polymer according to claim 2, wherein the compound containing a dopamine structure is selected from dopamine and/or levodopa.
5. The method for preparing a mussel biomimetic polymer according to any of claims 2-4, wherein in the step of polymerizing the acrylic acid monomer and the soft acrylate monomer, the molar ratio of the soft acrylate monomer to the acrylic acid monomer is 0.35-2.76; and/or
In the step of grafting the compound containing the dopamine structure by the polyacrylic acid-acrylate copolymer, the molar ratio of the polyacrylic acid-acrylate copolymer to the compound containing the dopamine structure is (2-5): 714.
6. A silicon-carbon negative electrode binder, comprising the mussel biomimetic polymer of claim 1 or the mussel biomimetic polymer prepared by the method of any one of claims 2 to 5.
7. A silicon-carbon anode material comprising the silicon-carbon anode binder according to claim 6.
8. The preparation method of the silicon-carbon negative electrode material is characterized by comprising the following steps of:
providing a silicon-carbon negative electrode active material, a silicon-carbon negative electrode binder, a conductive agent and a solvent;
mixing the silicon-carbon negative electrode binder with the solvent to obtain a glue solution;
mixing the glue solution with the silicon-carbon negative electrode active material and the conductive agent to obtain the silicon-carbon negative electrode material;
the silicon-carbon negative electrode binder comprises the mussel biomimetic polymer as claimed in claim 1 or the mussel biomimetic polymer prepared by the preparation method of the mussel biomimetic polymer as claimed in any one of claims 2 to 5.
9. A negative electrode, which is characterized by comprising the silicon-carbon negative electrode material of claim 7 or the silicon-carbon negative electrode material prepared by the preparation method of the silicon-carbon negative electrode material of claim 8.
10. A lithium ion battery comprising the negative electrode according to claim 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114899404A (en) * | 2022-05-27 | 2022-08-12 | 瑞固新能(上海)材料科技有限公司 | Anti-cracking agent for lithium battery |
| CN115020708A (en) * | 2022-06-13 | 2022-09-06 | 湖北亿纬动力有限公司 | Water-based binder suitable for negative electrode and preparation method and application thereof |
| CN115692703A (en) * | 2022-11-10 | 2023-02-03 | 苏州清陶新能源科技有限公司 | Battery binder, battery cathode, battery and preparation method of battery binder |
| CN117317234A (en) * | 2023-11-29 | 2023-12-29 | 瑞浦兰钧能源股份有限公司 | Silicon-based negative electrode slurry and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114899404A (en) * | 2022-05-27 | 2022-08-12 | 瑞固新能(上海)材料科技有限公司 | Anti-cracking agent for lithium battery |
| CN115020708A (en) * | 2022-06-13 | 2022-09-06 | 湖北亿纬动力有限公司 | Water-based binder suitable for negative electrode and preparation method and application thereof |
| CN115692703A (en) * | 2022-11-10 | 2023-02-03 | 苏州清陶新能源科技有限公司 | Battery binder, battery cathode, battery and preparation method of battery binder |
| CN115692703B (en) * | 2022-11-10 | 2024-05-03 | 苏州清陶新能源科技有限公司 | Battery binder, battery cathode, battery and preparation method of battery binder |
| CN117317234A (en) * | 2023-11-29 | 2023-12-29 | 瑞浦兰钧能源股份有限公司 | Silicon-based negative electrode slurry and preparation method and application thereof |
| CN117317234B (en) * | 2023-11-29 | 2024-05-10 | 瑞浦兰钧能源股份有限公司 | Silicon-based negative electrode slurry and preparation method and application thereof |
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