CN116463084A - Preparation method of polyacrylic acid negative electrode binder and high-silicon negative electrode piece - Google Patents
Preparation method of polyacrylic acid negative electrode binder and high-silicon negative electrode piece Download PDFInfo
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- CN116463084A CN116463084A CN202310582126.3A CN202310582126A CN116463084A CN 116463084 A CN116463084 A CN 116463084A CN 202310582126 A CN202310582126 A CN 202310582126A CN 116463084 A CN116463084 A CN 116463084A
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- negative electrode
- polyacrylic acid
- silicon
- electrode binder
- binder
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- 239000011883 electrode binding agent Substances 0.000 title claims abstract description 84
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 79
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 67
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 51
- 239000010703 silicon Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 nitrobenzyl ester Chemical class 0.000 claims abstract description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 22
- 239000006258 conductive agent Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 239000003292 glue Substances 0.000 claims description 20
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 14
- 239000004642 Polyimide Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011267 electrode slurry Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 101000962156 Homo sapiens N-acetylglucosamine-1-phosphodiester alpha-N-acetylglucosaminidase Proteins 0.000 claims 3
- LZCXCXDOGAEFQX-UHFFFAOYSA-N N-Acryloylglycine Chemical compound OC(=O)CNC(=O)C=C LZCXCXDOGAEFQX-UHFFFAOYSA-N 0.000 claims 3
- 102100039267 N-acetylglucosamine-1-phosphodiester alpha-N-acetylglucosaminidase Human genes 0.000 claims 3
- 230000014759 maintenance of location Effects 0.000 abstract description 16
- 238000000265 homogenisation Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- 229910052744 lithium Inorganic materials 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 238000012545 processing Methods 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 244000247812 Amorphophallus rivieri Species 0.000 description 3
- 235000001206 Amorphophallus rivieri Nutrition 0.000 description 3
- 229920002907 Guar gum Polymers 0.000 description 3
- 229920002752 Konjac Polymers 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000000665 guar gum Substances 0.000 description 3
- 235000010417 guar gum Nutrition 0.000 description 3
- 229960002154 guar gum Drugs 0.000 description 3
- 239000000252 konjac Substances 0.000 description 3
- 235000010485 konjac Nutrition 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002409 silicon-based active material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical class CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 229940097139 perfect choice Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Abstract
The invention discloses a preparation method of a polyacrylic acid negative electrode binder and a high-silicon negative electrode plate, wherein the polyacrylic acid negative electrode binder comprises a polyacrylic acid negative electrode binder grafted with nitrobenzyl ester and an amino modified polyacrylic acid negative electrode binder, and the mass ratio of the polyacrylic acid negative electrode binder grafted with nitrobenzyl ester to the amino modified polyacrylic acid negative electrode binder is (0.3-5): 1. according to the invention, through the use of the polyacrylic acid (PAA-g-NB) negative electrode binder grafted with the nitrobenzyl ester and the amino modified polyacrylic acid (APAA) negative electrode binder, the non-crosslinked binder is adopted for homogenization, and the binder can be crosslinked in situ under ultraviolet irradiation after coating, so that the high-silicon negative electrode plate is prepared, the expansion of a silicon negative electrode can be inhibited, the falling of a negative electrode active substance and an SEI film is reduced, and the retention rate of the circulating capacity of a battery is increased.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a negative electrode binder and a negative electrode plate, and particularly relates to a preparation method of a polyacrylic acid negative electrode binder and a high-silicon negative electrode plate.
Background
The current market places higher demands on the energy density, battery cost, safety in use, and life time of Lithium Ion Batteries (LIBs). For LIBs, silicon has the advantages of ultrahigh theoretical specific capacity (4200 mAh/g), safe lithium intercalation potential, low price, small initial irreversible capacity and the like, and is a cathode material with excellent application prospect. Silicon-based composite materials with silicon content of 1% -5% have been developed to a certain extent by current domestic and foreign negative electrode material manufacturers, but in the lithiation/delithiation process of silicon-based batteries, the volume expansion rate is as high as 300%, the defect directly causes the silicon negative electrode to be very easy to fall off, the surface solid electrolyte interface film (SEI) film is continuously broken, the battery capacity is rapidly reduced along with the increase of charge and discharge times, and commercial production of the high-silicon-content negative electrode with the silicon content of more than 10% is realized. The binder with the mass ratio lower than 10% in the LIBs pole piece tightly connects the active material, the conductive agent, the current collector and the like into a whole, and the polymer binder with the three-dimensional network structure can inhibit the expansion of the silicon negative electrode. Therefore, the binder with the elastic cross-linked network structure and the adaptation of the existing battery processing technology can provide a solution for the difficult production problem of the battery with high silicon content. Based on the technical background, the invention provides an in-situ crosslinking binder system and a preparation method for a high-silicon negative electrode plate.
CN109037689a discloses a polymer binder of lithium ion silicon-based negative electrode material and a preparation method of a pole piece thereof, acrylic acid, methacrylic acid, styrene and ester polymers are copolymerized to obtain the polymer binder, and the weight ratio of the polyacrylic acid is 2% -10%. After the battery is manufactured, compared with pure PAA, the cycle performance of the silicon anode material in charge and discharge is greatly improved, and the attenuation of the battery capacity is reduced, wherein the initial charge and discharge specific capacities of the optimal test group are 3851/4575mAh/g respectively, the initial coulomb efficiency is 84.18%, and the capacity retention rate after 100 times of cycles is 61.9%.
CN113629250a discloses a polyimide binder and a silicon-based negative plate for a lithium battery negative electrode, wherein the polyimide binder is prepared by copolymerizing and imidizing diamine containing imidazole groups, sulfonated diamine and dianhydride containing ketone groups. The polyimide binder has good adhesion to current collectors and silicon-based active materials, and has good performances in the aspects of flexibility and heat resistance. The capacity retention rate of the embodiment is greater than 80% when the polyimide binder is cycled for 100 times, and 66% -71% when the polyimide binder is cycled for 200 times, and 45% -60% when the polyimide binder is cycled, the volume expansion of the silicon-based active material in the charge and discharge process can be inhibited to a certain extent.
CN114142040a discloses a lithium battery negative electrode silicon-based material binder, which comprises konjac glucomannan-acrylic acid graft copolymer, guar gum, sodium alginate and hydroxyl-terminated polybutadiene. The konjac glucomannan-acrylic acid graft copolymer and guar gum contain rich ether groups to promote the transmission of lithium ions, and hydroxyl groups and carboxyl groups in the konjac glucomannan-acrylic acid graft copolymer and guar gum interact with the surface of silicon to ensure that the silicon particles can still keep electronic contact after differentiation, and the adhesive force of the adhesive is effectively enhanced. After the adhesive is applied to preparing the silicon-based material of the lithium battery cathode, the test shows that after 200 times of circulation, the capacity retention rate of the embodiment is 75-80%, and the circulation stability of the silicon-based cathode is improved.
CN111326738A discloses a formulation of an aqueous binder for silicon-based negative electrode materials: 1 to 10 parts of CMC, 6 to 40 parts of SBR and 4 to 20 parts of modified PAA. The modified PAA is PAA-Li, can be crosslinked with CMC in a small amount to relieve adverse effects caused by the volume change of the silicon-based anode material, and the capacity retention rate of the lithium battery of the embodiment (CMC/PAA/SBR) after 300 times of circulation is more than 90 percent, and the comparative example (CMC/SBR) is 84 percent, which shows that the PAA-Li can improve the circulation performance of the lithium battery.
The technology provides the adhesive which can generate stronger force with the silicon-based material so as to improve the adhesive force, inhibit the expansion of the silicon-based material to a certain extent, and has good prospect in the development of the lithium battery with low silicon content (0-10%). However, the cycle performance of the lithium battery prepared by the binder can not reach 1000 circles/80% capacity retention rate, and the lithium battery with high silicon content (more than 10%) can not be commercialized. The adhesive with the three-dimensional network structure provides possibility for developing the lithium battery with high silicon content.
CN11218391a discloses a crosslinked reticular silicon-carbon negative electrode binder and a silicon-carbon negative electrode sheet, wherein the binder is obtained by thermally crosslinking polyimide and polyvinyl alcohol, and the silicon-based material expansion rate is further inhibited by crosslinking while maintaining the high adhesion of polyimide. When the lithium ion battery is used for a silicon-carbon negative electrode plate, the capacity retention rate is more than 83% after 100 times of circulation, and the comparative example is only 63%, so that the circulation reversibility of the lithium ion battery can be effectively improved.
CN108063258A discloses a preparation method of a binder for improving the cycling stability of a silicon electrode of a lithium battery, after uniformly mixing acrylic acid, deionized water, graphene-coated cobalt molybdate network nano-sheets, carboxymethyl cellulose and a photoinitiator, directly performing ultraviolet photoinduced crosslinking by an in-situ polymerization method to obtain the binder containing polyacrylic acid grafted carboxymethyl cellulose copolymer. CN108063258A utilizes the network structure of the nanosheets, can effectively prevent the movement of the nano silicon particles in the circulation process, and when graphene: the ratio of the nano-sheets is increased to 1: and 3, the cycle times of the lithium battery in the embodiment can reach 800 times, which shows that the electrode structure is more stable, and the cycle stability of the electrode is facilitated.
The adhesive with the three-dimensional network structure prepared by the technology has strong elastic behavior and weak adhesive behavior before being crosslinked with the homogenate, so that the adhesive has poor processability, the processing conditions of the homogenate are improved, the processing yield of the pole piece section is reduced, and the production cost is increased. In addition, the binding agent crosslinked in advance is easy to agglomerate during homogenate, so that the binding force can not be fully exerted, the problems of poor slurry stability, large pole piece resistance and the like are solved, and the commercialized application of the binding agent in a high-silicon-content battery system is limited. In summary, it is known that the binders that have been crosslinked prior to homogenization are not a perfect choice for high silicon content lithium batteries.
The inhibition effect of various uncrosslinked silicon negative electrode binders on silicon-based expansion rate is limited, and the silicon-based expansion rate can be preliminarily applied to a low-silicon (0-10%) system, but the cycle performance of a lithium battery prepared by CN109037689A, CN113629250A, CN114142040A cannot reach 1000 circles/80% capacity retention rate, and the commercialization of a lithium battery with high silicon content (more than 10%) cannot be realized.
The adhesive with the three-dimensional network structure after crosslinking can further inhibit the expansion rate of the silicon-based material, and provides possibility for the difficult problem of the lithium battery with high silicon content. However, most of the binders with three-dimensional network structures are crosslinked before homogenization, as described in CN11218391A, CN108063258A, the binders have strong elastic behavior and weak viscosity behavior, so that the processability of the binders is poor, the processing conditions of homogenization are improved, the processing yield of pole piece segments is reduced, the production cost is increased, and the binders cannot be compatible with the existing processing technology, especially wet homogenization. In addition, the binder crosslinked in advance is easy to agglomerate in homogenate, so that the binding force cannot be fully exerted, the problems of poor slurry stability, large pole piece resistance and the like are solved, and the commercial application of the binder in a high-silicon-content battery system is limited.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a polyacrylic acid negative electrode binder and a high-silicon negative electrode plate, wherein the polyacrylic acid negative electrode binder grafted with nitrobenzyl ester and an amino modified polyacrylic acid (APAA) negative electrode binder are used, the non-crosslinked binder can be adopted for homogenization, and the binder can be crosslinked in situ under ultraviolet irradiation after coating, so that the high-silicon negative electrode plate is prepared, the expansion of a silicon negative electrode can be restrained, the falling of a negative electrode active substance and an SEI film is reduced, and the circulation capacity retention rate of a battery is increased. In addition, the invention can adjust the crosslinking degree and the flexibility of the polymer by changing the modification/grafting rate, thereby realizing compatibility with the processing requirement of the existing pole piece.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the polyacrylic acid negative electrode binder comprises a polyacrylic acid negative electrode binder grafted with nitrobenzyl ester and an amino modified polyacrylic acid negative electrode binder, wherein the mass ratio of the polyacrylic acid negative electrode binder grafted with nitrobenzyl ester to the amino modified polyacrylic acid negative electrode binder is (0.3-5): 1.
as a preferable scheme of the invention, the polyacrylic acid negative electrode binder grafted with the nitrobenzyl ester is prepared by grafting PAA and nitrobenzyl ester molecules NB through amidation reaction, and the preparation method comprises the following steps:
s1, adding PAA and NB into a flask filled with DMSO solvent for dissolving at normal temperature;
s2, after dissolution, adding N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and dissolving at normal temperature;
s3, stirring the reaction system at 40 ℃, dialyzing the mixture with deionized water after 24 hours, diluting, regulating the pH to be neutral, and enabling the glue solution to be yellow (if PAA is emulsion, the PAA-g-NB glue solution is light yellow and opaque), so that the polyacrylic acid negative electrode binder (PAA-g-NB) grafted with the nitrobenzyl ester can be obtained, and the grafting rate of the PAA-g-NB negative electrode binder can be regulated and controlled within the range of 0-90%.
As a preferable scheme of the invention, the nitrobenzyl ester molecule NB can be subjected to photo-cleavage under the irradiation of 200-400nm ultraviolet light, after photo-cleavage, an aldehyde group can be exposed from a polyacrylic acid side chain, and the nitrobenzyl ester molecule NB has the following structural formula:
wherein R is 1 Is polyacrylic acid chain, R 2 Alkanes, alkenes, alkynes, short or long chain, including hydroxymethyl, ether, ester or carbonyl groups, R 3 Alkanes, alkenes, alkynes, short or long chain including hydroxymethyl, ether linkage, ester linkage, or carbonyl.
As a preferable scheme of the invention, the amino modified polyacrylic acid negative electrode binder is prepared by amination of PAA through hydrazine hydrate, and has the structure as follows:
n is the number of segments, and the amount of n can be adjusted to be 0-90% of the total number of segments.
As a preferable scheme of the invention, the preparation process of the amino modified polyacrylic acid negative electrode binder comprises the following steps:
1) Adding PAA and excessive hydrazine hydrate into a flask, standing at normal temperature, and controlling the modification rate by adjusting the reaction time;
2) After the reaction, APAA is obtained through rotary evaporation, APAA glue solution is obtained after dissolution in water, the pH is adjusted to be neutral, the glue solution is colorless and transparent (if PAA is emulsion, the APAA glue solution is milky opaque), and the amino modified polyacrylic acid negative electrode binder is obtained; the amino modification rate of the APAA negative electrode binder is in the range of 0-90%.
As a preferable scheme of the invention, the main chain of the polyacrylic acid negative electrode binder is obtained by copolymerizing acrylic acid or other monomers, wherein the copolymerized monomers comprise one or more of acrylic acid, acrylonitrile, acrylic acid ester, butadiene, vinyl alcohol and the like, and the polymer has weight average molecular weight M w 50-500 ten thousand.
The invention also provides a preparation method of the high-silicon negative electrode plate using the polyacrylic acid negative electrode binder, which is characterized by comprising the following steps:
a) Uniformly mixing the polyacrylic acid negative electrode binder and a solvent in a dark place to obtain a glue solution;
b) Adding a conductive agent into the glue solution in the step a) and uniformly mixing to obtain a conductive glue solution;
c) Adding the anode active material into the conductive glue solution obtained in the step b) twice or more, uniformly stirring, and adjusting the viscosity and the solid content to obtain a mixture;
d) Adding one or more of styrene-butadiene rubber, styrene-acrylic rubber, polyimide, modified polyacrylic acid and polyacrylate as a third binder into the mixture in the step c), and uniformly stirring to obtain high-silicon-content negative electrode slurry;
e) And d) when the high-silicon-content negative electrode slurry in the step d) is coated on the current collector, ultraviolet light is added into a drying tunnel for irradiation for a period of time, and then the high-silicon negative electrode plate is obtained after baking and drying.
As a preferable scheme of the invention, the negative electrode active material is a composite material of nano silicon, silicon oxide or silicon carbide and graphite, wherein the mass fraction of the nano silicon, the silicon oxide or the silicon carbide in the negative electrode plate is 10-30%, and the graphite material is any one or a combination of at least two of artificial graphite, modified natural graphite, hard carbon and mesophase carbon microsphere materials; the conductive agent is at least one of conductive carbon black, acetylene black, ketjen black, carbon fiber, carbon nano tube and graphene, and the mass fraction of the conductive agent in the negative electrode plate is 0-4% and does not comprise 0.
Preferably, the mass fraction of nano silicon, silicon oxide or silicon carbide in the negative electrode plate is 20-30%.
As a preferable scheme of the invention, the mass fraction of the polyacrylic acid negative electrode binder grafted with the nitrobenzyl ester and the amino modified polyacrylic acid negative electrode binder in the negative electrode plate is 3-10%, and the mass fraction of one or more binders in styrene-butadiene rubber, styrene-acrylic, polyimide, modified polyacrylic acid and polyacrylate in the negative electrode plate is 1-5%.
Preferably, the mass fraction of the polyacrylic acid negative electrode binder grafted with the nitrobenzyl ester and the amino modified polyacrylic acid negative electrode binder in the negative electrode plate is 5-8%.
As a preferred scheme of the invention, in the step d), the solid content of the high-silicon-content anode slurry is 40-70wt% and the viscosity is 1000-10000mPa.s; in step e), ultraviolet light is irradiated during drying for 5-20min.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention bonds the photoresponsive nitrobenzyl ester with the polyacrylic acid binder to obtain the polyacrylic acid (PAA-g-NB) negative electrode binder grafted with the nitrobenzyl ester, and modifies the binder to obtain the amino polyacrylic acid (APAA) negative electrode binder, ultraviolet light can be added into a coating drying tunnel to crosslink the binder in situ, and the crosslinking degree and the flexibility of the binder can be adjusted to better adapt to various processing conditions and performance requirements.
2) The invention enables the high-silicon content battery to have higher capacity retention rate after circulation, and provides possibility for the high-silicon content lithium battery. Meanwhile, the cost of the used adhesive polymerization monomer polyacrylic acid is low, and the processing technology is mature.
3) The invention aims at preparing a high-silicon system negative electrode plate and preparing a lithium battery, and utilizes a polyacrylic acid (PAA-g-NB) negative electrode binder grafted with nitrobenzyl ester and an amino modified polyacrylic acid (APAA) negative electrode binder system to inhibit the expansion of the high-silicon system negative electrode plate, so that the high-silicon-content lithium battery can have higher battery capacity retention rate after circulation, and provides possibility for commercialization of the high-silicon-content lithium battery.
Detailed Description
In order to facilitate understanding of the technical means, the creation characteristics, the achievement of the objects and the effects achieved by the present invention, the present invention is further described below with reference to specific examples, but the following examples are only preferred examples of the present invention, not all of which are described in detail below. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the invention. The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
Example 1
The embodiment provides a preparation method of a nitrobenzyl polyacrylate (PAA-g-NB) negative electrode binder and an amino modified polyacrylic acid (APAA) negative electrode binder, and a preparation method of a high-silicon negative electrode plate:
preparation of a nitrobenzyl ester grafted polyacrylic acid (PAA-g-NB) negative electrode binder:
step (1) 20g of PAA and 0-200g of NB are added into a flask filled with DMSO solvent, and stirred at normal temperature for dissolution.
After the dissolution in the step (2), 10-30g N-hydroxysuccinimide (NHS) and 40-400g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC. HCL) were added and dissolved at room temperature.
And (3) stirring the reaction system at 40 ℃ for 24 hours, dialyzing the mixture with distilled water for 3 days, adding NaOH to the aqueous solution with pH=7.0, and diluting to the specified solid content to obtain the PAA-g-NB glue solution.
Preparation of amino modified polyacrylic acid (APAA) negative electrode binder:
step (1) 20g of PAA and excess hydrazine hydrate are added into a flask and kept stand for 12-48h at normal temperature.
And (3) after the reaction in the step (2), obtaining APAA through rotary evaporation, dissolving in water, and adding NaOH until the pH value of the aqueous solution is 7.0, thus obtaining the APAA glue solution.
PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (1.5:1.5:1:0.5:15:80:0.5).
Step (1) mixing 100g of PAA-g-NB negative electrode binder and 50g of APAA negative electrode binder with 1500-2000g of pure water, stirring and dispersing at 1500-2000rpm/min for 0.5-3h to obtain a glue solution.
Step (2), adding 50g of carbon black as a first conductive agent and 25g of carbon nano tube as a second conductive agent into the glue solution, mixing, stirring and dispersing for 1 hour at a rotating speed of 3000rpm/min to obtain conductive glue;
step (3) adding 750g of negative electrode silicon-oxygen main material into conductive adhesive, stirring for 1 hour at a rotating speed of 3000rpm/min, adding the rest 4000g of negative electrode graphite main material and 500-3000g of pure water after one-time stirring, stirring for 3 hours at a rotating speed of 3000rpm/min, and adding 50g of styrene-butadiene rubber (SBR) with a solid content of 50%, thereby obtaining high-silicon-content negative electrode slurry;
and (4) coating the high-silicon-content negative electrode slurry on the surface of a copper foil at a speed of 4-10m/min, irradiating for 5-60min by using 200-365nm ultraviolet rays, and drying at 70-150 ℃ to obtain the high-silicon-content negative electrode plate, wherein the cohesive force of the plate is 800-1000mN/mm.
Example 2
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and third binder in mass ratio of=1.5:1.5:1:0.5:20:75:0.5.
Otherwise, the same as in example 1 was used.
Example 3
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (1.5:1.5:1:0.5:25:70:0.5).
Otherwise, the same as in example 1 was used.
Example 4
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (1.5:1.5:1:0.5:30:65:0.5).
Otherwise, the same as in example 1 was used.
Example 5
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (1.75:1.25:1:0.5:15:80:0.5).
Otherwise, the same as in example 1 was used.
Example 6
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (1.25:1.75:1:0.5:15:80:0.5).
Otherwise, the same as in example 1 was used.
Example 7
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (1:2:1:0.5:15:80:0.5).
Otherwise, the same as in example 1 was used.
Example 8
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (2:1:1:0.5:15:80:0.5).
Otherwise, the same as in example 1 was used.
Example 9
The difference from example 1 is that: PAA-g-NB negative electrode binder, APAA negative electrode binder, first conductive agent, second conductive agent, negative electrode silicon oxide material, negative electrode graphite main material and styrene-butadiene rubber in a mass ratio of (1:1:1:0.5:15:81:0.5).
Otherwise, the same as in example 1 was used.
Comparative example 1
The difference from example 1 is that: in the step (1), 50g of conventional battery grade sodium carboxymethyl cellulose (CMC) (Mac 500L) and 1500-3000g of pure water are mixed and stirred uniformly to obtain a glue solution. 150g of Styrene Butadiene Rubber (SBR) with 50% solid content is added into the slurry in the step (3), and the cohesion is 500-700Mn/mm.
Otherwise, the same as in example 1 was used.
Performance test: and (3) rolling and punching the negative electrode plate with high silicon content in the step (4) to obtain the half battery.
TABLE 1 cycle performance of lithium batteries produced
It can be seen from Table 1 that examples 1 to 9 still have a capacity retention of 90% or more after 200 cycles, whereas comparative examples have a capacity retention of 43%. Examples 1-9 still had a capacity retention of 80% or more after 500 cycles, while the comparative example had a capacity retention that was too low to be measured. The cohesive force of the pole piece prepared in the example 1 is larger than that of the comparative example, and the adhesive can obviously improve the cohesive force of the pole piece. Comparative examples and comparative examples it is clear that the battery capacity retention of the examples is higher and the binder system according to the invention is more suitable for the preparation of high silicon content batteries.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The polyacrylic acid negative electrode binder is characterized by comprising a polyacrylic acid negative electrode binder grafted with nitrobenzyl ester and an amino modified polyacrylic acid negative electrode binder, wherein the mass ratio of the polyacrylic acid negative electrode binder grafted with nitrobenzyl ester to the amino modified polyacrylic acid negative electrode binder is (0.3-5): 1.
2. the polyacrylic acid negative electrode binder according to claim 1, wherein the polyacrylic acid negative electrode binder grafted with nitrobenzyl ester is prepared by grafting PAA and nitrobenzyl ester molecules NB through amidation reaction, and the preparation method comprises the following steps:
s1, adding PAA and NB into a flask filled with DMSO solvent for dissolving at normal temperature;
s2, after dissolution, adding N-hydroxysuccinimide and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, and dissolving at normal temperature;
s3, stirring the reaction system at 40 ℃, dialyzing the mixture with deionized water after 24 hours, diluting, and adjusting the pH value to be neutral to obtain the polyacrylic acid negative electrode binder grafted with the nitrobenzyl ester.
3. The polyacrylic acid negative electrode binder according to claim 2, wherein the nitrobenzyl ester molecules NB can undergo photo-cleavage under the irradiation of 200-400nm ultraviolet light, and after photo-cleavage, the polyacrylic acid side chains will have aldehyde groups exposed, and the nitrobenzyl ester molecules NB has the following structural formula:
wherein R is 1 Is polyacrylic acid chain, R 2 Alkanes, alkenes, alkynes, short or long chain, including hydroxymethyl, ether, ester or carbonyl groups, R 3 Alkanes, alkenes, alkynes, short or long chain including hydroxymethyl, ether linkage, ester linkage, or carbonyl.
4. The polyacrylic acid negative electrode binder according to claim 1, wherein the amino-modified polyacrylic acid negative electrode binder is prepared by amination of PAA with hydrazine hydrate, and has the structure:
n is the number of segments, and the amount of n can be adjusted to be 0-90% of the total number of segments.
5. The polyacrylic acid negative electrode binder according to claim 4, wherein the amino modified polyacrylic acid negative electrode binder is prepared by the steps of:
1) Adding PAA and excessive hydrazine hydrate into a flask, standing at normal temperature, and controlling the modification rate by adjusting the reaction time;
2) After the reaction, APAA is obtained through rotary evaporation, APAA glue solution is obtained through dissolution in water, and pH is adjusted to be neutral, so that the amino modified polyacrylic acid negative electrode binder is obtained; the amino modification rate of the APAA negative electrode binder is in the range of 0-90%.
6. The negative electrode binder of claim 1, wherein the main chain of the negative electrode binder is obtained by copolymerizing acrylic acid or other monomers, the copolymerized monomers comprise one or more of acrylic acid, acrylonitrile, acrylic acid ester, butadiene and vinyl alcohol, and the polymer has weight average molecular weight M w 50-500 ten thousand.
7. The preparation method of the high-silicon negative electrode plate is characterized by comprising the following steps of:
a) Uniformly mixing the polyacrylic acid negative electrode binder according to any one of claims 1-6 with a solvent in a dark place to obtain a glue solution;
b) Adding a conductive agent into the glue solution in the step a) and uniformly mixing to obtain a conductive glue solution;
c) Adding the anode active material into the conductive glue solution obtained in the step b) twice or more, uniformly stirring, and adjusting the viscosity and the solid content to obtain a mixture;
d) Adding one or more of styrene-butadiene rubber, styrene-acrylic rubber, polyimide, modified polyacrylic acid and polyacrylate as a third binder into the mixture in the step c), and uniformly stirring to obtain high-silicon-content negative electrode slurry;
e) And d) when the high-silicon-content negative electrode slurry in the step d) is coated on the current collector, ultraviolet light is added into a drying tunnel for irradiation for a period of time, and then the high-silicon negative electrode plate is obtained after baking and drying.
8. The preparation method of the high-silicon negative electrode plate according to claim 7, wherein the negative electrode active material is nano silicon, silicon oxide or a composite material of silicon carbide and graphite, wherein the mass fraction of the nano silicon, the silicon oxide or the silicon carbide in the negative electrode plate is 10-30%, and the graphite material is any one or a combination of at least two of artificial graphite, modified natural graphite, hard carbon and mesophase carbon microsphere materials; the conductive agent is at least one of conductive carbon black, acetylene black, ketjen black, carbon fiber, carbon nano tube and graphene, and the mass fraction of the conductive agent in the negative electrode plate is 0-4% and does not comprise 0.
9. The preparation method of the high-silicon negative electrode plate according to claim 7, wherein the mass fraction of the polyacrylic acid negative electrode binder grafted with the nitrobenzyl ester and the amino modified polyacrylic acid negative electrode binder in the negative electrode plate is 3-10%, and the mass fraction of one or more binders in styrene-butadiene rubber, styrene-acrylic, polyimide, modified polyacrylic acid and polyacrylate in the negative electrode plate is 1-5%.
10. The method for preparing a high silicon negative electrode sheet according to claim 7, wherein in the step d), the solid content of the high silicon negative electrode slurry is 40-70wt% and the viscosity is 1000-10000mpa.s; in step e), ultraviolet light is irradiated during drying for 5-20min.
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| 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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