CN117343663A - Silicon-based negative electrode binder, silicon-based negative electrode sheet and lithium ion battery - Google Patents
Silicon-based negative electrode binder, silicon-based negative electrode sheet and lithium ion battery Download PDFInfo
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- CN117343663A CN117343663A CN202311097741.1A CN202311097741A CN117343663A CN 117343663 A CN117343663 A CN 117343663A CN 202311097741 A CN202311097741 A CN 202311097741A CN 117343663 A CN117343663 A CN 117343663A
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- silicon
- negative electrode
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- based negative
- lithium
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000010703 silicon Substances 0.000 title claims abstract description 89
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 89
- 239000011883 electrode binding agent Substances 0.000 title claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 39
- 229920001661 Chitosan Polymers 0.000 claims abstract description 78
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 59
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 56
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 55
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 47
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 47
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 47
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000853 adhesive Substances 0.000 claims abstract description 24
- 230000001070 adhesive effect Effects 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000011267 electrode slurry Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000011884 anode binding agent Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 230000006196 deacetylation Effects 0.000 claims description 10
- 238000003381 deacetylation reaction Methods 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 9
- 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 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 239000011871 silicon-based negative electrode active material Substances 0.000 claims description 6
- 239000011866 silicon-based anode active material Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000006256 anode slurry Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 238000009417 prefabrication Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 abstract description 12
- 239000007773 negative electrode material Substances 0.000 abstract description 10
- 230000009469 supplementation Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 33
- 239000000243 solution Substances 0.000 description 32
- 239000003292 glue Substances 0.000 description 29
- 239000011259 mixed solution Substances 0.000 description 27
- 239000002174 Styrene-butadiene Substances 0.000 description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000006245 Carbon black Super-P Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 8
- 239000002388 carbon-based active material Substances 0.000 description 8
- 239000013256 coordination polymer Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000013589 supplement Substances 0.000 description 5
- -1 carboxylbutylene Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
Classifications
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- 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
- C09J113/00—Adhesives based on rubbers containing carboxyl groups
-
- 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
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/08—Cellulose derivatives
- C09J101/26—Cellulose ethers
- C09J101/28—Alkyl ethers
- C09J101/286—Alkyl ethers substituted with acid radicals
-
- 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
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- H01M4/134—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a silicon-based negative electrode adhesive, a silicon-based negative electrode sheet and a lithium ion battery, wherein the silicon-based negative electrode sheet adhesive comprises a component A and carboxyl styrene-butadiene rubber; component a comprises a mixture of chitosan and lithium carboxymethyl cellulose and/or component a comprises a complex of chitosan and lithium carboxymethyl cellulose; the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:0.2-5. The binder can play roles in lithium supplementation and binding at the same time, can effectively inhibit volume expansion of the silicon-based negative electrode material, improves stability of the silicon-based negative electrode material, and further improves initial efficiency, circulation and rate capability of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a silicon-based negative electrode binder, a silicon-based negative electrode plate and a lithium ion battery.
Background
As the demand for lithium ion batteries increases, research into higher energy density and higher power density lithium ion battery technology continues to refresh the records. Besides the improvement of the energy density of the battery by material modification and new material development, the microstructure parameters of the electrode such as porosity, pore size and distribution, electrode component distribution and the like are also key factors for determining the performance of the electrode and the battery.
Currently, the ordered development of lithium ion batteries has an important meaning for achieving the national 'double carbon' target, while graphite electrode materials used in conventional lithium ion batteries are increasingly difficult to meet the requirements of the current technical development due to the limited specific capacity (theoretical 372 mAh/g), and silicon is increasingly focused and researched as a lithium ion battery anode material with the highest specific capacity (theoretical 4200 mAh/g) currently known. The problem to be solved in the research of the silicon electrode is how to effectively solve the problems of low initial efficiency, poor multiplying power performance and poor cycle performance, especially solve the problem of initial efficiency in the cycle process of the silicon electrode, the main factor causing the low initial efficiency is the volume expansion of the silicon-based material, and the method for controlling the volume expansion of the silicon material not only carries out compound modification on the silicon material, but also has effective effects in relation to the adhesive and space optimization of the specific application environment of the silicon material. The invention of China patent application CN 107959027B discloses a silicon-based negative electrode binder of a lithium ion battery and a preparation method of a negative electrode plate containing the binder, wherein the self-made graphene oxide and modified SBR are compounded to obtain a novel binder, and the binder is used for preparing the negative electrode plate, so that the cycle performance of the silicon-based negative electrode can be improved, the first coulombic efficiency of a silicon-based negative electrode material is improved to a certain extent, the consumption of a conductive agent in the silicon-based negative electrode system is reduced, the overall energy density of the lithium ion battery is improved, and the method is simple in process and suitable for large-scale production. The Chinese patent application CN 115663310A discloses a lithium ion battery based on negative electrode in-situ lithium supplement and a preparation method thereof, wherein a negative electrode lithium supplement additive is mainly added into electrolyte, and under the condition that the charging voltage is more than 4V, the electrolyte is decomposed to generate free radicals or positively charged functional groups, so that the anions can be consumed by reaction or combined with the anions in lithium salt, part of lithium ions in the electrolyte are converted into active lithium ions, and the active lithium ions are deposited on the negative electrode side or supplement part of lithium consumed in the process of forming an SEI film on the negative electrode side, thereby achieving the effect of negative electrode in-situ lithium supplement and improving the cycle stability of the battery. The above process technology improves the cycle performance of the battery by improving the conductivity of the binder and adding the lithium supplementing agent, respectively, but the above process technology mainly aims at optimizing the conductivity and supplementing lithium, and has limited effect in controlling the volume expansion of the silicon negative electrode.
Therefore, the development of the electrode binder which has the functions of supplementing lithium and effectively inhibiting the expansibility of the silicon electrode so as to improve the initial efficiency, the cycle, the rate performance and the like of the battery has important significance in promoting the industrialized application process of the silicon electrode.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention provides the silicon-based negative electrode binder, the silicon-based negative electrode sheet and the lithium ion battery, wherein the binder can simultaneously perform lithium supplementing and bonding, can effectively inhibit the volume expansion of the silicon-based negative electrode material, improves the stability of the silicon-based negative electrode material, and further improves the initial efficiency, the circulation and the multiplying power performance of the battery.
According to a first aspect of the present invention, there is provided a silicon-based negative electrode binder comprising component a and a carboxylated styrene-butadiene rubber; component a comprises a mixture of chitosan and lithium carboxymethyl cellulose and/or component a comprises a complex of chitosan and lithium carboxymethyl cellulose; the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:0.2-5.
The adhesive is a composite adhesive formed by using chitosan modified carboxymethyl cellulose lithium and carboxyl styrene-butadiene rubber in a matching way, and firstly, the component A in the composite adhesive comprises chitosan and carboxymethyl cellulose, and the chitosan can be used for modifying the carboxymethyl cellulose lithium to a certain extent. On one hand, the carboxymethyl cellulose lithium modified by chitosan not only can play a role in pre-supplementing lithium to the silicon-based anode material, but also can improve the first effect of the battery; on the other hand, the composite adhesive has higher bonding strength and flexibility, can inhibit thickening, cracking and pulverization of an SEI film formed on the surface of a negative electrode, simultaneously provides expansion space for volume expansion of a silicon-based negative electrode active material, improves structural stability of a silicon-based negative electrode active material layer, reduces thickness variation of a silicon-based electrode plate, and improves battery cycle stability, capacity retention rate and rate capability. In addition, the component A and the carboxyl styrene-butadiene rubber are controlled in a certain proportion, so that the use amount of the binder can be further reduced, the overall energy density of the lithium ion battery is facilitated, and the problem that the battery performance is adversely affected by excessive use of the binder is solved.
Preferably, when component a comprises a complex of chitosan and lithium carboxymethyl cellulose, the preparation process of the complex comprises the following operations: s1, mixing chitosan with water, and regulating the pH value to obtain a clarified chitosan aqueous solution; s2, adding the carboxymethyl cellulose lithium into the chitosan aqueous solution obtained by prefabrication of the S1. By using acid to dissolve chitosan in water, the subsequent full reaction with the carboxyl styrene-butadiene rubber is ensured, and the quality of the obtained product chitosan modified carboxyl styrene-butadiene rubber is improved.
Preferably, the molecular weight of the chitosan is 15 ten thousand to 65 ten thousand, and the deacetylation degree is 85% -95%. The molecular weight and the deacetylation degree of the chitosan are controlled within a certain range, so that on one hand, the chitosan can be ensured to be dissolved in water under the condition of a small amount of acid, and the carboxymethyl cellulose lithium can be sufficiently modified, and meanwhile, the formed chitosan/carboxymethyl cellulose lithium mixture or compound has better bonding strength and flexibility.
Preferably, the solid content of the carboxylated styrene-butadiene rubber is 45-55%.
Preferably, in S1, the acid includes at least one of acetic acid, citric acid, formic acid, hydrochloric acid, nitric acid, sulfuric acid.
Preferably, the chitosan accounts for 0.01-8wt% of the mass of the chitosan aqueous solution.
Preferably, the mass ratio of the chitosan to the lithium carboxymethyl cellulose is 0.05-0.7: 1.5.
preferably, the adhesive further comprises at least one of styrene-butadiene rubber, sodium carboxymethyl cellulose and polyurethane acrylate.
According to a second aspect of the present invention, there is provided a silicon-based negative electrode sheet comprising the above-described lithium ion battery silicon-based negative electrode binder and a silicon-based negative electrode active material comprising at least one of Si, siO, si/C, siO/C.
Preferably, the silicon-based active material comprises at least one of Si, siO, si/C, siO/C.
Preferably, the silicon-based negative electrode sheet further comprises a conductive agent, wherein the conductive agent comprises at least one of conductive carbon black, carbon nanotubes, graphene, modified graphene and graphite oxide.
Preferably, the conductive carbon black includes at least one of Super P, acetylene black, ketjen black.
Preferably, the preparation method of the silicon-based negative plate comprises the following steps: preparing a silicon-based anode active material, a conductive agent, a silicon-based anode binder and a solvent into anode slurry; step two, coating the negative electrode slurry on a current collector, and drying and rolling to prepare a silicon-based negative electrode plate; in the first step, the mass ratio of the silicon-based anode active material to the conductive agent to the silicon-based anode binder is 80-95: 1 to 6:2 to 15. The silicon-based negative plate prepared by the adhesive has better stability, can have smaller thickness variation under multiple charge and discharge cycles, and is beneficial to improving the cycle stability and capacity retention rate of the battery.
Preferably, in the second step of the method for preparing a silicon-based negative electrode sheet, the thickness of the electrode paste coated on the current collector is 20 to 40 μm.
Preferably, in the second step of the preparation method of the silicon-based negative electrode sheet, the drying is one-step drying at a temperature of 50-350 ℃.
Preferably, in the second step of the preparation method of the silicon-based negative electrode sheet, the drying is multi-step drying at a temperature of 50-350 ℃.
According to a third aspect of the present invention, there is provided a battery comprising the above silicon-based negative electrode sheet. By using the silicon-based negative plate, the silicon-based negative plate has lower thickness expansion rate, so that the whole battery has lower thickness expansion rate in the charge and discharge processes, and the cycling stability of the battery is improved.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
Example 1
The adhesive used in this example comprises a mixture of component a and carboxylbutylene rubber (carboxyl modified SBR, solids content 50%), component a comprising a complex of chitosan and lithium carboxymethyl cellulose, and/or component a comprising a complex of chitosan and lithium carboxymethyl cellulose. Wherein the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:1.5.
(1) Preparation of silicon-based negative plate
The silicon-based negative electrode sheet is prepared according to the following method:
s1, mixing 0.5 part of chitosan with water, and then regulating the obtained mixed system to be clear by using acid to obtain a chitosan aqueous solution; the chitosan has a number average molecular weight of 45 ten thousand and a degree of deacetylation of 90%;
s2, adding 1.5 parts of lithium carboxymethyl cellulose into the chitosan aqueous solution, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; in the glue solution mixed solution, the mass ratio of the addition of the mass of the chitosan and the mass of the lithium carboxymethyl cellulose in the glue solution mixed solution is 2wt%;
s3, sequentially adding 3 parts of conductive carbon black Super-P, 92 parts of silicon carbon active material and 3 parts of carboxyl modified SBR (carboxyl styrene butadiene rubber) into the glue solution mixed solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, necessary water can be additionally added to regulate the viscosity to 2000-4000 CP when necessary, and the rotating speed is reduced to about 350rpm after carboxyl modified SBR is added;
s4, coating the obtained negative electrode slurry on a copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, and rolling to obtain the silicon-based negative electrode plate.
(2) Preparation of lithium ion batteries
Lithium sheet is used as positive plate, microporous polypropylene film is used as diaphragm, and 1mol/L LiPF 6 (the solvent is equal volume of dimethyl carbonate and dipropyl carbonate) as electrolyte, and the silicon-based anodeThe sheets were assembled into button lithium ion batteries in an argon filled glove box.
Example 2
The adhesive used in this example comprises a mixture of component a and carboxylbutylene rubber (carboxyl modified SBR, solids content 50%), component a comprising a complex of chitosan and lithium carboxymethyl cellulose, and/or component a comprising a complex of chitosan and lithium carboxymethyl cellulose. Wherein the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:1.25.
(1) Preparation of silicon-based negative plate
The silicon-based negative electrode sheet is prepared according to the following method:
s1, mixing 1 part of chitosan with water, and then regulating the obtained mixed system to be clear by using acid to obtain a chitosan aqueous solution; the chitosan has a number average molecular weight of 45 ten thousand and a degree of deacetylation of 90%;
s2, adding 1 part of lithium carboxymethyl cellulose into the chitosan aqueous solution, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; in the glue solution mixed solution, the mass ratio of the addition of the mass of the chitosan and the mass of the lithium carboxymethyl cellulose in the glue solution mixed solution is 2wt%;
s3, sequentially adding 1.5 parts of conductive carbon black Super-P, 94 parts of silicon carbon active material and 2.5 parts of carboxyl modified SBR (carboxyl styrene butadiene rubber) into the glue solution mixed solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, necessary water can be additionally added to regulate the viscosity to 2000-4000 CP when necessary, and the rotating speed is reduced to about 350rpm after carboxyl modified SBR is added;
s4, coating the obtained negative electrode slurry on a copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, and rolling to obtain the silicon-based negative electrode plate.
(2) Preparation of lithium ion batteries
The preparation of the lithium ion battery in this example was identical to that of example 1.
Example 3
(1) Preparation of silicon-based negative plate
The adhesive used in this example comprises a mixture of component a and carboxylbutylene rubber (carboxyl modified SBR, solids content 50%), component a comprising a complex of chitosan and lithium carboxymethyl cellulose, and/or component a comprising a complex of chitosan and lithium carboxymethyl cellulose. Wherein the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:1.25.
The silicon-based negative electrode sheet is prepared according to the following method:
s1, mixing 1 part of chitosan with water, and then regulating the obtained mixed system to be clear by using acid to obtain a chitosan aqueous solution;
s2, adding 1 part of lithium carboxymethyl cellulose into the chitosan aqueous solution, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; in the glue solution mixed solution, the mass ratio of the addition of the mass of the chitosan and the mass of the lithium carboxymethyl cellulose in the glue solution mixed solution is 2wt%;
s3, sequentially adding 1.5 parts of conductive carbon black Super-P, 94 parts of silicon carbon active material and 2.5 parts of carboxyl modified SBR (carboxyl styrene butadiene rubber) into the glue solution mixed solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, necessary water can be additionally added to regulate the viscosity to 2000-4000 CP when necessary, and the rotating speed is reduced to about 350rpm after carboxyl modified SBR is added;
s4, coating the obtained negative electrode slurry on copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, continuously performing heat treatment in the vacuum oven at 150 ℃ for 2 hours, and rolling to obtain the silicon-based negative electrode sheet.
(2) Preparation of lithium ion batteries
The preparation of the lithium ion battery in this example was identical to that of example 1.
Example 4
This example differs from example 2 in that the mass ratio of component A to carboxylated styrene-butadiene rubber is 1:0.2; the remainder was identical to example 2.
Example 5
This example differs from example 2 in that the mass ratio of component A to carboxylated styrene-butadiene rubber is 1:5; the remainder was identical to example 2.
Example 6
This example differs from example 2 in that in S1, the molecular weight of chitosan used was 15 ten thousand and the degree of deacetylation was 90%; the remainder was identical to example 2.
Example 7
This example differs from example 2 in that in S1, the molecular weight of chitosan used was 30 ten thousand and the degree of deacetylation was 90%; the remainder was identical to example 2.
Example 8
This example differs from example 2 in that in S1, the molecular weight of chitosan used was 60 ten thousand and the degree of deacetylation was 90%; the remainder was identical to example 2.
Comparative example 1
The adhesive used in the comparative example comprises sodium carboxymethyl cellulose and carboxyl styrene-butadiene rubber (carboxyl modified SBR, solid content is 50%), and the mass ratio of the sodium carboxymethyl cellulose to the carboxyl styrene-butadiene rubber is 1:1.
(1) Preparation of silicon-based negative plate
The comparative example was prepared as follows:
s1, adding 6 parts of sodium carboxymethyl cellulose into water, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; in the glue solution mixed solution, the mass fraction of sodium carboxymethyl cellulose is 2wt%;
s2, sequentially adding 3 parts of conductive carbon black Super-P, 85 parts of silicon carbon active material and 6 parts of carboxyl modified SBR (carboxyl styrene butadiene rubber) into the glue solution mixed solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, necessary water can be additionally added to regulate the viscosity to 2000-4000 CP when necessary, and the rotating speed is reduced to about 350rpm after carboxyl modified SBR is added;
s3, coating the obtained negative electrode slurry on a copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, and rolling to obtain the silicon-based negative electrode plate.
(2) Preparation of lithium ion batteries
The preparation of the lithium ion battery in this comparative example was identical to that of example 1.
Comparative example 2
(1) Preparation of silicon-based negative plate
The comparative example was prepared as follows:
the adhesive used in this comparative example comprises lithium carboxymethyl cellulose and carboxyl styrene-butadiene rubber (carboxyl modified SBR, solid content is 50%), and the mass ratio of the lithium carboxymethyl cellulose to the carboxyl styrene-butadiene rubber is 1:1.25.
The silicon-based negative electrode sheet is prepared according to the following method:
s1, adding 2 parts of lithium carboxymethyl cellulose into water, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; in the glue solution mixed solution, the mass fraction of sodium carboxymethyl cellulose is 2wt%;
s2, sequentially adding 1.5 parts of conductive carbon black Super-P, 94 parts of silicon carbon active material and 2.5 parts of carboxyl modified SBR (carboxyl styrene butadiene rubber) into the glue solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, necessary water can be additionally added to regulate the viscosity to 2000-4000 CP when necessary, and the rotating speed is reduced to about 350rpm after carboxyl modified SBR is added;
s3, coating the obtained negative electrode slurry on a copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, and rolling to obtain the silicon-based negative electrode plate.
(2) Preparation of lithium ion batteries
The preparation of the lithium ion battery in this comparative example was identical to that of example 1.
Comparative example 3
The binder used in this comparative example was only component a, which included a mixture of chitosan and lithium carboxymethyl cellulose, and/or component a included a complex of chitosan and lithium carboxymethyl cellulose.
(1) Preparation of silicon-based negative plate
The comparative example was prepared as follows:
s1, mixing 2.25 parts of chitosan with water, and then regulating the obtained mixed system to be clear by using acid to obtain a chitosan aqueous solution;
s2, adding 2.25 parts of lithium carboxymethyl cellulose into the chitosan aqueous solution, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; the mass fraction of the chitosan modified carboxymethyl cellulose lithium in the glue solution mixed solution is 2wt%;
s3, sequentially adding 1.5 parts of conductive carbon black Super-P and 94 parts of silicon carbon active material into the glue solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, and necessary water can be additionally added to regulate the viscosity to 2000-4000 CP if necessary;
s4, coating the obtained negative electrode slurry on a copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, and rolling to obtain the silicon-based negative electrode plate.
(2) Preparation of lithium ion batteries
The preparation of the lithium ion battery in this comparative example was identical to that of example 1.
Comparative example 4
The adhesive used in this example comprises a component a, a carboxylated styrene-butadiene rubber (carboxyl modified SBR, solids content 50%), a mixture of chitosan and lithium carboxymethyl cellulose, and/or a composite of chitosan and lithium carboxymethyl cellulose. Wherein the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:0.1.
(1) Preparation of silicon-based negative plate
The comparative example was prepared as follows:
s1, mixing 0.28 part of chitosan with water, and then regulating the obtained mixed system to be clear by using acid to obtain a chitosan aqueous solution;
s2, adding 0.28 part of carboxymethyl cellulose lithium into the chitosan aqueous solution, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; in the glue solution mixed solution, the mass ratio of the addition of the mass of the chitosan and the mass of the lithium carboxymethyl cellulose in the glue solution mixed solution is 2wt%;
s3, sequentially adding 1.5 parts of conductive carbon black Super-P, 94 parts of silicon carbon active material and 3.94 parts of carboxyl modified SBR (carboxyl styrene butadiene rubber) into the glue solution mixed solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, necessary water can be additionally added to regulate the viscosity to 2000-4000 CP when necessary, and the rotating speed is reduced to about 350rpm after carboxyl modified SBR is added;
s4, coating the obtained negative electrode slurry on a copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, and rolling to obtain the silicon-based negative electrode plate.
(2) Preparation of lithium ion batteries
The preparation of the lithium ion battery in this comparative example was identical to that of example 1.
Comparative example 5
The adhesive used in this example comprises a component a, a carboxylated styrene-butadiene rubber (carboxyl modified SBR, solids content 50%), a mixture of chitosan and lithium carboxymethyl cellulose, and/or a composite of chitosan and lithium carboxymethyl cellulose. Wherein the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:7.
(1) Preparation of silicon-based negative plate
The comparative example was prepared as follows:
s1, mixing 0.28 part of chitosan with water, and then regulating the obtained mixed system to be clear by using acid to obtain a chitosan aqueous solution;
s2, adding 0.28 part of carboxymethyl cellulose lithium into the chitosan aqueous solution, and stirring and mixing at a rotating speed of 600rpm to obtain a glue solution mixed solution; in the glue solution mixed solution, the mass ratio of the addition of the mass of the chitosan and the mass of the lithium carboxymethyl cellulose in the glue solution mixed solution is 2wt%;
s3, sequentially adding 1.5 parts of conductive carbon black Super-P, 94 parts of silicon carbon active material and 3.94 parts of carboxyl modified SBR (carboxyl styrene butadiene rubber) into the glue solution mixed solution, and uniformly mixing to obtain negative electrode slurry; wherein, each component is uniformly dispersed, necessary water can be additionally added to regulate the viscosity to 2000-4000 CP when necessary, and the rotating speed is reduced to about 350rpm after carboxyl modified SBR is added;
s4, coating the obtained negative electrode slurry on a copper foil with the thickness of 120 mu m, completely drying in a vacuum oven at 70 ℃, and rolling to obtain the silicon-based negative electrode plate.
(2) Preparation of lithium ion batteries
The preparation of the lithium ion battery in this comparative example was identical to that of example 1.
Comparative example 6
This example differs from example 2 in that in S1, the molecular weight of chitosan used was 10 ten thousand and the degree of deacetylation was 90%; the remainder was identical to example 2.
Comparative example 7
This example differs from example 2 in that in S1, the molecular weight of chitosan used was 75 ten thousand and the degree of deacetylation was 90%; the remainder was identical to example 2.
Test case
1. Experimental construction mode
(1) Lithium ion battery performance test
(1) First capacity and first efficiency test: standing the button lithium ion battery for more than 24 hours, and then performing a charge and discharge test, wherein the charge and discharge interval is between 0.01 and 3.0V; the first-turn discharge specific capacity is taken as the first capacity; the first-effect calculation formula is as follows: first effect (%) =first charge specific capacity/first-turn discharge specific capacity×100%.
(2) Capacity retention test: the percentage value of the specific charge capacity after cycling for a specific number of turns at a specified multiplying power and the first round of specific charge capacity at 0.05C;
(2) And (3) pole piece thickness variation test: measuring the thickness t0 of the current collector of the pole piece after baking, the thickness t1 of the pole piece, assembling the battery, recycling the battery for 1 circle, recharging to 3V, transferring into an inert atmosphere glove box, disassembling the battery, taking out the silicon-based pole piece, measuring the thickness t2 of the full-electric-state silicon-based pole piece by using an insulating thickness gauge, and calculating the thickness expansion rate (%) of the battery in the following manner: (t 2-t 1)/(t 1-t 0). Times.100%.
2. Experimental results
The properties of the batteries prepared in examples 1 to 8 and comparative examples 1 to 7 and the data of the thickness expansion ratio thereof are shown in table 1.
Table 1 battery performance and thickness expansion ratio data thereof in examples 1 to 8 and comparative examples 1 to 7
As can be seen from the test data in table 1, the specific capacity, initial efficiency and capacity retention rate of the battery can be effectively improved by adopting the silicon-based negative electrode binder in the scheme, and the thickness expansion rate of the negative electrode sheet can be reduced, and specific reference can be made to examples 1 to 8. The silicon-based negative electrode binder in the scheme not only has better bonding strength and flexibility, but also inhibits thickening, cracking and pulverization of an SEI film formed on the surface of a negative electrode, simultaneously provides expansion space for volume expansion of a silicon-based negative electrode active material, improves structural stability of a silicon-based negative electrode active material layer, reduces thickness variation of a silicon-based electrode plate, and improves battery cycle stability, capacity retention rate and rate capability. Meanwhile, the silicon-based negative electrode binder in the scheme can also play a role in pre-supplementing lithium to the silicon-based negative electrode material, so that the first effect of the battery is further improved.
Further comparing examples 2, 6 to 8 with comparative examples 6 to 7, and the binders of comparative examples 6 and 7, wherein the molecular weight of the chitosan used in example 4 is small, which results in insufficient viscosity of the silicon-based anode binder of comparative example 6, and thus the structural stability of the anode active material layer is not improved well, and the specific capacity, initial efficiency, capacity retention rate and other properties of the battery are reduced; while the molecular weight of the chitosan used in comparative example 7 is large, although the composite silicon-based negative electrode adhesive can highly improve the structural stability of the negative electrode active material, the excessive viscosity leads to too small pores in the negative electrode active material layer, and the lithium ion transmission efficiency is reduced, resulting in a reduction in the specific capacity, initial efficiency, capacity retention rate and other performances of the battery.
In the adhesives of comparative examples 1 and 2, since the adhesive was not modified with chitosan, the adhesive strength and flexibility of the adhesive were lowered, resulting in a decrease in the structural stability of the negative electrode active material layer, and finally, a significant decrease in the specific capacity, initial efficiency, capacity retention rate, and the like of the battery. And in comparative example 1, sodium carboxymethyl cellulose is used to replace lithium carboxymethyl cellulose, and pre-lithium supplement cannot be provided in the cycle process of the battery, so that the specific capacity, initial efficiency, capacity retention rate and other performances of the battery in comparative example 1 are lower than those of the battery in comparative example 2.
In the binder of comparative example 3, only the chitosan carboxymethyl cellulose lithium was used, which also resulted in a decrease in the performance of the binder, and the stability of the negative electrode active material layer was also decreased, resulting in a corresponding decrease in the specific capacity, initial efficiency, and capacity retention rate of the battery.
In the adhesives of comparative examples 4 and 5, the component a of comparative examples 4 and 5 is too much and too little, respectively, which results in the decrease of the specific capacity, the first effect and the capacity retention rate of the battery, which indicates that the component a and the carboxyl styrene-butadiene rubber can have a better collocation effect under a certain mass ratio, which is more beneficial to considering the structural stability and the lithium ion transmission performance of the anode active material layer and improving the specific capacity, the first effect and the capacity retention rate of the battery.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention, but these modifications or substitutions are all within the scope of the present invention.
Claims (10)
1. A silicon-based negative electrode binder is characterized in that: the adhesive comprises a component A and carboxyl styrene-butadiene rubber; the component A comprises a mixture of chitosan and lithium carboxymethyl cellulose, and/or the component A comprises a compound of chitosan and lithium carboxymethyl cellulose; the mass ratio of the component A to the carboxyl styrene-butadiene rubber is 1:0.2-5.
2. The silicon-based anode binder of claim 1, wherein when the component a comprises a complex of chitosan and lithium carboxymethyl cellulose, the preparation process of the complex comprises the following operations:
s1, mixing chitosan with water, and regulating the pH value to obtain a clarified chitosan aqueous solution;
s2, adding the carboxymethyl cellulose lithium into the chitosan aqueous solution obtained by prefabrication of the S1.
3. The silicon-based anode binder of claim 2, wherein: the chitosan has a number average molecular weight of 15-65 ten thousand and a deacetylation degree of 80-98%.
4. The silicon-based anode binder of claim 2, wherein: the chitosan accounts for 0.01 to 8 weight percent of the mass of the chitosan aqueous solution.
5. The silicon-based anode binder of claim 1, wherein: the mass ratio of the chitosan to the lithium carboxymethyl cellulose is 0.05-0.7: 1.5.
6. the silicon-based anode binder of claim 1, wherein: the adhesive also comprises at least one of styrene-butadiene rubber, sodium carboxymethyl cellulose and polyurethane acrylate.
7. A silicon-based negative electrode sheet, characterized in that: the silicon-based negative electrode sheet comprises the silicon-based negative electrode binder according to any one of claims 1 to 6 and a silicon-based negative electrode active material comprising at least one of Si, siO, si/C, siO/C.
8. The silicon-based negative electrode sheet of claim 7, wherein: the silicon-based negative plate further comprises a conductive agent, wherein the conductive agent comprises at least one of conductive carbon black, carbon nanotubes, graphene, modified graphene and graphite oxide.
9. The silicon-based negative electrode sheet according to claim 7, wherein the preparation method comprises the steps of:
preparing a silicon-based anode active material, a conductive agent, a silicon-based anode binder and a solvent into anode slurry;
step two, coating the negative electrode slurry on a current collector, and drying and rolling to prepare a silicon-based negative electrode plate;
in the first step, the mass ratio of the silicon-based anode active material to the conductive agent to the silicon-based anode binder is 80-95: 1 to 6:2 to 15.
10. A battery, characterized in that: a silicon-based negative electrode sheet comprising the silicon-based negative electrode sheet according to any one of claims 7 to 9.
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| CN117936793A (en) * | 2024-03-21 | 2024-04-26 | 深圳中芯能科技有限公司 | Sodium-electricity negative electrode modified binder, preparation method, negative plate and sodium battery |
| CN118016893A (en) * | 2024-04-08 | 2024-05-10 | 深圳中芯能科技有限公司 | Sodium-electricity negative electrode binder, sodium-electricity negative electrode sheet and sodium-ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117936793A (en) * | 2024-03-21 | 2024-04-26 | 深圳中芯能科技有限公司 | Sodium-electricity negative electrode modified binder, preparation method, negative plate and sodium battery |
| CN118016893A (en) * | 2024-04-08 | 2024-05-10 | 深圳中芯能科技有限公司 | Sodium-electricity negative electrode binder, sodium-electricity negative electrode sheet and sodium-ion battery |
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