CN114725313B - Silicon-based negative plate and preparation method and application thereof - Google Patents
Silicon-based negative plate and preparation method and application thereof Download PDFInfo
- Publication number
- CN114725313B CN114725313B CN202210422835.0A CN202210422835A CN114725313B CN 114725313 B CN114725313 B CN 114725313B CN 202210422835 A CN202210422835 A CN 202210422835A CN 114725313 B CN114725313 B CN 114725313B
- Authority
- CN
- China
- Prior art keywords
- silicon
- negative electrode
- electrode sheet
- polyacrylic acid
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 36
- 239000010703 silicon Substances 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 34
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 32
- 229920005596 polymer binder Polymers 0.000 claims description 30
- 239000002491 polymer binding agent Substances 0.000 claims description 30
- 239000004584 polyacrylic acid Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- 229920001732 Lignosulfonate Polymers 0.000 claims description 17
- 235000019357 lignosulphonate Nutrition 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 239000002409 silicon-based active material Substances 0.000 claims description 13
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- -1 polypropylene Polymers 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002916 wood waste 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 silicon-based negative electrode plate, a preparation method and application thereof. The invention provides a silicon-based negative plate, a preparation method and application thereof, and solves the technical problem of poor cycle performance caused by volume effect in the charging and discharging process of a silicon-based electrode.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-based negative electrode sheet and a preparation method and application thereof.
Background
At present, energy used by people is mainly concentrated on fossil energy sources such as coal, petroleum, natural gas and the like, but with the development of society and the massive consumption of resources, the energy sources and the environmental problems continuously draw great attention to the society. The lithium ion battery is used as a new generation of green secondary battery, and is widely applied to various fields such as electric automobiles, small-sized mobile household electrical appliance power supplies, power grids, traffic, electronic products and the like due to the advantages of higher voltage, higher energy density, longer cycle life and the like.
Along with the continuous improvement of the requirements of people on high-power energy storage devices, the graphite carbon cathode material serving as a lithium ion battery at present can not meet the use requirements of high energy density and high power density. In the aspect of the novel lithium ion battery cathode material, the theoretical specific capacity of the silicon cathode material is up to 4200 mAh/g, which is 10 times of that of the traditional graphite cathode. In addition, the material has abundant resource and low cost, and becomes a potential next-generation high-capacity anode material. However, the silicon anode material has the following main problems, which restrict the large-scale application: 1. when lithium ions are inserted into/extracted from the silicon material, huge volume change of the material occurs, so that the material is pulverized, the electric contact among Si particles is reduced, and finally the cycle life is greatly reduced; 2. in the circulation process, the huge volume change of the Si material causes the solid electrolyte membrane generated by the reaction of the surface of the silicon particles and the electrolyte to be continuously broken, so that the fresh surface of the Si material is continuously exposed in the electrolyte, a new solid electrolyte membrane is formed, and the coulomb efficiency, the circulation and the multiplying power performance of the battery are reduced.
The adhesive in the lithium ion battery can maintain the structural integrity of the electrode in the charge-discharge process, so that the selection of a proper adhesive with good strength is beneficial to inhibiting the volume expansion effect of the silicon negative electrode, and the lithium ion battery applying the silicon negative electrode plate is ensured to have longer cycle life.
Disclosure of Invention
The invention provides a silicon-based negative plate, a preparation method and application thereof, and solves the technical problem that the cycle performance is severely reduced due to the volume effect in the charging and discharging process of a silicon-based electrode.
The invention provides a silicon-based negative plate which comprises a silicon-based active material, a water-based polymer binder and a conductive agent, wherein the water-based polymer binder comprises polyacrylic acid, sulfonated lignin and metal ions, and the silicon-based active material and the water-based polymer binder form a multi-crosslinked network structure.
Further, the mass ratio of the polyacrylic acid to the sulfonated lignin is 10:1-1:10.
Further, the metal ion is Zr 4+ 。
Further, the Zr is 4+ Accounting for 0-10% of the weight of the water-based polymer binder.
Further, the polyacrylic acid is linear polyacrylic acid.
The invention also provides a preparation method of the water-based polymer binder, which comprises the following steps:
s1: dissolving acrylic acid in water, adding an ammonium persulfate initiator to obtain a polyacrylic acid solution, and dehydrating and drying the polyacrylic acid solution;
s2: dissolving sulfonated lignin and dried polyacrylic acid in deionized water, adding a metal ion solution, mixing and stirring uniformly to prepare a water-based polymer binder;
s3: and adding a silicon-based active material and a conductive agent into the aqueous polymer binder solution, stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the surface of a copper foil to prepare a negative electrode plate.
S4: drying and thermally esterifying the negative electrode sheet obtained in the step S3 at the temperature of 100-200 ℃ for 4-12 hours to obtain a dried negative electrode sheet;
s5: the dried negative electrode sheet is placed in a glove box filled with argon, and assembled into a button cell by taking a metal lithium sheet as a counter electrode, EC: EDC=1:1 as electrolyte and polypropylene as a diaphragm.
Further, the silicon-based active material in S3 is one of silicon, silicon oxide, and silicon-carbon composite.
Further, ethanol is added into the polyacrylic acid solution in the step S1 for washing, so as to remove unreacted acrylic acid and ammonium persulfate initiator.
Further, stirring is continuously carried out at a speed of 300 rpm-800 rpm in the step S3 for 1 h-10 h.
The invention also provides application of the lithium ion battery, and the silicon-based negative plate is used in the field of lithium ion batteries.
From the above technical scheme, the invention has the following advantages:
the silicon-based negative electrode substrate comprises a silicon-based active material, an aqueous polymer binder and a conductive agent, wherein the aqueous polymer binder comprises polyacrylic acid, sulfonated lignin and metal ions. Firstly, in the water-based polymer binder, in addition to the hydrogen bonding effect, hydroxyl groups of sulfonated lignin and carboxyl groups of polyacrylic acid can form covalent crosslinking structures through high-temperature esterification; and the metal ions can form coordination crosslinking with carboxyl groups of polyacrylic acid and sulfonic groups of sulfonated lignin, so that the water-based polymer binder forms a multi-crosslinking network structure. Secondly, between the silicon-based active material and the water-based polymer binder, the carboxyl of the polypropylene, the hydroxyl of the sulfonated lignin and the hydroxyl on the surface of the silicon-based active material can form hydrogen bonding, and enhanced covalent cross-linking bonds are formed through high-temperature thermal esterification, so that the silicon-based active material and the water-based polymer binder further form a multi-cross-linking network structure. The multi-crosslinked network structure is high in strength, the volume effect of the silicon-based negative electrode plate during charge and discharge can be effectively restrained, the cycle performance of the silicon-based negative electrode plate is improved, and the silicon-based negative electrode plate has longer cycle life while maintaining higher specific capacity. Meanwhile, the preparation process of the water-based polymer binder avoids the use of organic solvents, and is environment-friendly. The lithium ion battery prepared by the silicon-based negative plate has the characteristics of high energy density, high specific capacity and long cycle life.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a cyclic voltammogram of a cell obtained in accordance with an embodiment of the present invention;
fig. 2 is a graph showing constant current charge and discharge cycle performance of the battery obtained in the first embodiment and the fourth embodiment of the present invention.
1-first cycle of cyclic voltammetry, 2-second cycle of cyclic voltammetry.
Detailed Description
In order to make the objects, features and advantages of the present invention more comprehensible, the technical solutions in the embodiments of the present invention are described in detail below with reference to the accompanying drawings, and it is apparent that the embodiments described below are only some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
a preparation method of a lithium ion battery based on a silicon-based negative plate comprises the following steps:
s1: weighing 10mL Acrylic Acid (AA), placing the Acrylic Acid (AA) into a reaction bottle filled with 100 mL water, adding 0.01 g ammonium persulfate initiator, continuously stirring at 60 ℃ for 12 h, washing the obtained polyacrylic acid (PAA) with ethanol for 2-3 times after the reaction is finished, removing unreacted acrylic acid monomer and ammonium persulfate initiator, drying the obtained polyacrylic acid (PAA) at 50 ℃ by using a blast drying box to remove water, and drying for later use;
s2: 0.02. 0.02 g polyacrylic acid (PAA) was weighed, sulfonated lignin (MZS) and polyacrylic acid (PAA) were formulated in a mass ratio of 1:1, and mixed in 600. Mu.L deionized water, and 1wt% Zr was added 4+ Stirring uniformly to obtain a water-based polymer binder;
s3: weighing ball-milled silicon oxide and conductive agent, mixing at a mass ratio of 7:2 to obtain a mixture of 0.18: 0.18 g, adding PAA/MZS/Zr 4+ Stirring the solution at a rotation speed of 800 rpm for 10 h to carry out slurry mixing to obtain negative electrode slurry, and flatly coating the negative electrode slurry on a copper foil to obtain a negative electrode plate;
s4: drying and thermally esterifying the negative electrode sheet obtained in the step S3 at 200 ℃ for 10 h, and shearing the dried negative electrode sheet into a negative electrode sheet with the diameter of 14 mm;
s5: the negative electrode sheet of 14 mm was placed in a glove box filled with argon, and assembled into a button cell using a metallic lithium sheet as a counter electrode, EC: edc=1:1 as an electrolyte (containing 6wt% lipf 6), and polypropylene (PP) as a separator.
Comparative example one:
s1: weighing 10mL Acrylic Acid (AA), placing the Acrylic Acid (AA) into a reaction bottle filled with 100 mL water, adding 0.01 g ammonium persulfate initiator, continuously stirring at 60 ℃ for 12 h, washing the obtained polyacrylic acid (PAA) with ethanol for 2-3 times after the reaction is finished, removing unreacted acrylic acid monomer and ammonium persulfate initiator, drying the obtained polyacrylic acid (PAA) at 50 ℃ by using a blast drying box to remove water, and drying for later use;
s2: 0.02. 0.02 g polyacrylic acid (PAA) was weighed, the polyacrylic acid (PAA) and sulfonated lignin (MZS) were formulated in a mass ratio of 1:1, and mixed in 600. Mu.L deionized water, and 1wt% Zr was added 4+ Stirring uniformly to obtain a water-based polymer binder;
s3: weighing ball-milled silicon oxide and conductive agent, mixing at a mass ratio of 7:2 to obtain a mixture of 0.18: 0.18 g, adding PAA/MZS/Zr 4+ Stirring the solution at a rotation speed of 800 rpm for 10 h to carry out slurry mixing to obtain negative electrode slurry, and flatly coating the negative electrode slurry on a copper foil to obtain a negative electrode plate;
s4: drying the negative electrode sheet obtained in the step S3 at 40 ℃ for 10 h, and shearing the dried negative electrode sheet into a negative electrode sheet with the diameter of 14 mm;
s5: the negative electrode sheet of 14 mm was placed in a glove box filled with argon, and assembled into a button cell using a metallic lithium sheet as a counter electrode, EC: edc=1:1 as an electrolyte (containing 6wt% lipf 6), and polypropylene (PP) as a separator.
Embodiment two:
s1: weighing 10mL Acrylic Acid (AA), placing the Acrylic Acid (AA) into a reaction bottle filled with 100 mL water, adding 0.01 g ammonium persulfate initiator, continuously stirring at 60 ℃ for 12 h, washing the obtained polyacrylic acid (PAA) with ethanol for 2-3 times after the reaction is finished, removing unreacted acrylic acid monomer and ammonium persulfate initiator, drying the obtained polyacrylic acid (PAA) at 50 ℃ by using a blast drying box to remove water, and drying for later use;
s2: weighing 0.02 g of polyacrylic acid (PAA), preparing the polyacrylic acid (PAA) and sulfonated lignin (MZS) according to the mass ratio of 1:1, mixing the polyacrylic acid and the sulfonated lignin with 600 mu L of deionized water, and uniformly stirring to obtain a mixture;
s3: weighing ball-milled silicon oxide and a conductive agent, mixing in a mass ratio of 7:2 to obtain a mixture 0.18 g, adding the mixture obtained in the step S2, stirring 10 h at a rotation speed of 800 rpm for slurry mixing to obtain a negative electrode slurry, and flatly coating the negative electrode slurry on a copper foil;
s4: drying and thermally esterifying the negative electrode sheet obtained in the step S3 at 200 ℃ for 10 h, shearing the dried negative electrode sheet into a negative electrode sheet with the diameter of 14 mm,
s5: the negative electrode sheet of 14 mm was placed in a glove box filled with argon, and assembled into a button cell using a metallic lithium sheet as a counter electrode, EC: edc=1:1 as an electrolyte (containing 6wt% lipf 6), and polypropylene (PP) as a separator.
Comparative example two:
s1: weighing 10mL of Acrylic Acid (AA), placing the Acrylic Acid (AA) into a reaction bottle filled with 100 mL water, adding 0.01 g ammonium persulfate initiator, continuously stirring at 60 ℃ for 12 h, washing the obtained polyacrylic acid (PAA) with ethanol for 2-3 times after the reaction is finished, removing unreacted acrylic acid monomer and ammonium persulfate initiator, drying the obtained polyacrylic acid (PAA) at 50 ℃ by using a forced air drying box to remove water, and drying for later use;
s2: weighing 0.02 g of polyacrylic acid (PAA), preparing the polyacrylic acid (PAA) and sulfonated lignin (MZS) according to the mass ratio of 1:1, mixing the polyacrylic acid and the sulfonated lignin with 600 mu L of deionized water, and uniformly stirring to obtain a mixture;
s3: weighing ball-milled silicon oxide and a conductive agent, mixing in a mass ratio of 7:2 to obtain a mixture 0.18 g, adding the mixture into the mixture obtained in the step S2, stirring at a rotating speed of 800 rpm for 10 h to carry out slurry mixing to obtain negative electrode slurry, and flatly coating the negative electrode slurry on a copper foil;
s4: drying the negative electrode sheet obtained in the step S3 at 40 ℃ for 10 h, and shearing the dried negative electrode sheet into a negative electrode sheet with the diameter of 14 mm;
s5: the negative electrode sheet of 14 mm was placed in a glove box filled with argon, and assembled into a button cell using a metallic lithium sheet as a counter electrode, EC: edc=1:1 as an electrolyte (containing 6wt% lipf 6), and polypropylene (PP) as a separator.
Comparative example three:
s1: weighing 10mL Acrylic Acid (AA), placing the Acrylic Acid (AA) into a reaction bottle filled with 100 mL water, adding 0.01 g ammonium persulfate initiator, continuously stirring at 60 ℃ for 12 h, washing the obtained polyacrylic acid (PAA) with ethanol for 2-3 times after the reaction is finished, removing unreacted acrylic acid monomer and ammonium persulfate initiator, drying the obtained polyacrylic acid (PAA) at 50 ℃ by using a blast drying box to remove water, and drying for later use;
s2: weighing 0.02 g of polyacrylic acid (PAA) obtained in the step S1, and mixing the weighed 0.02 g with 600 mu L of deionized water to prepare PAA solution;
s3: weighing ball-milled silicon oxide and a conductive agent, mixing in a mass ratio of 7:2 to obtain a mixture 0.18: 0.18 g, adding PAA solution, stirring at a rotating speed of 800 rpm for 10: 10 h to carry out slurry mixing, and flatly coating the uniformly mixed slurry on a copper foil;
s4: drying and thermally esterifying the negative electrode sheet obtained in the step S3 at 200 ℃ for 10 h, and shearing the dried negative electrode sheet into a negative electrode sheet with the diameter of 14 mm;
s5: the negative electrode sheet of 14 mm was placed in a glove box filled with argon, and assembled into a button cell using a metallic lithium sheet as a counter electrode, EC: edc=1:1 as an electrolyte (containing 6wt% lipf 6), and polypropylene (PP) as a separator.
Comparative example four:
s1: weighing 10mL Acrylic Acid (AA), placing the Acrylic Acid (AA) into a reaction bottle filled with 100 mL water, adding 0.01 g ammonium persulfate initiator, continuously stirring at 60 ℃ for 12 h, washing the obtained polyacrylic acid (PAA) with ethanol for 2-3 times after the reaction is finished, removing unreacted acrylic acid monomer and ammonium persulfate initiator, drying the obtained polyacrylic acid (PAA) at 50 ℃ by using a blast drying box to remove water, and drying for later use;
s2: weighing 0.02 g of polyacrylic acid (PAA) obtained in the step S1, and mixing the weighed 0.02 g with 600 mu L of deionized water to prepare PAA solution;
s3: weighing ball-milled silicon oxide and a conductive agent, mixing in a mass ratio of 7:2 to obtain a mixture 0.18: 0.18 g, adding PAA solution, stirring at a rotating speed of 800 rpm for 10: 10 h to carry out slurry mixing, and flatly coating the uniformly mixed slurry on a copper foil;
s4: drying the negative electrode sheet obtained in the step S3 at 40 ℃ for 10 h, and shearing the dried negative electrode sheet into a negative electrode sheet with the diameter of 14 mm;
s5: the negative electrode sheet of 14 mm was placed in a glove box filled with argon, and assembled into a button cell using a metallic lithium sheet as a counter electrode, EC: edc=1:1 as an electrolyte (containing 6wt% lipf 6), and polypropylene (PP) as a separator.
The battery obtained in the first example was subjected to cyclic voltammetry, and as shown in fig. 1, a reduction peak was observed at about 0.2 and V, and an oxidation peak was observed at about 0.55 and V. From curves 1 and 2, the two-cycle curves have high overlap ratio and stable curves, which indicates that the electrode reaction has good reversibility and good chemical stability during the charge and discharge cycle. The batteries obtained in the first and fourth examples were subjected to constant current charge and discharge tests, as shown in fig. 2, and it is clear from the graph that in the cycle test of 0.2A, the specific capacity of 1000 mAh/g was maintained after 100 cycles in the first example, which was higher than the specific capacity of 770 mAh/g in the fourth example, and the first example was brought into a steady cycle state earlier.
The two tests indicated that, in the cell prepared by example one, PAA/MZS/Zr 4+ The aqueous polymer binder forms a multi-crosslinking network through high-temperature thermal esterification and ion coordination crosslinking, and is applied to the silicon-based negative electrode of the lithium ion battery, so that the volume benefit of the electrode circulation process is effectively inhibited, and the circulation performance of the battery is remarkably improved.
In the invention, the sulfonated lignin is a water-soluble polymer, is derived from wood waste, is environment-friendly and low in cost, and can realize effective utilization of renewable resources. And the sulfonated lignin contains a large amount ofThe aromatic hydroxyl group of (C) and the silicon hydroxyl group of silicon oxide can be esterified with the carboxyl of PAA to form a Si-based-PAA-MZS cross-linked network structure with higher strength, and meanwhile, the strength of the Si-based-PAA-MZS cross-linked network structure is enhanced again through high-temperature esterification in the preparation process, so that the volume expansion of the silicon-based negative electrode sheet in use is effectively inhibited. The silicon-based negative plate prepared by the water-based polymer binder has the performances of high specific capacity, long service life, high capacity retention rate and the like. The water-based polymer binder is a water-based binder, so that the use of an organic solvent is avoided, and the water-based polymer binder has the effect of environmental protection. Further, by adding Zr to the aqueous polymer binder 4+ The multi-coordination crosslinking effect is added in the Si-based-PAA-MZS hydrogen bond crosslinking network formed by the silicon-based active material and the water-based polymer binder, so that the action strength between the silicon-based active material and the water-based polymer binder is greatly enhanced, and the cycle life of the silicon-based negative electrode plate is prolonged. And the formed multi-crosslinked network structure is further dried at high temperature for thermal esterification, so that the strength of the multi-crosslinked network structure can be obviously improved, and the cycle service life of the battery can be prolonged. And the PAA/MZS/Zr 4+ The preparation process of the water-based polymer binder is simple, and the water-based polymer binder with a multiple cross-linked network structure can be obtained through blending and heating.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The preparation method of the silicon-based negative plate is characterized by comprising the following steps of:
s1: dissolving acrylic acid in water, adding an ammonium persulfate initiator to obtain a polyacrylic acid solution, and dehydrating and drying the polyacrylic acid solution;
s2: dissolving sulfonated lignin and dried polyacrylic acid in deionized water, adding a metal ion solution, mixing and stirring uniformly to prepare a water-based polymer binder;
s3: adding a silicon-based active material and a conductive agent into the water-based polymer binder solution, stirring to obtain negative electrode slurry, and coating the negative electrode slurry on the surface of a copper foil to prepare a negative electrode plate;
s4: placing the negative electrode sheet obtained in the step S3 at a temperature of 100-200 ℃ for drying and thermal esterification for 4-12 hours to obtain a dried negative electrode sheet;
the silicon-based negative electrode sheet includes: the silicon-based active material and the water-based polymer binder form a multi-crosslinked network structure;
the polyacrylic acid is linear polyacrylic acid;
the metal ion is Zr 4+ ；
The mass ratio of the polyacrylic acid to the sulfonated lignin is 10:1-1:10;
the Zr is 4+ 0-10% by weight of the aqueous polymer binder, and the Zr 4+ The percentage by weight of the aqueous polymer binder is not 0.
2. The method for preparing a silicon-based negative electrode sheet according to claim 1, further comprising the steps of:
s5: and (3) placing the dried negative electrode sheet in a glove box filled with argon, and assembling the negative electrode sheet into a button cell by taking a metal lithium sheet as a counter electrode, EC: EDC=1:1 as electrolyte and polypropylene as a diaphragm.
3. The method for preparing a silicon-based negative electrode sheet according to claim 2, wherein the silicon-based active material in step S3 is one of silicon, silicon oxide, and silicon-carbon composite.
4. The method for preparing a silicon-based negative electrode sheet according to claim 2, wherein the polyacrylic acid solution in the step S1 is washed by adding ethanol for removing unreacted acrylic acid and ammonium persulfate initiator.
5. The method for preparing a silicon-based negative electrode sheet according to claim 2, wherein the stirring condition in the step S3 is that stirring is continued at a rotation speed of 300 rpm to 800 rpm of 1 h to 10 h.
6. A silicon-based negative electrode sheet, characterized by being produced by the production method as claimed in any one of claims 1 to 5.
7. The use of a silicon-based negative electrode sheet according to claim 6, wherein the silicon-based negative electrode sheet is used in the field of lithium ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210422835.0A CN114725313B (en) | 2022-04-21 | 2022-04-21 | Silicon-based negative plate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210422835.0A CN114725313B (en) | 2022-04-21 | 2022-04-21 | Silicon-based negative plate and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114725313A CN114725313A (en) | 2022-07-08 |
| CN114725313B true CN114725313B (en) | 2024-01-23 |
Family
ID=82246534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210422835.0A Active CN114725313B (en) | 2022-04-21 | 2022-04-21 | Silicon-based negative plate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114725313B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116804138B (en) * | 2023-08-18 | 2023-12-08 | 广东工业大学 | Polyacrylic acid and sodium lignin sulfonate composite binder for silicon-based negative electrode of lithium ion battery, and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010050429A (en) * | 2008-07-23 | 2010-03-04 | Toyo Ink Mfg Co Ltd | Binder composition for electric double-layer capacitor electrode, the electric double-layer capacitor electrode, and the electric double-layer capacitor |
| CN107641487A (en) * | 2017-10-24 | 2018-01-30 | 广东工业大学 | A kind of lignin/polyacrylate composite adhesive and preparation method thereof |
| CN107681158A (en) * | 2017-09-17 | 2018-02-09 | 亚士创能科技(上海)股份有限公司 | Lithium battery silicon based anode material self-healing binding agent, lithium battery silicon based anode material and preparation method thereof, GND and lithium battery |
| CN109301248A (en) * | 2017-07-24 | 2019-02-01 | 南方科技大学 | Battery cathode sheet and preparation method thereof and lithium ion battery |
| CN110061239A (en) * | 2018-03-20 | 2019-07-26 | 南方科技大学 | Lignin-base binder and preparation method thereof and lithium ion battery |
| CN110752370A (en) * | 2019-10-29 | 2020-02-04 | 广州鹏辉能源科技股份有限公司 | Binder, positive electrode slurry, positive plate and lithium ion battery |
| JP2020102322A (en) * | 2018-12-20 | 2020-07-02 | 太平洋セメント株式会社 | Positive electrode active material for secondary battery, and method for producing the same |
| CN111446426A (en) * | 2019-01-16 | 2020-07-24 | 通用汽车环球科技运作有限责任公司 | Method for manufacturing high performance electrode |
| JPWO2020241547A1 (en) * | 2019-05-31 | 2020-12-03 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120225199A1 (en) * | 2010-02-05 | 2012-09-06 | International Battery, Inc. | Current collector coating for li-ion battery cells using aqueous binder |
| WO2016210419A1 (en) * | 2015-06-26 | 2016-12-29 | Florida State University Research Foundation, Inc. | Dry process method for producing electrodes for electrochemical devices and electrodes for electrochemical devices |
-
2022
- 2022-04-21 CN CN202210422835.0A patent/CN114725313B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010050429A (en) * | 2008-07-23 | 2010-03-04 | Toyo Ink Mfg Co Ltd | Binder composition for electric double-layer capacitor electrode, the electric double-layer capacitor electrode, and the electric double-layer capacitor |
| CN109301248A (en) * | 2017-07-24 | 2019-02-01 | 南方科技大学 | Battery cathode sheet and preparation method thereof and lithium ion battery |
| CN107681158A (en) * | 2017-09-17 | 2018-02-09 | 亚士创能科技(上海)股份有限公司 | Lithium battery silicon based anode material self-healing binding agent, lithium battery silicon based anode material and preparation method thereof, GND and lithium battery |
| CN107641487A (en) * | 2017-10-24 | 2018-01-30 | 广东工业大学 | A kind of lignin/polyacrylate composite adhesive and preparation method thereof |
| CN110061239A (en) * | 2018-03-20 | 2019-07-26 | 南方科技大学 | Lignin-base binder and preparation method thereof and lithium ion battery |
| JP2020102322A (en) * | 2018-12-20 | 2020-07-02 | 太平洋セメント株式会社 | Positive electrode active material for secondary battery, and method for producing the same |
| CN111446426A (en) * | 2019-01-16 | 2020-07-24 | 通用汽车环球科技运作有限责任公司 | Method for manufacturing high performance electrode |
| JPWO2020241547A1 (en) * | 2019-05-31 | 2020-12-03 | ||
| CN110752370A (en) * | 2019-10-29 | 2020-02-04 | 广州鹏辉能源科技股份有限公司 | Binder, positive electrode slurry, positive plate and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| Water-Soluble Trifunctional Binder for Sulfur Cathodes for Lithium− Sulfur Battery;yajun yang etal.;ACS Applied Materials & Interfaces;第13卷(第28期);33066-33074 * |
| 锂离子电池胶粘剂的研究进展;王超等;粘结(第6期);53-60 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114725313A (en) | 2022-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107221716B (en) | Rechargeable aqueous zinc ion battery | |
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| CN113113605B (en) | Network structure ion conductive adhesive and preparation method and application thereof | |
| CN110890545A (en) | PEDOT (polyethylene glycol terephthalate)/PSS (Polybutylece terephthalate)/CMC (carboxymethyl cellulose) composite binder as well as preparation method and application thereof | |
| CN113429504B (en) | Preparation method of semi-solid polyion liquid electrolyte for lithium battery | |
| CN105742695B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN103779568A (en) | Column quinone positive pole material for lithium ion battery and application thereof | |
| CN111934020B (en) | High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof | |
| CN109802107B (en) | Preparation method of polyalkenyl composite negative electrode material for sodium ion battery | |
| CN114725313B (en) | Silicon-based negative plate and preparation method and application thereof | |
| CN112133916A (en) | Silicon-based negative electrode material binder of lithium ion battery and preparation method and application thereof | |
| CN110311167A (en) | A kind of composite solid electrolyte piece and preparation method thereof and solid state battery | |
| CN111933945B (en) | High-capacity lithium ion battery pole piece and lithium ion secondary battery containing same | |
| CN113285050A (en) | Li-M-X-based solid lithium battery anode and preparation method thereof | |
| CN110993953B (en) | Positive plate, solid-state chemical power supply and preparation method | |
| CN116014079A (en) | Lignin water-based composite battery binder and preparation method and application of silicon-based negative plate thereof | |
| CN107425181A (en) | A kind of preparation method of manganese oxide/starch base hard carbon composite negative pole material | |
| CN108923033A (en) | A kind of preparation method of the lithium-sulfur cell porous carbon positive electrode based on phase transfer method | |
| CN115275106A (en) | Lithium ion battery negative pole piece with three-dimensional network structure binder | |
| CN115275096A (en) | Self-repairing flexible electrode, preparation method thereof and lithium-sulfur battery | |
| CN108807921B (en) | Lithium battery negative electrode material and preparation method thereof | |
| CN110323079B (en) | High-voltage-resistant anion exchange electrolyte membrane and solid-state battery capacitor thereof | |
| CN109546092B (en) | Lithium-sulfur thin film battery | |
| CN112250114A (en) | Preparation method and application of titanium-doped modified manganese dioxide electrode material | |
| CN111293297A (en) | Carbon-coated MoSe2Black phosphorus composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |