CN112467063B - Preparation method of silicon-based negative electrode plate of lithium ion battery - Google Patents

Preparation method of silicon-based negative electrode plate of lithium ion battery Download PDF

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CN112467063B
CN112467063B CN202011244368.4A CN202011244368A CN112467063B CN 112467063 B CN112467063 B CN 112467063B CN 202011244368 A CN202011244368 A CN 202011244368A CN 112467063 B CN112467063 B CN 112467063B
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silicon
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谭龙
汤昊
陈齐健
罗汉卿
孙润光
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Nanchang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a silicon-based negative electrode plate of a lithium ion battery. The preparation method comprises the following steps: fully mixing a silicon-based negative electrode material, a conductive agent, a binder and a modification additive in a certain mass ratio with a certain reagent to form a slurry-like substance, wherein the modification additive is an organic small molecule, the organic small molecule at least contains one of amino or carboxyl functional groups, and the molar mass of the organic small molecule is less than 210 g/mol; and then uniformly coating the mixture on the surface of copper foil, and respectively drying at 50-80 ℃ for 20-60 min and at 100-140 ℃ for 8-20 h to obtain the silicon-based negative pole piece. The preparation method of the silicon-based negative pole piece disclosed by the invention has the advantage of simple process, and the prepared pole piece is assembled into a battery, shows high specific capacity, good first coulombic efficiency and excellent cycle performance, and is suitable for a lithium ion power battery.

Description

Preparation method of silicon-based negative electrode plate of lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a silicon-based negative electrode plate of a lithium ion battery.
Background
Lithium ion batteries have received much attention due to their excellent energy storage and power supply characteristics. At present, the application of lithium ion batteries in the fields with low requirements on energy density, such as mobile phones, notebook computers, electric tools and the like, is nearly mature, but the application of lithium ion batteries in the fields with high requirements on energy density, such as automobile power batteries and the like, has a great space for improving the energy density. Therefore, silicon materials with high theoretical specific capacity have been the focus of research and are often used in combination with carbon, such as common silicon and silicon carbon composites with thin carbon layers coated on the surface.
Compared with the research on the silicon/carbon material, the research on the preparation process of the silicon/carbon negative electrode material pole piece is relatively less reported. It is known that, for example, Myung-Hyun Ryou et al (adv. mater.2013,25,1571) respectively develop a modified polyacrylic acid and a sodium alginate binder which are also modified, and compared with the traditional polyvinylidene fluoride (PVDF), the cycling stability of the silicon material is greatly improved. Therefore, the preparation research of the silicon/carbon negative electrode material pole piece process is very necessary, and the preparation method can play a vital role in the electrochemical performance of the relevant battery.
Although the theoretical capacity of silicon in the negative electrode material is far greater than that of graphite, the volume expansion of the negative electrode material is very high along with huge volume change, the pulverization of the silicon causes the instability and failure of an electrode structure, the collapse of the electrode structure and the peeling of an active material cause the loss of electric contact of the electrode, the capacity of the electrode is greatly reduced and even completely failed, and the electrochemical cycle performance of the silicon-based negative electrode is poor.
Disclosure of Invention
The invention aims to provide a method for preparing a silicon-based negative electrode film of a lithium ion battery, which has high specific capacity, good first coulombic efficiency and excellent cycle performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a silicon-based negative electrode plate of a lithium ion battery, which is characterized in that a silicon-based negative electrode material, a conductive agent, a binder, a modification additive with specific mass and a certain reagent are fully mixed to form a slurry-like substance, wherein the modification additive is an organic micromolecule, the organic micromolecule at least contains one of amino or carboxyl functional groups, and the molar mass of the organic micromolecule is less than 210 g/mol; and then uniformly coating the mixture on the surface of copper foil, and respectively drying at 50-80 ℃ (preferably 60 ℃) for 20-60 min (preferably 35min) and at 100-140 ℃ (preferably 120 ℃) for 8-20 h (preferably 12h) to obtain the silicon-based negative pole piece.
Preferably, the sum of the mass of the silicon-based negative electrode material, the mass of the conductive agent and the mass of the binder is taken as the total mass, the mass of the silicon-based negative electrode material accounts for 70-97% of the total mass, the mass of the conductive agent accounts for 1.5-15% of the total mass, and the mass of the binder accounts for 1.5-15% of the total mass.
Preferably, the mass of the silicon-based negative electrode material accounts for 85-95% of the total mass, the mass of the conductive agent accounts for 2.5-7.5% of the total mass, and the mass of the binder accounts for 2.5-7.5% of the total mass.
Preferably, the silicon-based negative electrode material is at least one of pure silicon, carbon-coated silicon and a silicon-carbon composite containing silicon components, and preferably pure silicon.
More preferably, the silicon-based material contains 1-100% by mass of silicon, preferably 90-100% by mass of silicon.
More preferably, the modifying additive is at least one of tyrosine, phenylalanine, aspartic acid, tryptophan, phenylpropargyl acid, acrylic acid, butylamine and diethylamine, preferably phenylalanine and phenylpropargyl acid; the content of the additive is not less than 0.05 percent of the total mass of silicon in the silicon-based negative pole piece, and preferably 1 to 25 percent.
The conductive agent, the binder and the reagent of the invention are all made of materials known to those skilled in the art, for example, the conductive agent is at least one of Super-P, Ketjen black, carbon nanotube, graphene and carbon fiber, preferably Super-P; the binder is one of sodium alginate, sodium carboxymethylcellulose, acrylic glue, sodium carboxymethylcellulose and a styrene-butadiene latex mixture, preferably the acrylic glue, the sodium carboxymethylcellulose and the styrene-butadiene latex mixture; the reagent is at least one of water, ethanol, isopropanol and ethylene glycol, preferably water and ethanol.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention realizes the modification of the preparation of the silicon-based pole piece by organic molecules for the first time, can improve the first efficiency and the cycling stability of the material at the same time, and is suitable for high-energy-density lithium ion batteries.
2. According to the invention, the special additive is added into the slurry for preparing the silicon/carbon negative electrode material pole piece, and the special additive can form a covalent bond with surface silicon atoms, so that the volume expansion effect of silicon in the charge-discharge process is effectively inhibited, and the electrochemical cycle performance of the material is stabilized.
3. The process adopted by the invention has the advantages of simple process, good consistency of the obtained result batches and the like, and is easy to industrialize.
Detailed Description
For further illustration of the present invention, the following will describe in detail the preparation method of a silicon-based negative electrode plate of a lithium ion battery provided by the present invention with reference to the examples, but they should not be construed as limiting the scope of the present invention. It is to be understood that the disclosed embodiments are merely exemplary of the invention, and are not intended to be exhaustive or exhaustive. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In the present invention, the components in the preparation process are commercially available products well known to those skilled in the art, unless otherwise specified.
Example 1
Respectively weighing 0.64g of pure silicon negative electrode material, 0.08g of Super-P, 0.04g of CMC, 0.04g of SBR and 0.08g of tyrosine according to the mass ratio of 16:2:1:1:2, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying for 0.5h at 60 ℃; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃; and finally, slicing to prepare the button cell, and carrying out charge-discharge cycle test at a current density of 300 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 2
Respectively weighing 0.64g of pure silicon negative electrode material, 0.08g of Super-P, 0.08g of acrylic adhesive and 0.08g of tryptophan according to the mass ratio of 8:1:1:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to form slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying for 0.5h at 60 ℃; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 300 mA/g. The test results are shown in table 1, which indicates that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 3
Respectively weighing 0.64g of pure silicon negative electrode material, 0.08g of Super-P, 0.08g of sodium alginate and 0.02g of phenylpropionic acid according to the mass ratio of 32:4:4:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to form slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying for 0.5h at 60 ℃; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 130 ℃; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 300 mA/g. The test results are shown in table 1, which indicates that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 4
Respectively weighing 0.64g of carbon-coated silicon negative electrode material (Si content: 98%), 0.08g of Super-P, 0.08g of sodium alginate and 0.04g of phenylpropionic acid according to the mass ratio of 16:2:2:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying at 60 ℃ for 35min to remove the solvent; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃ so as to ensure that the solvent is completely removed; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 400 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 5
Respectively weighing 0.64g of carbon-coated silicon negative electrode material (Si content: 98%), 0.08g of Super-P, 0.08g of acrylic adhesive and 0.08g of tryptophan according to the mass ratio of 8:1:1:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying at 60 ℃ for 35min to remove the solvent; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 130 ℃ so as to ensure that the solvent is completely removed; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 400 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 6
Respectively weighing 0.64g of carbon-coated silicon negative electrode material (Si content: 98%), 0.08g of Super-P, 0.04g of CMC, 0.04g of SBR and 0.04g of tyrosine according to the mass ratio of 16:2:1:1:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying at 60 ℃ for 35min to remove the solvent; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃ so as to ensure that the solvent is completely removed; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 400 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 7
Respectively weighing 0.92g of silicon-carbon composite material (Si content: 4%), 0.04g of Super-P, 0.02g of CMC, 0.02g of SBR and 0.01g of aspartic acid according to the mass ratio of 92:4:2:2:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying at 60 ℃ for 35min to remove the solvent; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃ so as to ensure that the solvent is completely removed; and finally, slicing to prepare the button cell, and carrying out charge-discharge cycle test at a current density of 100 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 8
Respectively weighing 0.92g of silicon-carbon composite material (Si content: 4%), 0.04g of Super-P, 0.02g of CMC, 0.02g of SBR and 0.01g of tyrosine according to the mass ratio of 92:4:2:2:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying at 60 ℃ for 35min to remove the solvent; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 110 ℃ so as to ensure that the solvent is completely removed; and finally, slicing to prepare the button cell, and carrying out charge-discharge cycle test at a current density of 100 mA/g. The test results are shown in table 1, which indicates that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 9
Respectively weighing 0.92g of silicon-carbon composite material (Si content: 4%), 0.04g of Super-P, 0.02g of CMC, 0.02g of SBR and 0.01g of phenylpropanoic acid according to the mass ratio of 92:4:2:2:1, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to form slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying at 60 ℃ for 35min to remove the solvent; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃ so as to ensure that the solvent is completely removed; and finally, slicing to prepare the button cell, and carrying out charge-discharge cycle test at a current density of 100 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 10
Respectively weighing 0.64g of pure silicon negative electrode material, 0.08g of Super-P, 0.04g of CMC, 0.04g of SBR and 0.08g of phenylalanine according to the mass ratio of 16:2:1:1:2, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying for 0.5h at 60 ℃; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 300 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 11
Respectively weighing 0.64g of pure silicon negative electrode material, 0.08g of Super-P, 0.04g of CMC, 0.04g of SBR and 0.16g of acrylic acid according to the mass ratio of 16:2:1:1:4, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, and magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying for 0.5h at 60 ℃; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 300 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 12
Respectively weighing 0.64g of pure silicon negative electrode material, 0.08g of Super-P, 0.04g of CMC, 0.04g of SBR and 0.16g of butylamine according to the mass ratio of 16:2:1:1:4, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying for 0.5h at 60 ℃; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃; and finally, slicing to prepare the button cell, and carrying out charge-discharge cycle test at a current density of 300 mA/g. The test results are shown in table 1, which shows that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Example 13
Respectively weighing 0.64g of pure silicon negative electrode material, 0.08g of Super-P, 0.04g of CMC, 0.04g of SBR and 0.16g of diethylamine according to the mass ratio of 16:2:1:1:4, adding 4ml of deionized water and 2ml of absolute ethyl alcohol, magnetically mixing and stirring to obtain slurry; then uniformly coating the copper foil on the surface of the copper foil, and drying for 0.5h at 60 ℃; then putting the mixture into a vacuum drying oven to be dried for 12 hours at the temperature of 120 ℃; and finally, slicing, preparing a button cell, and carrying out charge-discharge cycle test at a current density of 300 mA/g. The test results are shown in table 1, which indicates that the first coulombic efficiency and the cycle performance of the modified silicon-based negative pole piece are superior to those of the unmodified pole piece.
Table 1 shows the charge and discharge performance test results of the above examples and comparative examples, each of which refers to a silicon-based negative electrode plate prepared under the same raw materials, the same preparation procedures and the same reaction conditions as the corresponding examples, but without adding the organic small molecule modification additive. The final cycle performance result can also show that the silicon-based negative pole piece prepared by the process provided by the invention has high specific capacity and excellent cycle stability, and is suitable for lithium ion power batteries.
TABLE 1 test results of the charge and discharge performance of the silicon-based negative electrode plate and each comparative sample in each example
Figure BDA0002769292470000071
Figure BDA0002769292470000081

Claims (8)

1. A preparation method of a silicon-based negative electrode plate of a lithium ion battery is characterized by comprising the following steps: fully mixing a silicon-based negative electrode material, a conductive agent, a binder and a modified additive with a specific mass and a certain reagent to form a slurry-like substance, wherein the modified additive is an organic small molecule, the organic small molecule at least contains one of amino or carboxyl functional groups, and the molar mass of the organic small molecule is less than 210 g/mol; then uniformly coating the slurry-like substance on the surface of copper foil, and respectively drying at 50-80 ℃ for 20-60 min and at 100-140 ℃ for 8-20 h in vacuum to obtain a silicon-based negative pole piece;
the modified additive is at least one of tyrosine, phenylalanine, aspartic acid, tryptophan, phenylpropanoic acid, acrylic acid, butylamine and diethylamine.
2. The preparation method of the silicon-based negative electrode plate of the lithium ion battery according to claim 1, characterized in that: the silicon-based negative electrode material, the conductive agent and the binder are taken as the total mass, the mass of the silicon-based negative electrode material accounts for 70-97% of the total mass, the mass of the conductive agent accounts for 1.5-15% of the total mass, and the mass of the binder accounts for 1.5-15% of the total mass.
3. The preparation method of the silicon-based negative electrode plate of the lithium ion battery according to claim 2, characterized in that: the silicon-based negative electrode material accounts for 85-95% of the total mass, the conductive agent accounts for 2.5-7.5% of the total mass, and the binder accounts for 2.5-7.5% of the total mass.
4. The preparation method of the silicon-based negative electrode plate of the lithium ion battery according to claim 1, characterized in that: the silicon-based negative electrode material is at least one of pure silicon, carbon-coated silicon and a silicon-carbon composite containing silicon components.
5. The preparation method of the silicon-based negative electrode plate of the lithium ion battery according to claim 1 or 4, characterized in that: the mass content of silicon in the silicon-based material is 1-100%.
6. The preparation method of the silicon-based negative electrode plate of the lithium ion battery according to claim 5, characterized in that: the mass content of silicon in the silicon-based material is 90-100%.
7. The preparation method of the silicon-based negative electrode plate of the lithium ion battery according to claim 1, characterized in that: the content of the modified additive is not lower than 0.05 percent of the total mass of silicon in the silicon-based negative pole piece.
8. The preparation method of the silicon-based negative electrode plate of the lithium ion battery according to claim 7, characterized in that: the modified additive is phenylalanine or phenylpropargonic acid; the content of the modified additive accounts for 1-25% of the total mass of silicon in the silicon-based negative pole piece.
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