CN111499802B - Preparation method of silicon negative electrode battery binder emulsion - Google Patents

Preparation method of silicon negative electrode battery binder emulsion Download PDF

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CN111499802B
CN111499802B CN202010421956.4A CN202010421956A CN111499802B CN 111499802 B CN111499802 B CN 111499802B CN 202010421956 A CN202010421956 A CN 202010421956A CN 111499802 B CN111499802 B CN 111499802B
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emulsion
corn starch
mixture
waxy corn
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CN111499802A (en
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张庆华
金碧玉
詹晓力
陈丰秋
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Quzhou Research Institute of Zhejiang University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a lithium ion battery technology, and aims to provide a preparation method of a silicon negative electrode battery binder emulsion. The method comprises the following steps: adding the ferrous sulfate solution into the waxy corn starch hydrolysate for reaction, and then adding the hydrogen peroxide solution for continuous reaction; dissolving methyl methacrylate and (N-methyl) perfluorobutyl (hexyl) acrylate (sulfonamide) ethyl acrylate in a mixture of butyl acrylate and methyl methacrylate, dropwise adding the mixture into a reaction system, and dropwise adding a hydrogen peroxide solution; obtaining bonding emulsion after the reaction is finished; and uniformly mixing dopamine and the bonding emulsion to prepare emulsion, and uniformly mixing the emulsion and waxy corn starch to obtain the silicon cathode battery bonding agent emulsion. The invention can solve the problems of short cycle life, low capacity retention rate and the like of the conventional silicon cathode lithium ion battery. The reaction condition is mild, and no emulsifier is added; can effectively inhibit the damage of the silicon-carbon electrode caused by the volume expansion effect in the charging process and keep the structural integrity of the electrode.

Description

Preparation method of silicon negative electrode battery binder emulsion
Technical Field
The invention relates to a lithium ion battery technology, in particular to a preparation method of a silicon negative electrode battery binder emulsion.
Background
With the rapid development of society, lithium ion batteries with the advantages of high energy density, high working voltage, low self-discharge rate, long service life and the like are widely used in the aspects of power supplies, power grid storage systems and the like, and the lithium ion batteries with high performance and low cost become research and development hotspots. In the next generation of battery system, the high specific capacity anode and cathode materials are the key factors for improving the energy density of the lithium ion battery.
The carbon-based negative electrode material applied in the traditional commercialization is generally graphite, and has the advantages of long cycle life, low cost, rich resources and the like, but the theoretical specific capacity of the carbon-based negative electrode material is only 372mAh/g, and the requirement of high energy density of a lithium ion battery cannot be met. Since the silicon is inThe earth crust has rich content and higher theoretical specific capacity (3579 mAh g) -1 ) The method becomes a research hotspot of a new generation of high-energy density lithium ion battery cathode material in recent years. However, the silicon material has large volume change (about 300%) in the charging and discharging process, which causes electrode pulverization and falling, and the capacity is rapidly attenuated, thereby limiting the exertion of good performance of silicon in the lithium ion battery.
In order to solve the above problems, a binder in an electrode has received much attention, which binds an active material and a conductive agent to a current collector at a relatively low mass fraction so that the electrode can maintain its integrity and have good electrical connectivity. Although the binder belongs to an electrochemically inert component, considerable research shows that the performance of the binder has a significant influence on the performance of an electrode material, particularly a silicon-based negative electrode material. In the traditional preparation of the lithium battery pole piece, N-methyl pyrrolidone (NMP) is used as a solvent, polyvinylidene fluoride (PVDF) is used as an adhesive, but the defects of silicon and sulfur expansion are difficult to overcome by only adhering a current collector and an active substance by virtue of Van der Waals force. The expensive price of polyvinylidene fluoride and the toxicity of NMP increase the material recovery and recycling cost, and the green environment-friendly water-soluble/water-dispersible adhesive becomes a research hotspot.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a silicon cathode battery binder emulsion.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the silicon negative electrode battery binder emulsion comprises the following steps:
(1) Taking waxy corn starch and water according to the mass ratio of 1: 2, and dispersing the waxy corn starch in the water; heating to 90 ℃, and adding alpha-amylase accounting for 0.2 percent of the mass of the waxy corn starch; after hydrolysis reaction for 10min, cooling to 85 ℃;
(2) Taking ferrous sulfate according to 1.2% of the mass of the waxy corn starch, dissolving the ferrous sulfate in water, wherein the mass ratio of the ferrous sulfate to the water is 1: 10, and marking the obtained solution as a mixture A;
adding the mixture A into the reaction system in the step (1), and continuing to react for 10min;
(3) Taking a commercial hydrogen peroxide solution with the mass percentage concentration of 30 percent according to 1.5 percent of the mass of the waxy corn starch; adding the mixture into water, wherein the mass ratio of the commercial hydrogen peroxide solution to the water is 1: 40, and marking the obtained solution as a mixture B;
adding 1/3 of the mixture B into the reaction system in the step (2), and continuing to react for 30min;
(4) Taking butyl acrylate and methyl methacrylate according to the mass ratio of 4: 1, and uniformly mixing, wherein the total mass of the obtained mixture is 50% of the mass of the waxy corn starch; taking methyl methacrylate and (N-methyl) perfluorobutyl (hexyl) acrylate (sulfonamide) ethyl ester according to 100% of the mass of the waxy corn starch, dissolving the methyl methacrylate and the (N-methyl) perfluorobutyl (hexyl) acrylate (sulfonamide) ethyl ester in a mixture of butyl acrylate and methyl methacrylate, and marking the obtained solution as a mixture C;
(5) Dropwise adding the rest 2/3 mass of the mixture B into the reaction system in the step (3), and then dropwise adding the mixture C, wherein the total dropwise adding time is controlled to be 2h; after the dripping is finished, preserving the heat for 2 hours at 85 ℃, and then reducing the temperature to room temperature to finish the reaction to obtain bonding emulsion D;
(6) Uniformly mixing dopamine and the bonding emulsion D to prepare emulsion E, wherein the concentration of the emulsion E is 0.1-10 mg of dopamine/mL of emulsion D;
(7) Taking the emulsion E and waxy corn starch according to the mass ratio of the dry matter of the emulsion E to the waxy corn starch of 1: 1; and uniformly mixing to obtain the silicon cathode battery binder emulsion F.
In the present invention, the methyl methacrylate and the (N-methyl) perfluorobutyl (hexyl) acrylate (sulfonamide) ethyl ester are any one of the following: perfluorobutyl ethyl acrylate (C4A), perfluorohexyl ethyl acrylate (C6A), N-methylperfluorobutylsulfonamidoethyl acrylate (C4 SA), N-methylperfluorohexylsulfonamidoethyl acrylate (C6 SA).
Description of the inventive concept:
the fluorine-containing copolymer modified waxy corn starch prepared by the method of soap-free emulsion polymerization is used as a silicon cathode lithium ion battery binder, so that the cycle life of the silicon cathode lithium ion battery is greatly prolonged, and the capacity retention rate is improved. Particularly, dopamine is utilized to generate self-polymerization in emulsion, the poly-dopamine after self-polymerization can still keep good adhesion with a current collector (copper foil) in an electrolyte environment, and phenolic hydroxyl in the poly-dopamine can form a physical cross-linking binder network with hydrogen bond interaction between fluorine monomers grafted on waxy corn starch, so that the structural damage of an electrode caused by the volume expansion effect of a silicon-carbon electrode in the charging process can be effectively inhibited, and the structural integrity of the electrode is kept.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a fluorine-containing copolymer modified waxy corn starch used as a battery binder, which can solve the problems of short cycle life, low capacity retention rate and the like of the existing silicon cathode lithium ion battery.
2. In the invention, the fluorine monomer modified waxy corn starch is prepared by soap-free emulsion polymerization, the reaction condition is mild, and an emulsifier is not required to be added;
3. in the invention, because the catechol group in the dopamine not only provides the interfacial adhesion with a current collector (copper foil), but also forms a physical crosslinking binder network under the action of a hydrogen bond with a fluorine monomer grafted on waxy corn starch to wrap active substances, the structural damage of the electrode caused by the volume expansion effect of the silicon-carbon electrode in the charging process can be effectively inhibited, and the structural integrity of the electrode is maintained.
Detailed Description
The invention is further illustrated by the following examples:
example 1:
(1) Taking 5g of waxy corn starch and 10g of water, adding the waxy corn starch and the water into a 100mL single-neck flask, wherein the single-neck flask is provided with a mechanical stirring and condensing tube, raising the temperature to 90 ℃, adding 0.01g of alpha-amylase, and reducing the reaction temperature to 85 ℃ after 10min of hydrolysis. Dissolving 0.06g of ferrous sulfate in 0.6g of water, adding into the hydrolyzed corn starch solution, and reacting for 10min.
(2) 0.075g of 30% hydrogen peroxide and 3g of water are mixed, and 1.025g of diluted hydrogen peroxide is added into the reaction system in the step (1) to react for 30min.
(3) Dissolving 5g of perfluorobutyl ethyl acrylate (C4A) in a mixture of 2g of butyl acrylate and 0.5g of methyl methacrylate, dropwise adding the monomer mixture and the rest 2.05g of diluted hydrogen peroxide into the reaction system in the step (2) by using a constant-pressure dropping funnel respectively, controlling the total dropwise adding time to be 2h, continuing to keep the temperature at 85 ℃ for 2h after the dropwise adding is finished, and reducing the temperature to room temperature to finish the reaction to obtain the binder emulsion. 0.1mg of dopamine and 1mL of binder emulsion are mixed to obtain the final binder emulsion to be used, which is marked as FS1.
0.06g of silicon powder (with the particle size of 100 nm), 0.02g of carbon powder (super p), 0.01g of waxy corn starch, 0.01g of FS (dry substance) and 600 microliters of water are uniformly ground and coated on a copper foil, and the copper foil is dried at 60 ℃ for 12 hours and then dried at 180 ℃ for 2 hours. Cutting into electrode plates with the diameter of 14mm, taking a lithium plate as a counter electrode, taking a PP/PE/PP (Celgard 2325) composite diaphragm as a battery diaphragm, and mixing ethylene carbonate/diethyl carbonate/fluoroethylene carbonate (mass ratio 1 6 A button cell is equipped for the electrolyte, and the cycling performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycling tester of Shenzhen New Wei electronics Co.
Example 2:
(1) Adding 5g of waxy corn starch and 10g of water into a 100mL single-neck flask, wherein the single-neck flask is provided with a mechanical stirring and condensing tube, raising the temperature to 90 ℃, adding 0.01g of alpha-amylase, hydrolyzing for 10min, and then reducing the reaction temperature to 85 ℃. Dissolving 0.06g of ferrous sulfate in 0.6g of water, adding into the hydrolyzed corn starch solution, and reacting for 10min.
(2) 0.075g of 30% hydrogen peroxide and 3g of water are mixed, and 1.025g of diluted hydrogen peroxide is added into the reaction system in the step (1) to react for 30min.
(3) Dissolving 5g of perfluorohexyl ethyl acrylate (C6A) in a mixture of 2g of butyl acrylate and 0.5g of methyl methacrylate, dropwise adding the monomer mixture and the rest 2.05g of diluted hydrogen peroxide into the reaction system in the step (2) by using a constant-pressure dropping funnel respectively, controlling the total dropwise adding time to be 2 hours, keeping the temperature at 85 ℃ for 2 hours after the dropwise adding is finished, and reducing the temperature to room temperature to finish the reaction to obtain a binder emulsion. 1mg of dopamine and 1mL of binder emulsion are mixed to obtain the final binder emulsion to be used, which is recorded as FS2.
0.06g of silicon powder (with the particle size of 100 nm), 0.02g of carbon powder (super p), 0.01g of waxy corn starch, 0.01g of FS (dry substance) and 600 microliters of water are uniformly ground and coated on a copper foil, and the copper foil is dried at 60 ℃ for 12 hours and then dried at 180 ℃ for 2 hours. Cutting into electrode plates with the diameter of 14mm, taking a lithium plate as a counter electrode, taking a PP/PE/PP (Celgard 2325) composite diaphragm as a battery diaphragm, and mixing ethylene carbonate/diethyl carbonate/fluoroethylene carbonate (mass ratio 1 6 A button cell is equipped for electrolyte, and the cycle performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycle tester of Shenzhen New Wei electronic Limited.
Example 3:
(1) Taking 5g of waxy corn starch and 10g of water, adding the waxy corn starch and the water into a 100mL single-neck flask, wherein the single-neck flask is provided with a mechanical stirring and condensing tube, raising the temperature to 90 ℃, adding 0.01g of alpha-amylase, and reducing the reaction temperature to 85 ℃ after 10min of hydrolysis. Dissolving 0.06g of ferrous sulfate in 0.6g of water, adding into the hydrolyzed corn starch solution, and reacting for 10min.
(2) 0.075g of 30% hydrogen peroxide and 3g of water are mixed, and 1.025g of diluted hydrogen peroxide is added into the reaction system in the step (1) to react for 30min.
(3) Dissolving 5g of N-methyl perfluorobutyl sulfonamide ethyl acrylate (C4 SA) in a mixture of 2g of butyl acrylate and 0.5g of methyl methacrylate, dropwise adding the monomer mixture and the rest 2.05g of diluted hydrogen peroxide into the reaction system in the step (2) by using a constant-pressure dropping funnel respectively, controlling the total dropwise adding time to be 2h, keeping the temperature at 85 ℃ for 2h after the dropwise adding is finished, and reducing the temperature to room temperature to finish the reaction to obtain the binder emulsion. 1mg of dopamine and 10mL of binder emulsion are mixed to obtain the final binder emulsion to be used, which is denoted as FS3.
0.06g of silicon powder (with the particle size of 100 nm), 0.02g of carbon powder (super p), 0.01g of waxy corn starch, 0.01g of FS (dry substance) and 600 microliters of water are uniformly ground and coated on a copper foil, and the copper foil is dried at 60 ℃ for 12 hours and then dried at 180 ℃ for 2 hours. Cut into diameterThe electrode sheet was a 14mm electrode sheet, a lithium sheet was used as a counter electrode, a PP/PE/PP (Celgard 2325) composite separator was used as a battery separator, and a mixture of ethylene carbonate/diethyl carbonate/fluoroethylene carbonate (mass ratio 1 6 A button cell is equipped for electrolyte, and the cycle performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycle tester of Shenzhen New Wei electronic Limited.
Example 4:
(1) Adding 5g of waxy corn starch and 10g of water into a 100mL single-neck flask, wherein the single-neck flask is provided with a mechanical stirring and condensing tube, raising the temperature to 90 ℃, adding 0.01g of alpha-amylase, hydrolyzing for 10min, and then reducing the reaction temperature to 85 ℃. Dissolving 0.06g of ferrous sulfate in 0.6g of water, adding into the hydrolyzed corn starch solution, and reacting for 10min.
(2) 0.075g of 30% hydrogen peroxide and 3g of water are mixed, and 1.025g of diluted hydrogen peroxide is added into the reaction system in the step (1) to react for 30min.
(3) Dissolving 5g of N-methyl perfluorohexyl sulfonamide ethyl acrylate (C6 SA) in a mixture of 2g of butyl acrylate and 0.5g of methyl methacrylate, dropwise adding the monomer mixture and the rest 2.05g of diluted hydrogen peroxide into the reaction system in the step (2) by using a constant-pressure dropping funnel respectively, controlling the total dropwise adding time to be 2h, keeping the temperature at 85 ℃ for 2h after the dropwise adding is finished, and reducing the temperature to room temperature to finish the reaction to obtain the binder emulsion. 1mg of dopamine and 0.1mL of binder emulsion were mixed to obtain the final binder emulsion to be used, denoted as FS4.
0.06g of silicon powder (with the particle size of 100 nm), 0.02g of carbon powder (super p), 0.01g of waxy corn starch, 0.01g of FS (dry substance) and 600 microliters of water are uniformly ground and coated on a copper foil, and the copper foil is dried at 60 ℃ for 12 hours and then dried at 180 ℃ for 2 hours. Cutting into electrode plates with the diameter of 14mm, taking a lithium plate as a counter electrode, taking a PP/PE/PP (Celgard 2325) composite diaphragm as a battery diaphragm, and mixing ethylene carbonate/diethyl carbonate/fluoroethylene carbonate (mass ratio 1 6 A button cell is equipped for the electrolyte, and the cycling performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycling tester of Shenzhen New Wei electronics Co.
Example 5:
(1) Adding 5g of waxy corn starch and 10g of water into a 100mL single-neck flask, wherein the single-neck flask is provided with a mechanical stirring and condensing tube, raising the temperature to 90 ℃, adding 0.01g of alpha-amylase, hydrolyzing for 10min, and then reducing the reaction temperature to 85 ℃. Dissolving 0.06g of ferrous sulfate in 0.6g of water, adding into the hydrolyzed corn starch solution, and reacting for 10min.
(2) 0.075g of 30% hydrogen peroxide and 3g of water are mixed, and 1.025g of diluted hydrogen peroxide is added into the reaction system in the step (1) to react for 30min.
(3) 5g of N-methyl perfluorobutyl sulfonamide ethyl acrylate (C4 SA) is dissolved in a mixture of 2g of butyl acrylate and 0.5g of methyl methacrylate, the monomer mixture and the rest 2.05g of diluted hydrogen peroxide are respectively dripped into the reaction system in the step (2) by a constant pressure dropping funnel, the total dripping time is controlled to be 2h, after the dripping is finished, the temperature is kept at 85 ℃ for 2h, and the temperature is reduced to room temperature to finish the reaction, so that the adhesive emulsion is obtained. 0.1mg of dopamine was mixed with 10mL of binder emulsion to obtain the final binder emulsion to be used, denoted as FS5.
0.06g of silicon powder (with the particle size of 100 nm), 0.02g of carbon powder (super p), 0.01g of waxy corn starch, 0.01g of FS (dry substance) and 600 microliters of water are uniformly ground and coated on a copper foil, and after the copper foil is dried at 60 ℃ for 12 hours, the copper foil is dried at 180 ℃ for 2 hours. Cutting into electrode plates with the diameter of 14mm, taking a lithium plate as a counter electrode, taking a PP/PE/PP (Celgard 2325) composite diaphragm as a battery diaphragm, and mixing ethylene carbonate/diethyl carbonate/fluoroethylene carbonate (mass ratio 1 6 A button cell is equipped for electrolyte, and the cycle performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycle tester of Shenzhen New Wei electronic Limited.
Example 6:
(1) Adding 5g of waxy corn starch and 10g of water into a 100mL single-neck flask, wherein the single-neck flask is provided with a mechanical stirring and condensing tube, raising the temperature to 90 ℃, adding 0.01g of alpha-amylase, hydrolyzing for 10min, and then reducing the reaction temperature to 85 ℃. Dissolving 0.06g of ferrous sulfate in 0.6g of water, adding into the hydrolyzed corn starch solution, and reacting for 10min.
(2) 0.075g of 30% hydrogen peroxide and 3g of water are mixed, and 1.025g of diluted hydrogen peroxide is added into the reaction system in the step (1) to react for 30min.
(3) Dissolving 5g of perfluorobutyl ethyl acrylate (C4A) in a mixture of 2g of butyl acrylate and 0.5g of methyl methacrylate, dropwise adding the monomer mixture and the rest 2.05g of diluted hydrogen peroxide into the reaction system in the step (2) by using a constant-pressure dropping funnel respectively, controlling the total dropwise adding time to be 2h, continuing to keep the temperature at 85 ℃ for 2h after the dropwise adding is finished, and reducing the temperature to room temperature to finish the reaction to obtain the binder emulsion. 10mg of dopamine and 1mL of binder emulsion were mixed to obtain the final binder emulsion to be used, which was designated as FS6.
0.06g of silicon powder (with the particle size of 100 nm), 0.02g of carbon powder (super p), 0.01g of waxy corn starch, 0.01g of FS (dry substance) and 600 microliters of water are uniformly ground and coated on a copper foil, and the copper foil is dried at 60 ℃ for 12 hours and then dried at 180 ℃ for 2 hours. Cutting into electrode plates with the diameter of 14mm, taking a lithium plate as a counter electrode, taking a PP/PE/PP (Celgard 2325) composite diaphragm as a battery diaphragm, and mixing ethylene carbonate/diethyl carbonate/fluoroethylene carbonate (mass ratio 1 6 A button cell is equipped for the electrolyte, and the cycling performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycling tester of Shenzhen New Wei electronics Co.
Comparative example 1:
commercially available polyvinylidene fluoride powder (PVDF for short, type: kynar HSV 900 manufacturer: acoma PVDF) is used as the binder emulsion. The button cell is prepared according to the method of the embodiment 1, and the cycle performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycle tester of Shenzhen New Wei electronic Limited.
Comparative example 2:
a commercially available carboxymethyl cellulose II-styrene-butadiene rubber emulsion (CMC-SBR, wherein the carboxymethyl cellulose II (CMC) is of the average molecular weight of 250000Da and the viscosity of 1500-3100 mPa & s, and is purchased from an avastin reagent, and the styrene-butadiene latex has a mass solid content of 50% and is purchased from NIPPON A & L company). The button cell is prepared according to the method of the embodiment 1, and the cycle performance of the cell is tested by adopting a BTS-5V/50mA type charge-discharge cycle tester of Shenzhen New Wei electronic Limited.
Figure BDA0002497284100000071
As can be seen from the above table, the silicon anode lithium ion battery binder prepared by using N-methyl perfluorobutyl sulfonamide ethyl acrylate (C4 SA) modified corn starch and mixing 1mg of dopamine with 10mL of the binder emulsion has the highest capacity retention rate of the prepared silicon electrode.

Claims (2)

1. The preparation method of the silicon negative electrode battery binder emulsion is characterized by comprising the following steps of:
(1) Taking waxy corn starch and water according to the mass ratio of 1: 2, and dispersing the waxy corn starch in the water; heating to 90 ℃, adding alpha-amylase to carry out hydrolysis reaction for 10min, and then cooling to 85 ℃;
(2) Taking ferrous sulfate according to 1.2% of the mass of the waxy corn starch, dissolving the ferrous sulfate in water, wherein the mass ratio of the ferrous sulfate to the water is 1: 10, and marking the obtained solution as a mixture A;
adding the mixture A into the reaction system in the step (1), and continuing to react for 10min;
(3) Taking a commercial hydrogen peroxide solution with the mass percent concentration of 30% according to 1.5% of the mass of the waxy corn starch; adding the mixture into water, wherein the mass ratio of the commercial hydrogen peroxide solution to the water is 1: 40, and the obtained solution is marked as a mixture B;
adding 1/3 of the mixture B into the reaction system in the step (2), and continuing to react for 30min;
(4) Taking butyl acrylate and methyl methacrylate according to the mass ratio of 4: 1, and uniformly mixing, wherein the total mass of the obtained mixture is 50% of the mass of the waxy corn starch; taking fluorine-containing acrylate according to 100% of the mass of the waxy corn starch, dissolving the fluorine-containing acrylate in a mixture of butyl acrylate and methyl methacrylate, and marking the obtained solution as a mixture C;
the fluorine-containing acrylate is any one of the following: perfluorobutyl ethyl acrylate, perfluorohexyl ethyl acrylate, N-methylperfluorobutylsulfonamidoethyl acrylate, N-methylperfluorohexylsulfonamidoethyl acrylate;
(5) Dropwise adding the mixture B and the mixture C in the rest 2/3 of the mass into the reaction system in the step (3), and controlling the total dropwise adding time to be 2h; after the dripping is finished, preserving the heat for 2 hours at 85 ℃, and then reducing the temperature to room temperature to finish the reaction to obtain a bonding emulsion D;
(6) Uniformly mixing dopamine and bonding emulsion D to prepare emulsion E, wherein the concentration of the emulsion E is 0.1-10 mg of dopamine/mL of emulsion D;
(7) Taking the emulsion E and waxy corn starch according to the mass ratio of the dry matter of the emulsion E to the waxy corn starch of 1: 1; and uniformly mixing to obtain the silicon cathode battery binder emulsion F.
2. The method according to claim 1, wherein in the step (1), the amount of the alpha-amylase is 0.2% by mass of the waxy corn starch.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106711431A (en) * 2016-12-31 2017-05-24 武汉理工大学 Silicon-base cathode material for lithium ion battery and preparation method of silicon-base cathode material
CN106784538A (en) * 2017-01-24 2017-05-31 厦门大学 The spraying preparation method of poly-dopamine ceramic diaphragm and its application in lithium ion battery
CN110573544A (en) * 2017-04-28 2019-12-13 罗伯特·博世有限公司 Composite binder for lithium ion battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106711431A (en) * 2016-12-31 2017-05-24 武汉理工大学 Silicon-base cathode material for lithium ion battery and preparation method of silicon-base cathode material
CN106784538A (en) * 2017-01-24 2017-05-31 厦门大学 The spraying preparation method of poly-dopamine ceramic diaphragm and its application in lithium ion battery
CN110573544A (en) * 2017-04-28 2019-12-13 罗伯特·博世有限公司 Composite binder for lithium ion battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
锂离子电池硅基负极粘结剂研究进展;岳丽萍等;《电池工业》;20170228;第21卷(第1期);第31-44页 *

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