CN112133916A - Silicon-based negative electrode material binder of lithium ion battery and preparation method and application thereof - Google Patents
Silicon-based negative electrode material binder of lithium ion battery and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a silicon-based negative electrode binder of a lithium ion battery, and a preparation method and application thereof. The binder has the advantages of simple preparation process, low price, high viscoelasticity and mechanical strength, and can effectively resist the large-volume expansion of the silicon negative electrode material in the lithium intercalation/lithium deintercalation process, maintain the integrity of the electrode structure and improve the cycle performance of the battery. Therefore, the adhesive has high cost performance and good market potential.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a silicon-based negative electrode material binder of a lithium ion battery, and a preparation method and application thereof.
Background
The increasing popularity of portable electronic devices such as smart phones and notebook computers and new energy automobiles promotes the development and progress of lithium ion battery technology, and simultaneously puts higher requirements on lithium ion batteries, such as high energy density, rapid charge and discharge and the like. The traditional graphite cathode has low theoretical energy (375mAh/g), poor high-rate charge and discharge performance and the like, and the potential of the traditional graphite cathode cannot further meet the development requirement of a high-energy-density lithium ion battery. In addition, the lithium intercalation potential of the lithium ion battery is very close to the deposition potential of lithium, so that great potential safety hazard is brought to the battery. The emerging silicon negative electrode materials have high energy density (4200mAh/g) compared to graphite and lithium intercalation platforms (0.2V vs. Li)+Li) is higher than graphite, and the safety performance is higher. However, in the application process, the volume expansion is serious, which causes pulverization of silicon particles, damages the electrode structure, causes rapid attenuation of battery capacity and extremely poor cycle performance.
The polymer binder is one of important components of the lithium ion battery electrode, and is an effective way for improving the cycling stability of the silicon-based negative electrode. However, most of the currently used silicon-based negative electrode binders (polyacrylic acid, hydroxymethyl cellulose/styrene butadiene rubber, chitosan, polyvinylidene fluoride, etc.) are linear structures, and are difficult to bear the stress generated by the large volume expansion of the nano silicon particles.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a silicon-based negative electrode material binder and a preparation method and application thereof. The binding agent is formed by covalently modifying sodium alginate and polyacrylamide, the polyacrylamide endows the sodium alginate with elasticity, the sodium alginate endows the polyacrylamide with a hyperbranched backbone, the binding agent has rich polar functional groups and high elasticity, and the silicon negative electrode can effectively resist large-volume expansion in the process of lithium intercalation/lithium deintercalation.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the lithium ion battery silicon-based negative electrode material binder is formed by covalently modifying raw materials sodium alginate and polyacrylamide, wherein the mass ratio of the sodium alginate to the acrylamide is 1: 2-4: 1. The sodium alginate is a linear anionic heteropolysaccharide which is formed by connecting beta-D-mannuronic acid (beta-D-mannuronic, M) and alpha-L-guluronic acid (alpha-L-guluronic acid, G) by a (1 → 4) bond; the molecular weight of the acrylamide is 71.08, and the purity of the acrylamide is 99.0%.
The invention also provides a preparation method of the lithium ion battery silicon-based negative electrode material binder, which comprises the following steps:
(1) uniformly dispersing sodium alginate in deionized water, and stirring to form a uniform sodium alginate solution;
(2) preparing potassium persulfate and sodium bisulfite into a mixed solution to obtain an initiator solution;
(3) dissolving acrylamide in deionized water to obtain an acrylamide solution;
(4) rapidly stirring the sodium alginate solution, introducing high-purity nitrogen to discharge oxygen, keeping the whole reaction system in a nitrogen atmosphere all the time, and keeping the whole reaction process in a constant temperature state by adopting a water bath;
(5) after ventilating for 0.5-5 hours, dropwise adding an initiator solution into a sodium alginate solution; after the initiator solution is dripped for 0.5-5 hours, dropwise adding the acrylamide solution into the sodium alginate solution, continuously stirring for 1-10 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and then closing a high-purity nitrogen valve to obtain the silicon-based negative electrode material binder of the lithium ion battery.
In the technical scheme, further, the mass fraction of the solute in the sodium alginate solution in the step (1) is 0.5% -5%.
Further, the mass fraction of solute in the initiator solution used in the step (2) is 0.01% -10%, and the mass ratio of potassium persulfate to sodium bisulfite is 1: 1-10: 1.
Further, the mass fraction of the solute in the acrylamide solution used in the step (3) is 5% -50%.
Further, the temperature of the thermostatic water bath in the step (4) is 20-80 ℃.
Further, the dropping speed in the step (5) is 1 to 20 drops/min.
The application of the lithium ion battery negative electrode material binder prepared by the method as a lithium ion battery negative electrode plate.
The negative pole piece of the secondary battery is prepared from a current collector and negative pole slurry loaded on the current collector, wherein the negative pole slurry is prepared by mixing a negative pole active material, a conductive additive and a binder prepared by the method, and the mass ratio of the negative pole active material to the conductive additive to the binder is (70-80) to (10-20) to 10.
A secondary battery comprises a negative pole piece, an isolating membrane, electrolyte and the negative pole piece.
In the invention, the negative electrode active material is a silicon-based negative electrode material. The silicon-based negative electrode material is nano silicon particles (the particle size ranges from 50 nm to 500nm, the particle size is about 100nm in the invention) or a silicon-carbon composite. The conductive additive is any one of Super P, conductive carbon black, conductive graphite and carbon nano tubes.
Compared with the prior art, the invention has the beneficial effects that:
the prepared binder is a hyperbranched polymer synthesized by covalent modification of sodium alginate and polyacrylamide, has high viscoelasticity and mechanical strength, and is simple in preparation process and low in price. Compared with the common silicon-based negative electrode binder, the binder is unique in that the binder contains abundant carboxyl, hydroxyl and amino, and the binding power of the binder is that the functional groups can not only form more hydrogen bonds with a silicon oxide layer on the surface of a negative electrode material, but also enhance the acting force between the functional groups and a copper foil. In addition, the polyacrylamide endows the sodium alginate with elasticity, and the sodium alginate endows the polyacrylamide with a hyperbranched skeleton, so that the binder has high mechanical strength. The raw materials used by the adhesive are low in cost, and the preparation process is simple and easy to operate. Therefore, the binder is a potential silicon-based anode material binder.
The hyperbranched binder prepared by the invention is applied to silicon-based negative electrode materials, and the high elasticity of polyacrylamide can effectively buffer the large-volume expansion of the silicon-based negative electrode in the process of lithium intercalation/lithium deintercalation, maintain the structural integrity of the silicon-based electrode and improve the cycle performance of the battery.
Drawings
Fig. 1 is a graph of the cycle performance of the battery in example 1.
Fig. 2 is a graph of the cycle performance of the battery in example 4.
Fig. 3 is SEM and TEM images before and after electrode cycling in example 4 and comparative examples 1 and 2: FIGS. a-c are SEM images before cycling of Si-SA, Si-PAM and Si-SA-g-PAM electrodes, respectively, FIGS. d-f are SEM images after cycling of Si-SA, Si-PAM and Si-SA-g-PAM electrodes, respectively, and FIGS. g-i are TEM images before and after cycling of Si, Si-SA-g-PAM, respectively.
Detailed Description
The silicon-based negative electrode binder of the lithium ion battery is a hyperbranched polymer synthesized by covalent modification of sodium alginate and polyacrylamide. In addition, sodium alginate or polyacrylamide alone was used as a comparison.
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
The embodiment provides a silicon-based negative electrode binder of a lithium ion battery, and a preparation method and application thereof, wherein the silicon-based negative electrode binder of the lithium ion battery is formed by covalently modifying sodium alginate and polyacrylamide, and the preparation method and the application are as follows:
preparation of the binder:
adding 1.5g of sodium alginate into 48.5mL of deionized water, stirring for half an hour to form a uniform solution with the mass concentration of 3%, and transferring the solution into a four-neck round-bottom flask; dissolving potassium persulfate and sodium bisulfite in a mass ratio of 4:1 in 10.0mL of deionized water to prepare an initiator solution with a mass concentration of 1%, and then transferring the initiator solution into a constant-pressure funnel and placing the initiator solution on a four-neck round-bottom flask; dissolving 2.0g of acrylamide in 8.0mL of deionized water to form a solution with the mass concentration of 20%, transferring the solution into a constant-pressure funnel, and placing the constant-pressure funnel on a four-neck round-bottom flask; placing the four-mouth round-bottom flask in a constant-temperature water bath kettle, magnetically stirring, setting the temperature of the water bath kettle at 45 ℃, introducing high-purity nitrogen to discharge oxygen in the flask, and keeping the whole reaction system in a nitrogen atmosphere all the time; after ventilating for half an hour, opening a constant pressure funnel valve filled with an initiator, and dropwise adding the initiator into the flask at a dropping speed of 10 drops/minute; and opening a constant-pressure funnel valve filled with acrylamide after the initiator is dripped for half an hour, dripping the initiator into the flask at the dripping speed of 10 drops/min, continuously stirring for 3 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and then closing the high-purity nitrogen valve to obtain the binder A.
The application of the binder:
homogenizing according to the mass ratio of the nano silicon particles, the Super P and the binder A being 80: 10; uniformly coating the uniform slurry on a copper foil, drying for 12h at 100 ℃ under a vacuum condition, and slicing; and (3) moving the dried pole piece into a glove box, and assembling the 2025 button cell by using a lithium piece as a counter electrode. Wherein the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF6Is EC/DMC/DEC solution with conductive salt volume ratio of 1: 1, and FEC with mass fraction of 25% is added as additive. And sealing the assembled battery, and standing for 12 hours. And (4) carrying out constant current electrochemical performance test on the battery after standing on a charge-discharge tester. Wherein the charge-discharge multiplying power is 0.2C, and the voltage range is 0.01-1.2V. The first discharge capacity reaches 2968mAh/g, after 200 cycles, the discharge capacity is 1918mAh/g, and the coulombic efficiency is 99 percent (shown in figure 1). It can be seen from the figure that when the hyperbranched polymer formed by crosslinking copolymerization of sodium alginate and polyacrylamide is used as the binder, the cycle performance of the hyperbranched polymer is significantly better than that of the hyperbranched polymer formed by crosslinking copolymerization of sodium alginate and polyacrylamide which is used as the silicon negative electrode binder alone.
Example 2
The embodiment provides a silicon-based negative electrode binder of a lithium ion battery, and a preparation method and application thereof, wherein the silicon-based negative electrode binder of the lithium ion battery is formed by covalently modifying sodium alginate and polyacrylamide, and the preparation method and the application are as follows:
preparation of the binder:
adding 1.0g of sodium alginate into 49.0mL of deionized water, stirring for half an hour to form a uniform solution with the mass concentration of 2%, and transferring the solution into a four-neck round-bottom flask; dissolving potassium persulfate and sodium bisulfite in a mass ratio of 4:1 in 10.0mL of deionized water to prepare an initiator solution with a mass concentration of 1%, and then transferring the initiator solution into a constant-pressure funnel and placing the initiator solution on a four-neck round-bottom flask; dissolving 2.5g of acrylamide in 7.5mL of deionized water to form a solution with the mass concentration of 25%, transferring the solution into a constant-pressure funnel, and placing the constant-pressure funnel on a four-neck round-bottom flask; placing the four-mouth round-bottom flask in a constant-temperature water bath kettle, magnetically stirring, setting the temperature of the water bath kettle at 45 ℃, introducing high-purity nitrogen to discharge oxygen in the flask, and keeping the whole reaction system in a nitrogen atmosphere all the time; after ventilating for half an hour, opening a constant pressure funnel valve filled with an initiator, and dropwise adding the initiator into the flask at a dropwise adding speed of 5 drops/min; and opening a constant-pressure funnel valve filled with acrylamide after the initiator is dripped for half an hour, dripping the initiator into the flask at the dripping speed of 5 drops/min, continuously stirring for 3 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and then closing a high-purity nitrogen valve to obtain the binder B.
The application of the binder:
homogenizing according to the mass ratio of the nano silicon particles, the Super P and the binder B of 80: 10; uniformly coating the uniform slurry on a copper foil, drying for 12h at 100 ℃ under a vacuum condition, and slicing; and (3) moving the dried pole piece into a glove box, and assembling the 2025 button cell by using a lithium piece as a counter electrode. Wherein the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF6Is EC/DMC/DEC solution with conductive salt volume ratio of 1: 1, and FEC with mass fraction of 25% is added as additive. And sealing the assembled battery, and standing for 12 hours. Carrying out constant current electrochemistry on the battery after standing on a charge-discharge testerAnd (5) testing the performance. Wherein the charge-discharge multiplying power is 0.2C, and the voltage range is 0.01-1.2V.
Example 3
The embodiment provides a silicon-based negative electrode binder of a lithium ion battery, and a preparation method and application thereof, wherein the silicon-based negative electrode binder of the lithium ion battery is synthesized by covalently modifying sodium alginate and polyacrylamide, and the preparation method and the application are as follows:
preparation of the binder:
adding 2.0g of sodium alginate into 48.0mL of deionized water, stirring for half an hour to form a uniform solution with the mass concentration of 4%, and transferring the solution into a four-neck round-bottom flask; dissolving potassium persulfate and sodium bisulfite in a mass ratio of 4:1 in 10.0mL of deionized water to prepare an initiator solution with a mass concentration of 1%, and then transferring the initiator solution into a constant-pressure funnel and placing the initiator solution on a four-neck round-bottom flask; dissolving 1.5g of acrylamide in 8.5mL of deionized water to form a solution with the mass concentration of 15%, transferring the solution into a constant-pressure funnel, and placing the constant-pressure funnel on a four-neck round-bottom flask; placing the four-mouth round-bottom flask in a constant-temperature water bath kettle, magnetically stirring, setting the temperature of the water bath kettle at 45 ℃, introducing high-purity nitrogen to discharge oxygen in the flask, and keeping the whole reaction system in a nitrogen atmosphere all the time; after ventilating for half an hour, opening a constant pressure funnel valve filled with an initiator, and dropwise adding the initiator into the flask at a dropping speed of 10 drops/minute; and opening a constant-pressure funnel valve filled with acrylamide after the initiator is dripped for half an hour, dripping the initiator into the flask at the dripping speed of 10 drops/min, continuously stirring for 3 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and then closing a high-purity nitrogen valve to obtain the binder C.
The application of the binder:
homogenizing according to the mass ratio of the nano silicon particles, the Super P and the binder C of 80: 10; uniformly coating the uniform slurry on a copper foil, drying for 12h at 100 ℃ under a vacuum condition, and slicing; and (3) moving the dried pole piece into a glove box, and assembling the 2025 button cell by using a lithium piece as a counter electrode. Wherein the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF6The conductive salt is EC/DMC/DEC solution with the volume ratio of 1: 1, and FEC with the mass fraction of 25 percent is added as an additiveAdding the agent. And sealing the assembled battery, and standing for 12 hours. And (4) carrying out constant current electrochemical performance test on the battery after standing on a charge-discharge tester. Wherein the charge-discharge multiplying power is 0.2C, and the voltage range is 0.01-1.2V.
Example 4
The embodiment provides a silicon-based negative electrode binder of a lithium ion battery, and a preparation method and application thereof, wherein the silicon-based negative electrode binder of the lithium ion battery is formed by covalently modifying sodium alginate and polyacrylamide, and the preparation method and the application are as follows:
preparation of the binder:
adding 1.5g of sodium alginate into 48.5mL of deionized water, stirring for half an hour to form a uniform solution with the mass concentration of 3%, and transferring the solution into a four-neck round-bottom flask; dissolving initiators of potassium persulfate and sodium bisulfite in a mass ratio of 4:1 in 10mL of deionized water to prepare a solution with the mass concentration of 1%, and then transferring the solution into a constant-pressure funnel to be placed on a four-mouth round-bottom flask; dissolving 2.0g of acrylamide in 8.0mL of deionized water to form a solution with the mass concentration of 20%, transferring the solution into a constant-pressure funnel, and placing the constant-pressure funnel on a four-neck round-bottom flask; placing the four-mouth round-bottom flask in a constant-temperature water bath kettle, magnetically stirring, setting the temperature of the water bath kettle at 45 ℃, introducing high-purity nitrogen to discharge oxygen in the flask, and keeping the whole reaction system in a nitrogen atmosphere all the time; after ventilating for half an hour, opening a constant pressure funnel valve filled with an initiator, and dropwise adding the initiator into the flask at a dropping speed of 10 drops/minute; and opening a constant-pressure funnel valve filled with acrylamide after the initiator is dripped for half an hour, dripping the initiator into the flask at the dripping speed of 10 drops/min, continuously stirring for 3 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and then closing the high-purity nitrogen valve to obtain the binder A.
The application of the binder:
homogenizing according to the mass ratio of the nano silicon particles, the Super P and the binder A being 80: 10; uniformly coating the uniform slurry on a copper foil, drying for 12h at 100 ℃ under a vacuum condition, and slicing; and (3) moving the dried pole piece into a glove box, and assembling the 2025 button cell by using a lithium piece as a counter electrode. Wherein the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF6Is EC/DMC/DEC solution with conductive salt volume ratio of 1: 1, and FEC with mass fraction of 25% is added as additive. And sealing the assembled battery, and standing for 12 hours. And (4) carrying out constant current electrochemical performance test on the battery after standing on a charge-discharge tester. The voltage range is 0.01-1.2V, and the discharge capacity is controlled to be 1000 mAh/g. As shown in fig. 2, when the charge/discharge capacity of the battery is controlled to be 1000mAh/g (coulombic efficiency is always close to 100%), the binder formed by covalently modifying sodium alginate and polyacrylamide has a longer cycle life, the cycle performance of the binder is remarkably superior to that of the binder formed by singly using sodium alginate or polyacrylamide as a silicon negative electrode binder, and the integrity of an electrode structure can be better maintained (as shown in fig. 3).
Example 5
The binder was prepared in the same manner as in example 1, except that the nano-silicon particles were replaced with a silicon-carbon composite.
Example 6
The preparation method of the binder is the same as that of example 1, except that the mass ratio of the nano silicon particles, the Super P and the binder A is 70: 20: 10.
Comparative example 1
The embodiment provides a silicon-based negative electrode material binder of a lithium ion battery and application thereof, wherein the silicon-based negative electrode binder of the lithium ion battery is sodium alginate, and the specific application is as follows:
preparing a sodium alginate aqueous solution with the mass concentration of 5% as a binder for later use, and homogenizing according to the mass ratio of the nano silicon particles, the Super P and the sodium alginate of 80: 10; uniformly coating the uniform slurry on a copper foil, drying for 12h at 100 ℃ under a vacuum condition, and slicing; and (3) moving the dried pole piece into a glove box, and assembling the 2025 button cell by using a lithium piece as a counter electrode. Wherein the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF6Is EC/DMC/DEC solution with conductive salt volume ratio of 1: 1, and FEC with mass fraction of 25% is added as additive. And sealing the assembled battery, and standing for 12 hours. And (4) carrying out constant current electrochemical performance test on the battery which is well stood on a charge-discharge tester. Wherein the charge-discharge multiplying power is 0.2C, and the voltage range is 0.01-1.2V. First dischargeThe capacity was 2599mAh/g, and after 200 cycles, the discharge capacity was 786mAh/g (as shown in FIG. 1).
Comparative example 2
The embodiment provides a silicon-based negative electrode material binder of a lithium ion battery and application thereof, wherein the silicon-based negative electrode binder of the lithium ion battery is polyacrylamide, and the specific application is as follows:
preparing 2% polyacrylamide aqueous solution as a binder for later use, wherein the mass ratio of the nano silicon particles to the Super P to the polyacrylamide is 80: 10: 10, homogenizing; uniformly coating the uniform slurry on a copper foil, drying for 12h at 100 ℃ under a vacuum condition, and slicing; and (3) moving the dried pole piece into a glove box, and assembling the 2025 button cell by using a lithium piece as a counter electrode. Wherein the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF6Is EC/DMC/DEC solution with conductive salt volume ratio of 1: 1, and FEC with mass fraction of 25% is added as additive. And sealing the assembled battery, and standing for 12 hours. And (4) carrying out constant current electrochemical performance test on the battery which is well stood on a charge-discharge tester. Wherein the charge-discharge multiplying power is 0.2C, and the voltage range is 0.01-1.2V. The first discharge capacity reaches 2084mAh/g, the discharge capacity is 879mAh/g after 200 cycles, and the coulombic efficiency is kept stable all the time (as shown in figure 1).
Claims (10)
1. The lithium ion battery silicon-based negative electrode material binder is characterized by being prepared by graft copolymerization of raw materials of sodium alginate and polyacrylamide, wherein the mass ratio of the sodium alginate to the acrylamide is 1: 2-4: 1;
the sodium alginate is a linear anionic heteropolysaccharide which is formed by connecting beta-D-mannuronic acid (beta-D-mannuronic, M) and alpha-L-guluronic acid (alpha-L-guluronic acid, G) by a (1 → 4) bond; the molecular weight of the acrylamide is 71.08, and the purity of the acrylamide is 99.0%.
2. The preparation method of the lithium ion battery silicon-based negative electrode material binder disclosed by claim 1 is characterized by comprising the following specific steps of:
(1) uniformly dispersing sodium alginate in deionized water, and stirring to form a uniform sodium alginate solution;
(2) preparing potassium persulfate and sodium bisulfite into a mixed solution to obtain an initiator solution;
(3) dissolving acrylamide in deionized water to obtain an acrylamide solution;
(4) rapidly stirring the sodium alginate solution, introducing high-purity nitrogen to discharge oxygen, keeping the whole reaction system in a nitrogen atmosphere all the time, and keeping the whole reaction process in a constant temperature state by adopting a water bath;
(5) after ventilating for 0.5-5 hours, dropwise adding an initiator solution into a sodium alginate solution; after the initiator solution is dripped for 0.5-5 hours, dropwise adding the acrylamide solution into the sodium alginate solution, continuously stirring for 1-10 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and then closing a high-purity nitrogen valve to obtain the silicon-based negative electrode material binder of the lithium ion battery.
3. The preparation method of the silicon-based anode material binder of the lithium ion battery as claimed in claim 2, wherein the mass fraction of sodium alginate in the sodium alginate solution in the step (1) is 0.5-5%.
4. The preparation method of the silicon-based anode material binder of the lithium ion battery as claimed in claim 2, wherein the mass fraction of the solute in the initiator solution in the step (2) is 0.01% -10%, and the mass ratio of potassium persulfate to sodium bisulfite is 1: 1-10: 1.
5. The preparation method of the silicon-based anode material binder of the lithium ion battery as claimed in claim 2, wherein the mass fraction of the solute in the acrylamide solution in the step (3) is 5% -50%.
6. The preparation method of the silicon-based anode material binder of the lithium ion battery as claimed in claim 2, wherein the temperature of the water bath in the step (4) is 20-80 ℃.
7. The preparation method of the silicon-based anode material binder of the lithium ion battery as claimed in claim 2, wherein the dropping speed in the step (5) is 1-20 drops/min.
8. The application of the silicon-based negative electrode material binder of the lithium ion battery as defined in claim 1, which is used for preparing a negative electrode plate of the lithium ion battery.
9. A negative electrode plate of a secondary battery is characterized by being prepared from a current collector and negative electrode slurry loaded on the current collector, wherein the negative electrode slurry is prepared by mixing a negative electrode active material, a conductive additive and a binder prepared by the method of any one of claims 2 to 7, and the mass ratio of the negative electrode active material to the conductive additive to the binder is (70-80) to (10-20) to 10.
10. A secondary battery comprising a negative electrode sheet, a separator, an electrolyte, and the negative electrode sheet according to claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113851653A (en) * | 2021-09-15 | 2021-12-28 | 浙江大学 | Modified natural binder for lithium ion battery, preparation method of modified natural binder and silicon electrode piece |
| CN114605937A (en) * | 2021-12-30 | 2022-06-10 | 嘉兴学院 | Adhesive, preparation method and application thereof |
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| CN114605937A (en) * | 2021-12-30 | 2022-06-10 | 嘉兴学院 | Adhesive, preparation method and application thereof |
| CN114605937B (en) * | 2021-12-30 | 2023-09-22 | 嘉兴学院 | Adhesive, and preparation method and application thereof |
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Application publication date: 20201225 |