CN114597413B - Preparation method of silicon-based negative electrode battery binder - Google Patents
Preparation method of silicon-based negative electrode battery binder Download PDFInfo
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- CN114597413B CN114597413B CN202210247155.XA CN202210247155A CN114597413B CN 114597413 B CN114597413 B CN 114597413B CN 202210247155 A CN202210247155 A CN 202210247155A CN 114597413 B CN114597413 B CN 114597413B
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—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
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The application discloses a preparation method of a silicon-based negative electrode battery binder, and belongs to the technical field of preparation of battery binders. The preparation method of the silicon-based negative electrode battery binder is characterized by comprising the following steps of: connecting methacrylic anhydride and polysaccharide polymer through condensation reaction to obtain methacrylic anhydride modified polysaccharide polymer; and polymerizing monomers containing anionic groups and unsaturated double bonds, water-soluble monomers and methacrylic anhydride modified polysaccharide polymers under the action of an initiator by a solution polymerization method to obtain the binder. The initial capacity of the silicon-based negative electrode battery prepared by the binder is 3476mAh g ‑1 ，1A g ‑1 After 80 circles of circulation under the multiplying power, the capacity is 2070mAh g ‑1 The capacity retention after 80 cycles was 59.55%.
Description
Technical Field
The application relates to the technical field of preparation of battery binders, in particular to a preparation method of a silicon-based negative electrode battery binder.
Background
Silicon is the second most abundant element in the crust, and is inexpensive and widely available. Silicon has an extremely high stoichiometric capacity (about ten times that of graphite), and therefore lithium ion batteries using silicon as the negative electrode have received widespread attention from the battery industry. However, silicon has a volume change of approximately 300% before and after charge and discharge, resulting in difficulty in maintaining the structural integrity of the silicon-based anode for a long period of time, and active particles are easily detached from the surface of the current collector. The repeated and severe volume changes at the same time can lead to the formation of a large number of intermediate interfaces of the solid electrolyte, thereby consuming a large amount of electrolyte and causing dry cell phenomenon. Under the influence of the factors, the capacity of the silicon-based negative electrode lithium ion battery is seriously attenuated, and the commercialization process of the silicon-based negative electrode lithium ion battery is greatly hindered.
Battery binders are one of the key materials required for lithium ion battery fabrication that adhere active particles and conductive additives to the surface of a conductive current collector. Although the binder is used in an amount which is small in proportion to the total mass of the electrode (typically less than 10% or even 5%), the impact of the binder on the battery performance is significant for silicon-based cathodes with severe volume changes, and the binder with suitable strength and excellent volume change adaptability can greatly maintain the structural integrity of the electrode, thereby improving the service life of the battery. In addition, silicon is a semiconductor material, the ionic conductivity and the electronic conductivity of the silicon are low, most silicon-based negative electrode battery binders at present do not have the effect of promoting lithium ion or electronic transmission, and the addition of an inactive binder can greatly obstruct the reaction kinetics of the battery and reduce the discharge capacity of the battery. Natural polysaccharide has good water solubility, thickening property and rich sources, and becomes one of the raw materials of the adhesive which is currently under important research. The monomer with the function of promoting lithium ion transmission or electron transfer is grafted on the natural polysaccharide molecular chain, so that the ionic or electron conductivity of the natural polysaccharide can be improved, and the component with the proper glass transition temperature is copolymerized and grafted on the natural polysaccharide molecular chain, so that the Young modulus and the elongation at break of the adhesive can be improved, and the capacity of adapting to the volume change of the electrode can be further improved. However, most of the silicon-based negative electrode binders reported so far do not combine good ionic and electronic conductivity with suitable mechanical strength. In addition, in order to reduce the environmental pollution caused in the electrode preparation process, the preparation of the green and environment-friendly water-soluble adhesive is also the direction of efforts in the current battery adhesive research field.
Disclosure of Invention
The application aims to provide a preparation method of a silicon-based negative electrode battery binder, which aims to solve the problems in the prior art.
In order to achieve the above object, the present application provides the following solutions:
one of the technical schemes of the application is as follows: a preparation method of a silicon-based negative electrode battery binder comprises the following steps:
(1) Connecting methacrylic anhydride and polysaccharide polymer through condensation reaction to obtain methacrylic anhydride modified polysaccharide polymer;
(2) And polymerizing monomers containing anionic groups and unsaturated double bonds, water-soluble monomers and methacrylic anhydride modified polysaccharide polymers under the action of an initiator by a solution polymerization method to obtain the binder.
The condensation reaction of methacrylic anhydride with the polysaccharide polymer (substance C) is via an ester linkage, methacrylic anhydride being attached to the end of the hydroxymethyl side chain of the polysaccharide polymer.
Further, the polysaccharide polymer is a natural polysaccharide polymer; the natural polysaccharide polymer comprises chitosan, alginic acid, peach gum, hyaluronic acid, amylopectin, amylose, kappa-carrageenan or konjac gum.
Further, the monomer (substance a) containing an anionic group and an unsaturated double bond includes 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt, 3-sulfopropyl methacrylate potassium salt, p-styrenesulfonic acid sodium salt, or 2-methyl-2-propylene-1-sulfonic acid sodium salt.
Further, the water-soluble monomer (substance B) includes acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylamide, methacrylamide, polyethylene glycol methacrylate, N-acrylamide or N-methylolacrylamide.
Further, the initiator comprises ammonium persulfate or potassium persulfate.
Further, the mass ratio of the methacrylic anhydride to the polysaccharide polymer in the step (1) is 1:1.5 to 18; the condensation reaction is carried out under the conditions that the content is lower than 3ppm and the pH value is 7.5-8.5; the time of the condensation reaction was 24 hours.
Further, the step (2) specifically comprises: mixing and dissolving 12-18 parts by mass of monomer containing anionic groups and unsaturated double bonds, 6-13 parts by mass of water-soluble monomer and 15-35 parts by mass of methacrylic anhydride modified polysaccharide polymer, heating under the action of 1.0-2.5 parts by mass of initiator, and polymerizing by a solution polymerization method to obtain the binder; the heating temperature is 65-80 ℃; the polymerization time was 12 hours.
Further, the initiator is added in 2 times, the 1 st time is the initial period of the reaction, and the 2 nd time is the middle period of the reaction.
The second technical scheme of the application is as follows: the silicon-based negative electrode battery binder prepared by the preparation method.
The application discloses the following technical effects:
(1) The silicon-based negative electrode battery prepared by the adhesive can obviously improve the electrical property of the silicon-based negative electrode battery, and the initial capacity of the silicon-based negative electrode battery reaches 3476mAh g -1 ，1A g -1 After 80 circles of circulation under the multiplying power, the capacity reaches 2070mAh g -1 The capacity retention rate reaches 59.55% after 80 cycles.
(2) The preparation method is environment-friendly and simple to operate, takes the environment-friendly water as a solvent and the natural polysaccharide with low price as a main raw material, introduces the monomer with low glass transition temperature and the monomer containing sulfonate groups, and prepares the water-soluble modified natural polysaccharide lithium ion battery silicon-based negative electrode binder with good ionic conductivity and mechanical property by using a one-pot polymerization method.
(3) The binder prepared by the method provided by the application contains a large amount of negatively charged sulfonate ions, so that lithium ion transmission can be promoted, and the lithium ion conductivity is improved; the monomer containing polar groups such as carbonyl, ester and amide groups can form hydrogen bonding with the surfaces of the active material silicon particles, so that the bonding effect is improved. Therefore, the prepared modified binder has obviously improved ionic conductivity and bonding effect, and the electrochemical performance of the silicon-based negative electrode button half cell prepared by the modified binder is obviously improved.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
(1) Dissolving 2g of methacrylic anhydride and 15g of alginic acid (substance C) in 100g of water, stirring and dissolving, placing in a glass reactor, cooling to 3 ℃, introducing high-purity nitrogen gas to remove oxygen until the oxygen content is lower than 3ppm, regulating the pH value of the mixture solution to 7.5-8.5 by using 1mol/L NaOH solution, stirring and reacting for 24 hours, placing the product in a dialysis bag (MW: 3500D), dialyzing for 3 days (the water changing frequency is more than 8 times), and freeze-drying to obtain the product methacrylic anhydride modified alginic acid (substance D).
(2) 12g of 2-acrylamide-2-methylpropanesulfonic acid (substance A), 6g of methacrylic acid (substance B), 15g of methacrylic anhydride modified alginic acid (substance D) and 0.5g of ammonium persulfate are dissolved in 100g of water, stirred and dissolved in a glass reactor, heated to 65 ℃, and reacted for 6 hours after introducing high-purity nitrogen to exclude oxygen for 20 minutes, and then added with 0.5g of ammonium persulfate to continue to react for 6 hours, and then freeze-dried to prepare the poly (methacrylic acid-co-2-acrylamide-2-methylpropanesulfonic acid) modified alginic acid (binder).
(3) Grinding 0.16g of silica powder (grain size 100 nm) 0.02g of super p (small-grain conductive carbon black, ultra high graphite Co., ltd.), 0.02g of the binder prepared in the step (2) and 800 mu L of water uniformly, coating the mixture on copper foil, drying at 120 ℃ for 12 hours, cutting into electrode slices with the diameter of 12mm, taking a lithium slice as a counter electrode, taking a PP diaphragm (Celgard 2400) as a battery diaphragm, and assembling the 2032 button battery. Wherein the electrolyte is 1M LiPF 6 (the electrolyte solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1), and meanwhile, the additive of fluoroethylene carbonate with the mass fraction of 10% is added. A BTS-5V/50mA charge-discharge circulation tester of Shenzhen Xinwei electronic limited company is adopted to carry out constant-current charge-discharge test on the circulation performance of the battery by adopting a constant-current charge-discharge mode, the assembled button battery is static for 12 hours before the test, the current is 1A/g multiplied by the mass g of silicon in each electrode slice (the first-circle current is 0.3A/g multiplied by the mass g of silicon in each electrode slice), and the voltage range is 0.05-1.2V. Silicon content of 1.02mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 57.48%. The electrode slurry is coated on copper foil, after drying, 180 DEG peeling test is carried out on the pole piece at the room temperature at the speed of 100mm/min by referring to the method of 180 DEG peeling test of adhesive 180 DEG peeling strength test of flexible material on rigid material of GB/T2790-1995, and the bonding strength of the adhesive is 2.97kN/m.
Example 2
(1) 9g of methacrylic anhydride and 35g of konjak gum (substance C) are dissolved in 100g of water, stirred and dissolved, placed in a glass reactor, cooled to 3 ℃, and high-purity nitrogen is introduced to remove oxygen until the oxygen content is lower than 3ppm, the pH value of the mixture solution is regulated to 7.5-8.5 by using 1mol/L NaOH solution, the product is placed in a dialysis bag (MW: 3500D) after stirring and reacting for 24 hours, and the product is subjected to dialysis for 3 days (the water changing frequency is more than 8 times) and then is subjected to freeze drying to obtain the methacrylic anhydride modified konjak gum (substance D).
(2) 18g of 3-sulfopropyl methacrylate potassium salt (substance A), 13g of hydroxyethyl acrylate (substance B), 35g of methacrylic anhydride modified konjak gum (substance D) and 1.25g of potassium persulfate are dissolved in 100g of water, stirred and dissolved in a glass reactor, heated to 70 ℃, and reacted for 6 hours after high-purity nitrogen is introduced to exclude oxygen for 20 minutes, 1.25g of potassium persulfate is added to continue the reaction for 6 hours, and then the poly (hydroxyethyl acrylate-co-3-sulfopropyl methacrylate potassium salt) modified konjak gum (binder) is prepared by freeze drying.
(3) Grinding 0.16g of silica powder (grain size 100 nm) 0.02g of super p (small-grain conductive carbon black, ultra high graphite Co., ltd.), 0.02g of the binder prepared in the step (2) and 800 mu L of water uniformly, coating the mixture on copper foil, drying at 120 ℃ for 12 hours, cutting into electrode slices with the diameter of 12mm, taking a lithium slice as a counter electrode, taking a PP diaphragm (Celgard 2400) as a battery diaphragm, and assembling the 2032 button battery. Wherein the electrolyte is 1M LiPF 6 (the electrolyte solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1), and meanwhile, the additive of fluoroethylene carbonate with the mass fraction of 10% is added. A BTS-5V/50mA charge-discharge circulation tester of Shenzhen Xinwei electronic limited company is adopted to carry out constant-current charge-discharge test on the circulation performance of the battery by adopting a constant-current charge-discharge mode, the assembled button battery is static for 12 hours before the test, the current is 1A/g multiplied by the mass g of silicon in each electrode slice (the first-circle current is 0.3A/g multiplied by the mass g of silicon in each electrode slice), and the voltage range is 0.05-1.2V. Silicon content of 1.05mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 59.55%. The electrode slurry is coated on copper foil, after drying, 180 DEG peeling test is carried out on the pole piece at the room temperature at the speed of 100mm/min by referring to the method of 180 DEG peeling test of adhesive 180 DEG peeling strength test of flexible material on rigid material of GB/T2790-1995, and the bonding strength of the adhesive is 3.68kN/m.
Example 3
(1) Dissolving 5g of methacrylic anhydride and 20g of peach gum (substance C) in 100g of water, stirring and dissolving, placing the mixture in a glass reactor, cooling to 3 ℃, introducing high-purity nitrogen to remove oxygen until the oxygen content is lower than 3ppm, regulating the pH value of the mixture solution to 7.5-8.5 by using 1mol/L NaOH solution, stirring and reacting for 24 hours, placing the product in a dialysis bag (MW: 3500D), dialyzing for 3 days (the water changing frequency is more than 8 times), and freeze-drying to obtain the methacrylic anhydride modified peach gum (substance D).
(2) 9g of sodium p-styrenesulfonate (substance A), 8g of acrylamide (substance B), 20g of methacrylic anhydride modified peach gum (substance D) and 1.2g of ammonium persulfate are dissolved in 100g of water, the mixture is stirred and dissolved in a glass reactor, the temperature is raised to 75 ℃, high-purity nitrogen is introduced to exclude oxygen for 20min and then the reaction is carried out for 6h, 1.2g of ammonium persulfate is added to continue the reaction for 6h, and then the poly (acrylamide-co-sodium p-styrenesulfonate) modified peach gum (binder) is prepared by freeze drying.
(3) Grinding 0.16g of silica powder (grain size 100 nm) 0.02g of super p (small-grain conductive carbon black, ultra high graphite Co., ltd.), 0.02g of the binder prepared in the step (2) and 800 mu L of water uniformly, coating the mixture on copper foil, drying at 120 ℃ for 12 hours, cutting into electrode slices with the diameter of 12mm, taking a lithium slice as a counter electrode, taking a PP diaphragm (Celgard 2400) as a battery diaphragm, and assembling the 2032 button battery. Wherein the electrolyte is 1M LiPF 6 (the electrolyte solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1), and meanwhile, the additive of fluoroethylene carbonate with the mass fraction of 10% is added. A BTS-5V/50mA charge-discharge circulation tester of Shenzhen Xinwei electronic limited company is adopted to carry out constant-current charge-discharge test on the circulation performance of the battery by adopting a constant-current charge-discharge mode, the assembled button battery is static for 12 hours before the test, the current is 1A/g multiplied by the mass g of silicon in each electrode slice (the first-circle current is 0.3A/g multiplied by the mass g of silicon in each electrode slice), and the voltage range is 0.05-1.2V. Silicon content of 1.07mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 54.16%. The electrode slurry is coated on copper foil, after drying, 180 DEG peeling test is carried out on the pole piece at the room temperature at the speed of 100mm/min by referring to the method of 180 DEG peeling test of adhesive 180 DEG peeling strength test of flexible material on rigid material of GB/T2790-1995, and the bonding strength of the adhesive is 2.04kN/m.
Example 4
(1) Dissolving 4g of methacrylic anhydride and 22g of chitosan (substance C) in 100g of water, stirring and dissolving, placing the mixture in a glass reactor, cooling to 3 ℃, introducing high-purity nitrogen to remove oxygen until the oxygen content is lower than 3ppm, regulating the pH value of the mixture solution to 7.5-8.5 by using 1mol/L NaOH solution, stirring and reacting for 24 hours, placing the product in a dialysis bag (MW: 3500D), dialyzing for 3 days (the water changing frequency is more than 8 times), and freeze-drying to obtain methacrylic anhydride modified chitosan (substance D).
(2) 15g of 2-methyl-2-propylene-1-sulfonic acid sodium salt (substance A), 9g N- (hydroxymethyl) acrylamide (substance B), 24g of methacrylic anhydride modified chitosan (substance D) and 0.6g of potassium persulfate are dissolved in 100g of water, stirred and dissolved in a glass reactor, heated to 80 ℃, introduced with high-purity nitrogen to exclude oxygen for 20min and then reacted for 6h, added with 0.6g of potassium persulfate to continue to react for 6h, and freeze-dried to prepare the poly (N- (hydroxymethyl) acrylamide-co-2-methyl-2-propylene-1-sulfonic acid sodium salt) modified chitosan (binder).
(3) Grinding 0.16g of silica powder (grain size 100 nm) 0.02g of super p (small-grain conductive carbon black, ultra high graphite Co., ltd.), 0.02g of the binder prepared in the step (2) and 800 mu L of water uniformly, coating the mixture on copper foil, drying at 120 ℃ for 12 hours, cutting into electrode slices with the diameter of 12mm, taking a lithium slice as a counter electrode, taking a PP diaphragm (Celgard 2400) as a battery diaphragm, and assembling the 2032 button battery. Wherein the electrolyte is 1M LiPF 6 (the electrolyte solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1), and meanwhile, the additive of fluoroethylene carbonate with the mass fraction of 10% is added. A BTS-5V/50mA charge-discharge circulation tester of Shenzhen Xinwei electronic limited company is adopted to carry out constant-current charge-discharge test on the circulation performance of the battery by adopting a constant-current charge-discharge mode, the assembled button battery is static for 12 hours before the test, the current is 1A/g multiplied by the mass g of silicon in each electrode slice (the first-circle current is 0.3A/g multiplied by the mass g of silicon in each electrode slice), and the voltage range is 0.05-1.2V. Silicon content of 1.08mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 37.2%. Coating the electrode slurry on copper foil, drying and referring to
Method for 180 DEG peel Strength test of adhesive for GB/T2790-1995 Flexible Material vs. rigid Material 180 DEG peel test of Pole pieces at 100mm/min was performed at room temperature, the adhesive bond strength was 1.92kN/m.
Example 5
(1) 8g of methacrylic anhydride and 27g of kappa-carrageenan (substance C) are dissolved in 100g of water, stirred and dissolved in a glass reactor, cooled to 3 ℃, high-purity nitrogen is introduced to remove oxygen until the oxygen content is lower than 3ppm, the pH value of the mixture solution is regulated to 7.5-8.5 by using 1mol/L NaOH solution, the product is placed in a dialysis bag (MW: 3500D) after stirring and reacting for 24 hours, and the methacrylic anhydride modified carrageenan (substance D) is obtained after dialysis for 3 days (the water changing times are more than 8 times) and freeze drying.
(2) 16g of 2-acrylamide-2-methylpropanesulfonic acid sodium salt (substance A), 10g of polyethylene glycol methacrylate (substance B), 26g of methacrylic anhydride modified carrageenan (substance D) and 0.7g of ammonium persulfate are dissolved in 100g of water, stirred and dissolved in a glass reactor, heated to 80 ℃, and reacted for 6 hours after oxygen is removed by introducing high-purity nitrogen for 20min, and then the poly (polyethylene glycol methacrylate-co-2-acrylamide-2-methylpropanesulfonic acid sodium salt) modified carrageenan (binder) is prepared by adding 0.7g of ammonium persulfate for continuous reaction for 6 hours and then freeze-drying.
(3) Grinding 0.16g of silica powder (grain size 100 nm) 0.02g of super p (small-grain conductive carbon black, ultra high graphite Co., ltd.), 0.02g of the binder prepared in the step (2) and 800 mu L of water uniformly, coating the mixture on copper foil, drying at 120 ℃ for 12 hours, cutting into electrode slices with the diameter of 12mm, taking a lithium slice as a counter electrode, taking a PP diaphragm (Celgard 2400) as a battery diaphragm, and assembling the 2032 button battery. Wherein the electrolyte is 1M LiPF 6 (the electrolyte solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1), and meanwhile, the additive of fluoroethylene carbonate with the mass fraction of 10% is added. A BTS-5V/50mA charge-discharge circulation tester of Shenzhen Xinwei electronic limited company is adopted to carry out constant-current charge-discharge test on the circulation performance of the battery by adopting a constant-current charge-discharge mode, the assembled button battery is static for 12 hours before the test, the current is 1A/g multiplied by the mass g of silicon in each electrode slice (the first-circle current is 0.3A/g multiplied by the mass g of silicon in each electrode slice), and the voltage range is 0.05-1.2V. Silicon content of 1.09mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 31.4%. Coating the electrode slurry on copper foil, drying, and performing 180-degree peeling test on the pole piece at the speed of 100mm/min at room temperature by referring to the method of 180-degree peeling test of adhesive 180-degree peeling Strength test of Flexible Material on rigid Material of adhesive of GB/T2790-1995The strength was 1.87kN/m.
Example 6
(1) 7g of methacrylic anhydride and 30g of hyaluronic acid (substance C) are dissolved in 100g of water, stirred and dissolved in a glass reactor, cooled to 3 ℃, high-purity nitrogen is introduced to remove oxygen until the oxygen content is lower than 3ppm, the pH value of the mixture solution is regulated to 7.5-8.5 by using 1mol/L NaOH solution, the product is placed in a dialysis bag (MW: 3500D) after stirring and reacting for 24 hours, and the methacrylic anhydride modified hyaluronic acid (substance D) is obtained after dialysis for 3 days (the water changing frequency is more than 8 times) and freeze drying.
(2) 15g of sodium p-styrenesulfonate (substance A), 12g of hydroxyethyl methacrylate (substance B), 32g of methacrylic anhydride modified hyaluronic acid (substance D) and 0.95g of potassium persulfate are dissolved in 100g of water, stirred and dissolved in a glass reactor, heated to 80 ℃, and reacted for 6 hours after introducing high-purity nitrogen to exclude oxygen for 20 minutes, and then added with 0.95g of potassium persulfate to continue to react for 6 hours, and freeze-dried to prepare the poly (hydroxyethyl methacrylate-co-sodium p-styrenesulfonate) modified hyaluronic acid (binder).
(3) Grinding 0.16g of silica powder (grain size 100 nm) 0.02g of super p (small-grain conductive carbon black, ultra high graphite Co., ltd.), 0.02g of the binder prepared in the step (2) and 800 mu L of water uniformly, coating the mixture on copper foil, drying at 120 ℃ for 12 hours, cutting into electrode slices with the diameter of 12mm, taking a lithium slice as a counter electrode, taking a PP diaphragm (Celgard 2400) as a battery diaphragm, and assembling the 2032 button battery. Wherein the electrolyte is 1M LiPF 6 (the electrolyte solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1), and meanwhile, the additive of fluoroethylene carbonate with the mass fraction of 10% is added. A BTS-5V/50mA charge-discharge circulation tester of Shenzhen Xinwei electronic limited company is adopted to carry out constant-current charge-discharge test on the circulation performance of the battery by adopting a constant-current charge-discharge mode, the assembled button battery is static for 12 hours before the test, the current is 1A/g multiplied by the mass g of silicon in each electrode slice (the first-circle current is 0.3A/g multiplied by the mass g of silicon in each electrode slice), and the voltage range is 0.05-1.2V. Silicon content of 1.12mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 46.38%. Coating electrode slurry onOn the copper foil, 180-degree peeling test is carried out on the pole piece at the room temperature by referring to a flexible material to rigid material according to a 180-degree peeling strength test method of GB/T2790-1995 adhesive at the room temperature, and the bonding strength of the adhesive is 2.15kN/m.
The properties of the button cells prepared using the binders prepared in examples 1 to 6 are shown in table 1.
TABLE 1
As can be seen from Table 1 above, the silicon anode lithium ion battery binder prepared by mixing 35g of methacrylic anhydride modified konjac glucomannan (example 2), 18g of sulfopropyl 3-methacrylate potassium salt and 13g of hydroxyethyl acrylate, the prepared silicon electrode has the highest capacity retention.
Comparative example 1
A commercially available polyvinylidene fluoride powder (PVDF for short, model: kynar HSV 900 manufacturer: acoma PVDF) is used as the binder emulsion. A button cell was prepared as in example 1, and the cycle performance of the cell was tested using a BTS-5V/50mA charge-discharge cycle tester from Shenzhen Xinwei electronic Co. Silicon content of 1.02mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 6.52%. The electrode slurry is coated on copper foil, after drying, 180 DEG peeling test is carried out on the pole piece at the room temperature at the speed of 100mm/min by referring to the method of 180 DEG peeling test of adhesive 180 DEG peeling strength test of flexible material on rigid material of GB/T2790-1995, and the bonding strength of the adhesive is 0.25kN/m.
Comparative example 2
Commercial carboxymethyl cellulose II-styrene butadiene rubber emulsion (CMC-SBR for short), wherein the type of carboxymethyl cellulose II (CMC) is 250000Da, the viscosity is 1500-3100 mPa.s, the styrene butadiene latex is purchased from Aba Ding Shiji, the mass solid content of the styrene butadiene latex is 50%, the styrene butadiene rubber emulsion is purchased from NIPPON A&L corporation). A button cell was prepared as in example 1, and the cycle performance of the cell was tested by using a BTS-5V/50mA charge-discharge cycle tester of Shenzhen Xinwei electronic Co., ltd. Silicon content of 1.04mg/cm 2 The discharge capacity retention rate of the electrode sheet after 80 turns was 12.31%. The electrode slurry is coated on copper foil, after drying, 180 DEG peeling test is carried out on the pole piece at the room temperature at the speed of 100mm/min by referring to the method of 180 DEG peeling test of adhesive 180 DEG peeling strength test of flexible material on rigid material of GB/T2790-1995, and the bonding strength of the adhesive is 0.37kN/m.
The above embodiments are only illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solutions of the present application should fall within the protection scope defined by the claims of the present application without departing from the design spirit of the present application.
Claims (6)
1. The preparation method of the silicon-based negative electrode battery binder is characterized by comprising the following steps of:
(1) Connecting methacrylic anhydride and polysaccharide polymer through condensation reaction to obtain methacrylic anhydride modified polysaccharide polymer;
the polysaccharide polymer is a natural polysaccharide polymer; the natural polysaccharide polymer comprises chitosan, alginic acid, peach gum, hyaluronic acid, amylopectin, amylose, kappa-carrageenan or konjak gum;
(2) The monomer containing anionic groups and unsaturated double bonds, water-soluble monomer and methacrylic anhydride modified polysaccharide polymer are polymerized by a solution polymerization method under the action of an initiator to obtain the binder;
the monomer containing anionic groups and unsaturated double bonds comprises 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid sodium salt, 3-sulfopropyl methacrylate potassium salt, sodium p-styrenesulfonate or 2-methyl-2-propylene-1-sulfonic acid sodium salt;
the water-soluble monomer comprises acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylamide, methacrylamide, polyethylene glycol methacrylate, N-acrylamide or N-methylolacrylamide;
the polymerization reaction is carried out under heating; the heating temperature is 65-80 ℃; the polymerization time was 12 hours.
2. The method for preparing a silicon-based anode battery binder according to claim 1, wherein the initiator comprises ammonium persulfate or potassium persulfate.
3. The method for preparing a silicon-based anode battery binder according to claim 1, wherein the mass ratio of methacrylic anhydride to polysaccharide polymer in the step (1) is 1: 1.5-18; the condensation reaction is carried out under the conditions that the content is lower than 3ppm and the pH value is 7.5-8.5; the time of the condensation reaction was 24 hours.
4. The method for preparing a silicon-based anode battery binder according to claim 1, wherein the step (2) specifically comprises: mixing and dissolving 12-18 parts by mass of monomer containing anionic groups and unsaturated double bonds, 6-13 parts by mass of water-soluble monomer and 15-35 parts by mass of methacrylic anhydride modified polysaccharide polymer, heating under the action of 1.0-2.5 parts by mass of initiator, and polymerizing by a solution polymerization method to obtain the binder.
5. The method for preparing a silicon-based anode battery binder according to claim 1, wherein the initiator is added in 2 times, 1 st time being an initial period of reaction and 2 nd time being a middle period of reaction.
6. A silicon-based negative electrode battery binder prepared by the preparation method of any one of claims 1-5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337656A (en) * | 2013-07-05 | 2013-10-02 | 中国科学院青岛生物能源与过程研究所 | Modified biomass lithium ion battery adhesive |
| CN108232109A (en) * | 2017-12-26 | 2018-06-29 | 华中科技大学 | Konjaku glucomannan is used for the application of binding agent |
| 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 |
| CN112072106A (en) * | 2020-08-28 | 2020-12-11 | 浙江大学 | Conductive adhesive material, preparation method thereof, negative electrode plate and lithium ion battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337656A (en) * | 2013-07-05 | 2013-10-02 | 中国科学院青岛生物能源与过程研究所 | Modified biomass lithium ion battery adhesive |
| 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 |
| CN108232109A (en) * | 2017-12-26 | 2018-06-29 | 华中科技大学 | Konjaku glucomannan is used for the application of binding agent |
| CN112072106A (en) * | 2020-08-28 | 2020-12-11 | 浙江大学 | Conductive adhesive material, preparation method thereof, negative electrode plate and lithium ion battery |
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| Title |
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| "Coordinatively-intertwined dual anionic polysaccharides as binder with 3D network conducive for stable SEI formation in advanced silicon-based anodes";Yao Li等;《Chemical Engineering Journal》;第429卷;132235第1～10页 * |
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