CN114242990B - Polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder and preparation method and application thereof - Google Patents
Polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder and preparation method and application thereof Download PDFInfo
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- 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
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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
- 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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Abstract
The invention discloses a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based adhesive, and a preparation method and application thereof. The adhesive is prepared by hydrogen bond crosslinking of polyvinyl alcohol and an acrylic acid-acrylamide- (2-acrylamide-2-methylpropanesulfonic acid) terpolymer. The adhesive has an interpenetrating network structure, excellent bonding strength and good capability of promoting lithium ion transmission. The adhesive is applied to a liquid lithium ion battery, so that the rate capability can be effectively improved, and the cycle service life of the battery can be prolonged. According to the invention, the adhesive with an interpenetrating network structure is obtained by forming hydrogen bond crosslinking through the free radical copolymerization of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid monomers in a polyvinyl alcohol aqueous solution. The adhesive prepared by the method has a plurality of functional groups which endow the adhesive with strong adhesive capacity and lithium ion affinity.
Description
Technical Field
The invention relates to the technical field of liquid lithium ion batteries, in particular to a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based adhesive, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high discharge voltage, high energy density, long cycle life, green and pollution-free properties, and the like, and rapidly takes the dominant role in the fields of mobile electronic equipment and electric automobiles. As the demand for batteries for portable electronic devices and electric vehicles continues to increase, the pursuit of high energy density and long cycle life electrodes has never been discontinued. The lithium ion battery commonly used at present mainly uses graphite material as a negative electrode, but the theoretical specific capacity of the graphite electrode is only 372mAh/g, which limits the further application of the lithium ion battery in the aspect of high-energy-density battery industry.
Silicon has high specific capacity (4200 mAh/g), rich reserves in the crust, and low cost, and becomes a hot spot for current research. Although silicon-based materials have many excellent properties, a series of problems still need to be solved in practical applications of lithium ion batteries. Silicon has significant volume change (about 400%) in the process of intercalation and deintercalation with lithium ions, which easily causes cracking of electrode materials, and exposure to active surfaces, so that the electrolyte is continuously decomposed. In addition, mechanical breakage of the electrode internal frame and loss of active material accelerates the decay of the electrode material capacity, resulting in a reduction in the battery cycle life. This disadvantage of silicon anodes makes commercialization thereof difficult. Silicon and graphite are effectively and uniformly mixed to form a silicon-carbon composite material, so that the specific capacity is improved, the problem caused by volume expansion is reduced, and the silicon-carbon composite material becomes a hot spot for current commercial exploration.
The polymer binder is used as a key part of the lithium ion battery, can effectively connect the active material, the conductive agent and the current collector, provides a structure and mechanical strength for the interconnection of the electrodes, and maintains electron/ion transfer in the battery cycle process. Conventional binders, such as PVDF, have poor mechanical strength due to their relatively low adhesion and poor performance for high energy density lithium ion batteries. CMC/SBR binders, while providing good cycling ability and mechanical stability to the electrode, are unevenly distributed and SBR tends to migrate with the solvent during drying. In order to effectively improve the influence of volume change generated in the charging and discharging process of the silicon-carbon anode material on the battery performance, the design and modification of the binder are needed. In order to meet the requirements of green, high efficiency and high performance of the current battery electrode, the development of a lithium ion battery cathode aqueous binder with high bonding strength and elasticity is urgent.
There are documents in which Acrylic Acid (AA), lithium acrylate (LiAA) and hydroxyethyl acrylate (HEA) are used as monomers, and free radical graft polymerization is carried out on polyvinyl alcohol (PVA) to synthesize a partially lithiated ternary graft copolymer, which has good flexibility, elasticity and adhesive strength. (Liu S, zhang L.partial lithiated ternary graft copolymer with enhanced elasticity as aqueous binder for Si anode [ J ]. Journal of Applied Polymer Science,2021,138.) but the molecular weight of the graft copolymer is limited by the molecular weight of the polymer (polyvinyl alcohol), a polymer of higher molecular weight cannot be synthesized, and it is difficult to form a dense network structure. In comparison, the free radical copolymerization is directly carried out in the polymer aqueous solution, so that the process is simple and convenient to operate, the polymer with high molecular weight and interpenetrating network structure can be obtained, and the bonding strength and the elasticity are further improved.
Disclosure of Invention
The invention aims to solve the problems that the existing silicon-carbon negative electrode adhesive is poor in adhesive performance and is difficult to inhibit volume expansion of active substances, and provides a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous adhesive and a preparation method thereof.
The second purpose of the invention is to provide the application of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder, which can be used for preparing a silicon-carbon negative electrode of a liquid lithium ion battery.
The adhesive provided by the invention contains a large number of polar groups, and the adhesive has an interpenetrating network structure due to hydrogen bond crosslinking between polyvinyl alcohol and allyl copolymer molecular chains, so that strong adhesive force can be provided, and the silicon-carbon composite can be tightly adhered on a current collector.
The invention provides a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder, which comprises the following raw materials of polyvinyl alcohol, acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid.
The invention provides a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared by crosslinking intermolecular hydrogen bonds.
The object of the invention is achieved by at least one of the following technical solutions.
The invention provides a preparation method of a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder, which comprises the following steps:
(1) Adding polyvinyl alcohol (PVA) into water, heating and stirring until the PVA is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution;
(2) Adding an alkaline substance into water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, slowly adding Acrylic Acid (AA), stirring uniformly, adding Acrylamide (AM) and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, and carrying out ultrasonic treatment until the Acrylamide (AM) and the 2-acrylamide-2-methylpropanesulfonic acid are completely dissolved to obtain a comonomer mixed aqueous solution; the comonomer comprises a basic substance, acrylic Acid (AA), acrylamide (AM) and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS);
(3) Ammonium Persulfate (APS) is added into water, and ultrasonic dissolution is completed, so as to obtain an APS water solution; sodium bisulphite (NaHSO) 3 ) Adding into water, and ultrasonic dissolving to obtain NaHSO 3 An aqueous solution;
(4) Mixing the PVA aqueous solution in the step (1), the comonomer mixed aqueous solution in the step (2), the APS aqueous solution in the step (3) and NaHSO 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) under the heating condition for reaction to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, carrying out suction filtration, and then carrying out vacuum drying to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
Further, the polyvinyl alcohol in the step (1) is of a PVA1788 type or a PVA1797 type; the concentration of the PVA aqueous solution in the step (1) is 5-10wt%; the heating temperature in the step (1) is 80-90 ℃.
Further, the alkaline substance in the step (2) is sodium hydroxide (NaOH), potassium hydroxide (KOH) or lithium hydroxide monohydrate (LiOH.H) 2 O); the concentration of the comonomer mixed aqueous solution in the step (2) is 20-30wt%; the mol ratio of the alkaline substance to the acrylic acid in the step (2) is 80-90:100 (mol: mol); the molar ratio of the acrylic acid to the acrylamide to the 2-acrylamide-2-methylpropanesulfonic acid in the step (2) is 1-5:1:1 (mol: mol).
Preferably, the alkaline substance in step (2) is lithium hydroxide monohydrate (lioh.h 2 O)。
Further, the concentration of the APS aqueous solution in the step (3) is 1 to 5 weight percent; step (3) the NaHSO 3 The concentration of the aqueous solution is 1-5 wt%.
Further, APS and NaHSO in step (4) 3 The molar ratio of (2) is 1-2:1; the mass ratio of the comonomer (alkaline matters, AA, AM and AMPS) in the mixed aqueous solution of the APS and the comonomer in the step (4) is 0.1-0.5:100; in the step (4), the mass ratio of the PVA to the comonomer (alkaline substances, AA, AM and AMPS) in the mixed aqueous solution of the PVA and the comonomer is 5-20:100.
Further, the heating temperature in the step (5) is 30-50 ℃; the reaction time in the step (5) is 12-24 h.
Further, the temperature of the vacuum drying in the step (6) is 40-60 ℃, and the time of the vacuum drying is 10-12 hours.
In the preparation method, the water is ultrapure water, the resistivity is more than 18.2MΩ & cm, and the magnetic stirring rotating speed is 400rad/min.
The invention provides a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder prepared by the preparation method.
The invention provides an application of a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder in preparing a silicon-carbon negative electrode of a liquid lithium ion battery.
The silicon-carbon negative electrode of the liquid lithium ion battery comprises: silicon-carbon composite and polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder; the silicon-carbon composite is a mixture of silicon-carbon active material (SiC 400, siC450, siC500 or SiC 550), conductive agent (Super P) and carboxymethyl cellulose water solution (CMC).
The application of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder in preparing a silicon-carbon negative electrode of a liquid lithium ion battery comprises the following steps:
(1) Adding a certain mass of silicon-carbon active material into a freezing tube, then adding a conductive agent (Super P) and a carboxymethyl cellulose water solution (CMC) into the freezing tube according to a certain proportion, and fully and uniformly shaking the mixture on a small ball mill to obtain a uniformly mixed silicon-carbon compound;
(2) Adding a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder into the silicon-carbon composite obtained in the step (1), and fully and uniformly shaking the silicon-carbon composite on a small ball mill to obtain uniform silicon-carbon negative electrode slurry;
(3) Uniformly coating the silicon-carbon negative electrode slurry obtained in the step (2) on a current collector copper foil to obtain a sheet to be dried, putting the sheet to be dried into an oven to be thoroughly dried, and cutting the sheet to a wafer with a certain size on a slicing machine to obtain the silicon-carbon negative electrode sheet of the liquid lithium ion battery.
Further, the silicon carbon active material in the step (1) is SiC400, siC450, siC500 or SiC550; the concentration of the carboxymethyl cellulose water solution (CMC) in the step (1) is 1wt%; the mass ratio of the solid contents of the silicon-carbon active material, the conductive agent (Super P) and the carboxymethyl cellulose water solution (CMC) in the step (1) is 94:1.5:0.75; the volume of the freezing storage tube in the step (1) is 2mL; the rotating speed of the ball mill in the step (1) is 3000-4000 rad/min; the homogenization time in the step (1) is 3-6 min.
Further, the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder in the step (2) is 96.25:3.75; the rotating speed of the ball mill in the step (2) is 3000-4000 rad/min; the homogenization time in the step (2) is 9-15 min.
Further, the drying temperature in the oven in the step (3) is 60 ℃; drying in the oven for 12-24 hours; and (3) the diameter of the wafer in the step (3) is 12mm.
The silicon-carbon negative electrode piece of the liquid lithium ion battery provided by the invention can be applied to the preparation of the liquid lithium ion battery. The liquid lithium ion battery includes: the lithium ion battery comprises a silicon-carbon negative electrode plate, a polymer diaphragm, electrolyte and a metal lithium plate.
The liquid lithium ion battery prepared by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder is loaded with 3.76mg/cm in SiC400 2 The initial charge specific capacity is 390.840mAh/g, the initial coulomb efficiency is 92.604%, the charge specific capacity is up to 372.383mAh/g after 80 circles of circulation under the current density of 0.2C, and the capacity retention rate is 95.278%.
The third object of the invention is to provide a liquid lithium ion battery, which comprises a liquid lithium ion battery silicon-carbon negative electrode plate, a polymer diaphragm, electrolyte and a metal lithium plate, wherein the liquid lithium ion battery silicon-carbon negative electrode plate is the liquid lithium ion battery silicon-carbon negative electrode plate.
Further, the polymer separator is one of a Polyethylene (PE) single-layer separator, a polypropylene (PP) single-layer separator or a PP/PE/PP three-layer separator, preferably a polypropylene (PP) single-layer separator.
Further, the electrolyte component is LiPF with a concentration of 1.0M 6 Dissolved in mass ratio Ethylene Carbonate (EC): diethyl carbonate (DEC): dimethyl carbonate (DMC) =1:1:1 (wt%) and 10wt% fluoroethylene carbonate (FEC) and 2wt% Vinylene Carbonate (VC) are added.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the preparation method provided by the invention, polyvinyl alcohol, acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid are used as basic raw materials, and hydrogen bond crosslinking is generated through free radical copolymerization of a monomer in another polymer aqueous solution, so that the interpenetrating network aqueous binder is obtained. Compared with the existing single-functional group linear structure negative electrode binder in the market, the binder can firmly adhere a negative electrode active material silicon carbon material and a conductive agent to a current collector in the charge-discharge process, and effective electron conduction is ensured.
(2) According to the preparation method provided by the invention, the selected commercial polymer polyvinyl alcohol has higher bonding strength, in addition, the interpenetrating network structure between the polyvinyl alcohol and the molecular chain of the acrylic acid-acrylamide- (2-acrylamide-2-methylpropanesulfonic acid) copolymer further improves the bonding strength of the adhesive, the silicon carbon material of the negative electrode active substance and the conductive agent can be tightly bonded on the current collector in the charge and discharge process, the expansion of the negative electrode active substance is effectively inhibited, the dropping of the negative electrode active substance is avoided, and the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous adhesive further prolongs the cycle life of the battery.
(3) The invention providesThe preparation method comprises that the aqueous binder contains a large amount of polar functional groups (-COOH, -NH) 2 ) Improves the adhesion to silicon and copper foil, and simultaneously contains sulfonic acid groups (-SO) 3 ) The aqueous binder of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode has stronger affinity with lithium ions, is favorable for lithium ion conduction, and can further improve the rate capability of the battery.
(4) The preparation method provided by the invention uses water as a solvent in the whole reaction process, and compared with the traditional binders such as polyvinylidene fluoride, the preparation method avoids the use of toxic organic solvents, is environment-friendly and efficient, and has low equipment cost, simplicity and easy operation.
Drawings
FIG. 1 is a schematic diagram of a peel force test apparatus used in the examples and comparative examples of the present invention;
FIG. 2a is a graph of the silicon carbon negative electrode peel test data prepared from the binders described in example 4, example 6, comparative example 1 and comparative example 2;
FIG. 2b is a graph of the silicon carbon negative electrode peel test data prepared from the binders described in example 3, example 5, comparative example 1 and comparative example 2;
FIG. 2c is a graph of average peel force data for silicon carbon anodes prepared from the binders described in example 1, example 2, example 3, example 6, comparative example 1 and comparative example 2;
Fig. 3a is an ac impedance plot at 50% SOC for liquid lithium ion batteries prepared using the binders described in example 2, example 3, example 6, comparative example 1, and comparative example 2 after 3 cycles of activation at 0.05C;
fig. 3b is a graph showing the actual impedance values at 50% SOC of a liquid lithium ion battery prepared using the binders described in example 2, example 3, example 6, comparative example 1 and comparative example 2 after 3 cycles of activation at 0.05C;
fig. 4 is a graph of rate performance data for 10 cycles at 0.1C, 0.2C, 0.5C, 1C, and 0.1C, respectively, after 3 cycles of activation at 0.05C for liquid lithium ion batteries prepared using the binders described in example 1, example 3, example 4, example 6, comparative example 1, and comparative example 2;
fig. 5 is a specific capacity-voltage diagram of charge and discharge under 1C conditions of liquid lithium ion batteries prepared using the binders described in example 2, example 3, and comparative example 2;
fig. 6 is a graph of the cycle curves and coulombic efficiencies at 0.2C for liquid lithium ion batteries prepared using the binders described in example 2, example 3, example 4, example 5, example 6, comparative example 1, and comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. Any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent substitutes for those that do not depart from the spirit and principles of the invention.
Example 1
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder comprises the following steps:
(1) Adding 5g of PVA1788 into 95g of water, heating to 80 ℃, stirring until the PVA is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution with the mass fraction of 5 wt%;
(2) 3.3568g (0.08 mol) of lithium hydroxide monohydrate (LiOH. H) 2 Adding 153.5832g of water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding 7.206g (0.1 mol) of Acrylic Acid (AA), stirring uniformly, adding 7.108g (0.1 mol) of Acrylamide (AM) and 20.725g (0.1 mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, carrying out ultrasonic dissolution completely, and obtaining a comonomer mixed aqueous solution with the mass fraction of 20 wt%;
(3) 0.1g of Ammonium Persulfate (APS) was added to 9.9g of water and the ultrasonic dissolution was completed to obtain a 1wt% APS aqueous solution; sodium bisulphite (NaHSO) 0.1g was added 3 ) Adding into 9.9g of water, and completely dissolving by ultrasonic to obtain 1wt% NaHSO 3 An aqueous solution;
(4) 153.5832g of the aqueous PVA solution from step (1), the total aqueous comonomer mixture from step (2), 3.8396g of the aqueous APS solution from step (3) and 0.8754g of NaHSO are mixed 3 Mixing the water solution uniformly to obtain An aqueous reaction solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 30 ℃ for reaction for 24 hours to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, vacuum-drying at 60 ℃ for 10 hours after suction filtration, and obtaining the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared in the embodiment 1 as the binder comprises the following steps:
A. sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 3min in a small ball mill with shaking speed of 3000rad/min to obtain a uniformly mixed silicon-carbon compound;
B. according to the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of 96.25:3.75, adding 0.7500g of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder with mass fraction of 3wt% into a 2mL freezing tube, and shaking for 15min in a small ball mill with shaking speed of 3000rad/min to obtain uniform silicon-carbon negative electrode slurry;
C. Coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 12 hours, and cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
D. based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Is anhydrous and filled with argon (H) 2 O<0.01ppm，O 2 <0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the embodiment is used for electrochemical testing after standing for 24 hours. The cycle performance and the multiplying power performance of the assembled liquid lithium ion button cell are tested by adopting a new wilt CT2001A cell testing system at 30 ℃, and the cycle testing conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is performed under the current density of 0.2C; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. EIS (electrochemical impedance spectroscopy) test of the assembled liquid lithium ion button cell before circulation is carried out by adopting Solartron Analytical electrochemical workstation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Example 2
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder comprises the following steps:
(1) 10g of PVA1797 is added into 90g of water, heated to 90 ℃, stirred until being completely dissolved, cooled to room temperature, and PVA aqueous solution with the mass fraction of 10wt% is obtained;
(2) Adding 3.6g (0.09 mol) of sodium hydroxide (NaOH) into 74.1675g of water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding 7.206g (0.1 mol) of Acrylic Acid (AA), stirring uniformly, adding 3.554g (0.05 mol) of Acrylamide (AM) and 10.3625g (0.05 mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, and carrying out ultrasonic treatment until the solution is completely dissolved to obtain a comonomer mixed aqueous solution with the mass fraction of 25 wt%;
(3) 0.2g of Ammonium Persulfate (APS) was added to 9.8g of water and the ultrasonic dissolution was completed to obtain a 2wt% APS aqueous solution; sodium bisulphite (NaHSO) 0.2g was added 3 ) Adding into 9.8g of water, and completely dissolving by ultrasonic to obtain 2wt% NaHSO 3 An aqueous solution;
(4) 37.0838g of the aqueous PVA solution from step (1), the total aqueous comonomer mixture from step (2), 2.4723g of the aqueous APS solution from step (3) and 1.1273g of NaHSO are mixed 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for reaction for 18 hours to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, vacuum-drying at 50 ℃ for 12 hours after suction filtration, and obtaining the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder prepared in the embodiment 2 as the binder comprises the following steps:
A. sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 3min in a small ball mill with shaking speed of 4000rad/min to obtain a uniformly mixed silicon-carbon compound;
B. according to the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of 96.25:3.75, adding 0.7500g of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder with mass fraction of 3wt% into a 2mL freezing tube, and shaking for 9min in a small ball mill with shaking speed of 4000rad/min to obtain uniform silicon-carbon negative electrode slurry;
C. Coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 18 hours, and cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
D. based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Is anhydrous and filled with argon (H) 2 O<0.01ppm，O 2 <0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the embodiment is staticAfter 24h for electrochemical testing. The cycle performance and the multiplying power performance of the assembled liquid lithium ion button cell are tested by adopting a new wilt CT2001A cell testing system at 30 ℃, and the cycle testing conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is performed under the current density of 0.2C; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. EIS (electrochemical impedance spectroscopy) test of the assembled liquid lithium ion button cell before circulation is carried out by adopting Solartron Analytical electrochemical workstation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Example 3
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder comprises the following steps:
(1) 10g of PVA1788 is added into 90g of water, heated to 80 ℃, stirred until being completely dissolved, cooled to room temperature, and PVA aqueous solution with the mass fraction of 10wt% is obtained;
(2) Adding 5.7228g (0.102 mol) of potassium hydroxide (KOH) into 59.5075g of water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding 8.6472g (0.12 mol) of Acrylic Acid (AA), stirring uniformly, adding 2.8432g (0.04 mol) of Acrylamide (AM) and 8.29g (0.04 mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, and carrying out ultrasonic treatment until the solution is completely dissolved to obtain a comonomer mixed aqueous solution with the mass fraction of 30 wt%;
(3) 0.5g of Ammonium Persulfate (APS) was added to 9.5g of water, and the ultrasonic dissolution was completed to obtain 5wt% APS aqueous solution; sodium bisulphite (NaHSO) 0.5g was added 3 ) Adding into 9.5g of water, and completely dissolving by ultrasonic to obtain 5wt% NaHSO 3 An aqueous solution;
(4) 25.5032g of the aqueous PVA solution from step (1), the total aqueous comonomer mixture from step (2), 2.5503g of the aqueous APS solution from step (3) and 0.5815g of NaHSO are mixed 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 50 ℃ for reaction for 12 hours to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, vacuum-drying at 40 ℃ for 11 hours after suction filtration, and obtaining the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared in the embodiment 3 as the binder comprises the following steps:
A. sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 6min in a small ball mill with shaking speed of 3600rad/min to obtain a uniformly mixed silicon-carbon compound;
B. according to the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of 96.25:3.75, adding 0.7500g of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder with mass fraction of 3wt% into a 2mL freezing tube, and shaking for 12min in a small ball mill with shaking speed of 3600rad/min to obtain uniform silicon-carbon negative electrode slurry;
C. Coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 24 hours, and cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
D. based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Is anhydrous and filled with argon (H) 2 O<0.01ppm，O 2 <0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the embodiment is used for electrochemical testing after standing for 24 hours. New Will CT2001A battery test systemThe assembled liquid lithium ion button cell is tested at 30 ℃ for cycle and multiplying power performance, and the cycle test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is performed under the current density of 0.2C; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. EIS (electrochemical impedance spectroscopy) test of the assembled liquid lithium ion button cell before circulation is carried out by adopting Solartron Analytical electrochemical workstation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Example 4
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder comprises the following steps:
(1) 8g of PVA1797 is added into 92g of water, heated to 85 ℃, stirred until being completely dissolved, cooled to room temperature, and PVA aqueous solution with the mass fraction of 8wt% is obtained;
(2) 4.0282g (0.096 mol) of lithium hydroxide monohydrate (LiOH. H) 2 Adding 84.1012g of water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding 8.6472g (0.12 mol) of Acrylic Acid (AA), stirring uniformly, adding 2.1324g (0.03 mol) of Acrylamide (AM) and 6.2175g (0.03 mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, carrying out ultrasonic dissolution completely, and obtaining a comonomer mixed aqueous solution with the mass fraction of 20 wt%;
(3) 0.1g of Ammonium Persulfate (APS) was added to 9.9g of water and the ultrasonic dissolution was completed to obtain a 1wt% APS aqueous solution; sodium bisulphite (NaHSO) 0.1g was added 3 ) Adding into 9.9g of water, and completely dissolving by ultrasonic to obtain 1wt% NaHSO 3 An aqueous solution;
(4) 13.1408g of the aqueous PVA solution from step (1), the total aqueous comonomer mixture from step (2), 2.1025g of the aqueous APS solution from step (3) and 0.9588g of NaHSO are mixed 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for reaction for 24 hours to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, vacuum-drying at 50 ℃ for 10 hours after suction filtration, and obtaining the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared in the embodiment 4 as the binder comprises the following steps:
A. sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 3min in a small ball mill with shaking speed of 4000rad/min to obtain a uniformly mixed silicon-carbon compound;
B. according to the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of 96.25:3.75, adding 0.7500g of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder with mass fraction of 3wt% into a 2mL freezing tube, and shaking for 12min in a small ball mill with shaking speed of 4000rad/min to obtain uniform silicon-carbon negative electrode slurry;
C. Coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 18 hours, and cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
D. based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Is anhydrous and filled with argon (H) 2 O<0.01ppm，O 2 <0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the embodiment is used for electrochemical testing after standing for 24 hours. Testing the assembled liquid lithium ions at 30 ℃ using a New Will CT2001A battery test SystemThe cycle test conditions of the cycle and multiplying power performance of the sub-button battery are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is performed under the current density of 0.2C; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. EIS (electrochemical impedance spectroscopy) test of the assembled liquid lithium ion button cell before circulation is carried out by adopting Solartron Analytical electrochemical workstation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Example 5
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder comprises the following steps:
(1) 10g of PVA1788 is added into 90g of water, heated to 80 ℃, stirred until being completely dissolved, cooled to room temperature, and PVA aqueous solution with the mass fraction of 10wt% is obtained;
(2) Adding 6.8g (0.17 mol) of sodium hydroxide (NaOH) into 97.0356g of water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding 14.412g (0.2 mol) of Acrylic Acid (AA), stirring uniformly, adding 2.8432g (0.04 mol) of Acrylamide (AM) and 8.29g (0.04 mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, and carrying out ultrasonic treatment until the solution is completely dissolved to obtain a comonomer mixed aqueous solution with the mass fraction of 25 wt%;
(3) 0.1g of Ammonium Persulfate (APS) was added to 9.9g of water and the ultrasonic dissolution was completed to obtain a 1wt% APS aqueous solution; sodium bisulphite (NaHSO) 0.1g was added 3 ) Adding into 9.9g of water, and completely dissolving by ultrasonic to obtain 1wt% NaHSO 3 An aqueous solution;
(4) 32.3452g of the aqueous PVA solution from step (1), the total aqueous comonomer mixture from step (2), 6.4690g of the aqueous APS solution from step (3) and 1.4749g of NaHSO are mixed 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for reaction for 18 hours to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, vacuum-drying at 60 ℃ for 11 hours after suction filtration, and obtaining the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared in the embodiment 5 as the binder comprises the following steps:
A. sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 6min in a small ball mill with shaking speed of 3000rad/min to obtain a uniformly mixed silicon-carbon compound;
B. according to the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of 96.25:3.75, adding 0.7500g of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder with mass fraction of 3wt% into a 2mL freezing tube, and shaking for 15min in a small ball mill with shaking speed of 3000rad/min to obtain uniform silicon-carbon negative electrode slurry;
C. Coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 24 hours, and cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
D. based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Is anhydrous and filled with argon (H) 2 O<0.01ppm，O 2 <0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the embodiment is used for electrochemical testing after standing for 24 hours. The cycle performance and the multiplying power performance of the assembled liquid lithium ion button cell are tested by adopting a new wilt CT2001A cell testing system at 30 ℃, and the cycle testing conditions are as follows: charging and dischargingWindow selection is between 0.01 and 2V, and test is performed under the current density of 0.2C; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. EIS (electrochemical impedance spectroscopy) test of the assembled liquid lithium ion button cell before circulation is carried out by adopting Solartron Analytical electrochemical workstation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Example 6
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder comprises the following steps:
(1) 10g of PVA1788 is added into 90g of water, heated to 80 ℃, stirred until being completely dissolved, cooled to room temperature, and PVA aqueous solution with the mass fraction of 10wt% is obtained;
(2) 4.5317g (0.108 mol) of lithium hydroxide monohydrate (LiOH. H) 2 Adding 56.7282g of water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding 8.6472g (0.12 mol) of Acrylic Acid (AA), stirring uniformly, adding 2.8432g (0.04 mol) of Acrylamide (AM) and 8.29g (0.04 mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, and carrying out ultrasonic treatment until the solution is completely dissolved to obtain a comonomer mixed aqueous solution with the mass fraction of 30 wt%;
(3) 0.5g of Ammonium Persulfate (APS) was added to 9.5g of water, and the ultrasonic dissolution was completed to obtain 5wt% APS aqueous solution; sodium bisulphite (NaHSO) 0.5g was added 3 ) Adding into 9.5g of water, and completely dissolving by ultrasonic to obtain 5wt% NaHSO 3 An aqueous solution;
(4) 24.3121g of the aqueous PVA solution from step (1), the total aqueous comonomer mixture from step (2), 0.4862g of the aqueous APS solution from step (3) and 0.1109g of NaHSO are mixed 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for reaction for 24 hours to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, vacuum-drying at 60 ℃ for 12 hours after suction filtration, and obtaining the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared in the embodiment 6 as the binder comprises the following steps:
A. sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 3min in a small ball mill with shaking speed of 3600rad/min to obtain a uniformly mixed silicon-carbon compound;
B. according to the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of 96.25:3.75, adding 0.7500g of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder with mass fraction of 3wt% into a 2mL freezing tube, and shaking for 12min in a small ball mill with shaking speed of 3600rad/min to obtain uniform silicon-carbon negative electrode slurry;
C. Coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 18 hours, and cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
D. based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Is anhydrous and filled with argon (H) 2 O<0.01ppm，O 2 <0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the embodiment is used for electrochemical testing after standing for 24 hours. The cycle performance and the multiplying power performance of the assembled liquid lithium ion button cell are tested by adopting a new wilt CT2001A cell testing system at 30 ℃, and the cycle testing conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is 0.2C current density; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. EIS (electrochemical impedance spectroscopy) test of the assembled liquid lithium ion button cell before circulation is carried out by adopting Solartron Analytical electrochemical workstation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Comparative example 1
Liquid lithium ion batteries using PVA1788 as binder were prepared:
(1) 10g of PVA1788 is added into 90g of water, heated to 80 ℃, stirred until being completely dissolved, cooled to room temperature, and PVA aqueous solution with the mass fraction of 10wt% is obtained;
(2) Sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 3min in a small ball mill with shaking speed of 3600rad/min to obtain a uniformly mixed silicon-carbon compound;
(3) According to the solid content mass ratio of the silicon-carbon compound in the step (2) to the PVA aqueous solution in the step (1) being 96.25:3.75, adding 0.2250g of the PVA aqueous solution into a 2mL freezing tube, and shaking for 12min in a small ball mill with shaking speed of 3600rad/min to obtain uniform silicon-carbon negative electrode slurry;
(4) Coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 18 hours, and then cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
(5) Based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Anhydrous and filled with argon (H2O)<0.01ppm，O2<0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the comparative example is used after standing for 24 hoursAnd (5) electrochemical testing. The cycle performance and the multiplying power performance of the assembled liquid lithium ion button cell are tested by adopting a new wilt CT2001A cell testing system at 30 ℃, and the cycle testing conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is performed under the current density of 0.2C; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. EIS (electrochemical impedance spectroscopy) test of the assembled liquid lithium ion button cell before circulation is carried out by adopting Solartron Analytical electrochemical workstation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Comparative example 2
Preparing a liquid lithium ion battery using an allyl copolymer as a binder:
(1) 3.3568g (0.08 mol) of lithium hydroxide monohydrate (LiOH. H) 2 Adding 153.5832g of water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding 7.206g (0.1 mol) of Acrylic Acid (AA), stirring uniformly, adding 7.108g (0.1 mol) of Acrylamide (AM) and 20.725g (0.1 mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, carrying out ultrasonic dissolution completely, and obtaining a comonomer mixed aqueous solution with the mass fraction of 20 wt%;
(2) 0.1g of Ammonium Persulfate (APS) was added to 9.9g of water and the ultrasonic dissolution was completed to obtain a 1wt% APS aqueous solution; sodium bisulphite (NaHSO) 0.1g was added 3 ) Adding into 9.9g of water, and completely dissolving by ultrasonic to obtain 1wt% NaHSO 3 An aqueous solution;
(3) Mixing the total comonomer aqueous solution of step (1), the 3.8396g APS aqueous solution of step (2) and 0.8754g NaHSO 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(4) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (3) at 40 ℃ for reaction for 24 hours to obtain a product solution;
(5) And (3) freeze-drying the product solution obtained in the step (4), grinding into fine powder, washing with absolute ethyl alcohol, vacuum-drying at 60 ℃ for 12 hours after suction filtration, and obtaining the allyl copolymer binder.
A method for assembling a liquid lithium ion battery using the allyl copolymer binder prepared in comparative example 2 as a binder, comprising the steps of:
A. Sequentially adding 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1wt% carboxymethyl cellulose water solution (CMC) into a 2mL freezing tube, and shaking for 3min in a small ball mill with shaking speed of 3000rad/min to obtain a uniformly mixed silicon-carbon compound;
B. according to the solid content mass ratio of the silicon-carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of 96.25:3.75, adding 0.7500g of allyl copolymer binder with mass fraction of 3wt% into a 2mL freezing tube, and shaking for 15min in a small ball mill with shaking speed of 3000rad/min to obtain uniform silicon-carbon negative electrode slurry;
C. coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying the copper foil in a 60 ℃ oven for 12 hours, and cutting the copper foil into a silicon-carbon negative electrode plate of a liquid lithium ion battery with the diameter of 12mm on a slicer;
D. based on the silicon-carbon negative electrode piece of the liquid lithium ion battery, lithium metal is used as a counter electrode, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte comprises LiPF with the concentration of 1.0M 6 Dissolved in a mixed solvent of mass ratio EC: DEC: dmc=1:1:1 (wt%), and 10wt% FEC and 2wt% VC were added. Is anhydrous and filled with argon (H) 2 O<0.01ppm，O 2 <0.01 ppm) and assembling the CR2025 type button cell according to corresponding operation in a glove box to obtain the liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the comparative example is subjected to electrochemical test after standing for 24 hours. The cycle performance and the multiplying power performance of the assembled liquid lithium ion button cell are tested by adopting a new wilt CT2001A cell testing system at 30 ℃, and the cycle testing conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is performed under the current density of 0.2C; the multiplying power test conditions are as follows: the charge and discharge window is selected to be between 0.01 and 2V, and the test is respectively carried out for 10 circles under the current density of 0.1C, 0.2C, 0.5C, 1C and 0.1C. Using Solartron Analytical electrochemical workersThe workstation performs EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation, and the frequency range is 10 6 HZ～10 -2 HZ, amplitude 5mV.
Effect analysis
The silicon carbon negative electrode sheets prepared using the binders described in example 1, example 2, example 3, example 4, example 5, example 6, comparative example 1 and comparative example 2 were subjected to 180 ° peel test using the peel force test apparatus shown in fig. 1, respectively, and the effective widths were 1.9cm, and the results are shown in fig. 2a, 2b and 2c. As can be seen from fig. 2a, 2b, the peel strength of the silicon carbon negative electrode sheet using the binder (allyl copolymer) described in comparative example 2 was lower than that of the silicon carbon negative electrode sheet using the binder (PVA 1788) described in example 1 because polyvinyl alcohol itself has a very strong binding ability as a binder. The peel force of the silicon carbon negative electrode sheets using the binders described in example 3, example 4, example 5 and example 6 was higher than the peel force of the silicon carbon negative electrode sheets using the binders described in the comparative examples. As can be seen from fig. 2c, the average peel force of the silicon carbon negative electrode sheet using the binder described in example 6 was 3.44N/cm, which is almost 2 times the average peel force (1.83N/cm) of the silicon carbon negative electrode sheet using the binder (allyl copolymer) described in comparative example 2, indicating that the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder prepared in example was further improved in its binding ability due to hydrogen bonding crosslinking of molecular chains and the presence of numerous polar functional groups. The binder can tightly bond the active substance and the conductive agent on the current collector in the battery circulation process, so that the stability of the electrode structure is ensured, and the long-term circulation stability of the battery is improved. The silicon-carbon negative electrode sheet prepared by the adhesive in other embodiments has a strong peeling force as well, and reference may be made to fig. 2a, 2b and 2c.
Fig. 3a is an ac impedance plot at 50% SOC for liquid lithium ion batteries prepared using the binders described in example 2, example 3, example 6, comparative example 1, and comparative example 2 after 3 cycles of activation at 0.05C. The alternating current impedance curve consists of two semicircular arcs and one inclined lineStraight line composition, the intersection of the first semicircle and the x-axis corresponds to the ohmic impedance (R s ) The diameter of the first semicircle corresponds to SEI film resistance (R SEI ) The diameter of the second semicircle corresponds to the charge transfer impedance (R ct ). Fig. 3b is a graph showing the actual impedance values at 50% SOC of the liquid lithium ion batteries prepared using the binders described in example 2, example 3, example 6, comparative example 1 and comparative example 2 after 3 rounds of activation at 0.05C. As can be seen from the graph, the SEI film resistance and the charge transfer resistance of the liquid lithium ion battery prepared by using the binder described in the examples are lower than those of the liquid lithium ion battery prepared by using the binder described in the comparative examples, which demonstrates that the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder in the examples can maintain the integrity of the silicon-carbon negative electrode structure during battery cycle, and the interpenetrating network structure and the sulfonic acid group (-SO) 3 ) The lithium ion transmission is facilitated, so that the impedance of the battery is reduced, and the electrochemical reaction speed of the battery is accelerated. Other embodiments the binders also maintain the structural integrity of the silicon carbon negative electrode during battery cycling and their structural characteristics facilitate lithium ion transport, see in particular fig. 3a and 3b.
Fig. 4 is a graph of rate performance data for 10 cycles at 0.1C, 0.2C, 0.5C, 1C, and 0.1C, respectively, after 3 cycles of activation at 0.05C for liquid lithium ion batteries prepared using the binders described in example 1, example 3, example 4, example 6, comparative example 1, and comparative example 2. As can be seen from fig. 4, the specific discharge capacities of the liquid lithium ion batteries prepared by using the binders of examples 1, 3, 4 and 6 are higher than those of the liquid lithium ion batteries prepared by using the binders of comparative examples 1 and 2, and particularly, the liquid lithium ion batteries prepared by using the binders of examples have excellent rate performance under the condition of high current density (0.5C and 1C), which indicates that the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of the examples can effectively reduce the influence of the volume expansion problem of the silicon-carbon negative electrode on the battery performance, thereby improving the rate performance of the battery. The binders described in other examples also produced liquid lithium ion batteries with excellent rate capability, see fig. 4.
Fig. 5 is a specific capacity-voltage graph of charge and discharge under 1C conditions of liquid lithium ion batteries prepared using the binders described in example 2, example 3, and comparative example 2. As can be seen from fig. 5, the specific discharge capacities of the liquid lithium ion batteries prepared by using the binders described in example 2 and example 3 under the condition of 1C are respectively 216.45mAh/g and 260mAh/g, which are far higher than the specific discharge capacities of the liquid lithium ion batteries prepared by using the binders described in comparative example 2 by 91.11mAh/g, which indicates that the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder in the examples can effectively inhibit the expansion of the silicon-carbon negative electrode under the condition of high current density, and maintain the structural integrity of the electrode, thereby keeping the specific capacity of the battery higher. The liquid lithium ion battery prepared by the binder in other examples also has a higher specific discharge capacity at 1C, and fig. 5 is specifically referred to.
Fig. 6 is a graph of the cycle curves and coulombic efficiencies at 0.2C for liquid lithium ion batteries prepared using the binders described in example 2, example 3, example 4, example 5, example 6, comparative example 1, and comparative example 2. As can be seen from fig. 6, the first charge specific capacities (400.1322 mAh/g, 388.1998mAh/g, 395.7251mAh/g, 388.4452mAh/g, 390.8396 mAh/g) of the liquid lithium ion batteries prepared by the binders described in examples 2, 3, 4, 5, and 6 were higher than those of the liquid lithium ion batteries prepared by the binders described in comparative examples 1 and 2 (380.7542 mAh/g, 375.0647mAh/g, respectively). After 80 circles of circulation at 0.2C, the liquid lithium ion battery prepared by the binder in the embodiment 6 has a specific charge capacity of 372.3827mAh/g, a capacity retention rate of 95.28% and a coulomb efficiency of 99.7%, which further proves that the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared in the embodiment has strong binding force, can firmly bind a silicon-carbon active material and a conductive agent on a current collector, well adapts to huge volume changes of active substances, and further improves the cycle service life of the battery.
In summary, the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared in the above embodiment has excellent bonding strength and good lithium ion transmission promoting capability compared with the binder prepared in the comparative example, so that the binder can well adapt to huge volume changes of active substances, and the silicon-carbon active material and the conductive agent are tightly bonded on the current collector to prevent slurry from falling off. Thus, compared with the polyvinyl alcohol binder of comparative example 1 and the allyl copolymer binder of comparative example 2, the specific capacity, coulombic efficiency, rate capability and long-term cycling stability of the liquid lithium ion battery based on the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder of the embodiment of the invention are greatly improved.
The above examples are only preferred embodiments of the present invention, and are merely for illustrating the present invention, not for limiting the present invention, and those skilled in the art should not be able to make any changes, substitutions, modifications and the like without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder is characterized by comprising the following steps of:
(1) Adding polyvinyl alcohol (PVA) into water, heating and stirring until the PVA is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution;
(2) Adding an alkaline substance into water, carrying out ultrasonic dissolution completely, putting into an ice water bath, cooling to room temperature, adding acrylic acid, stirring uniformly, adding acrylamide and 2-acrylamide-2-methylpropanesulfonic acid after the temperature of the solution is lower than the room temperature again, and carrying out ultrasonic treatment until the solution is completely dissolved to obtain a comonomer mixed aqueous solution; the comonomer comprises basic substances, acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid;
(3) Ammonium Persulfate (APS) is added into water, and ultrasonic dissolution is completed, so as to obtain an APS water solution; sodium bisulphite (NaHSO) 3 ) Adding into water, and ultrasonic dissolving to obtain NaHSO 3 An aqueous solution;
(4) Mixing the PVA aqueous solution in the step (1) and the comonomer in the step (2)Combining the aqueous solution, the APS aqueous solution of step (3), and NaHSO 3 Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) After fully replacing air with argon, magnetically stirring the reaction aqueous solution obtained in the step (4) under the heating condition for reaction to obtain a product solution;
(6) And (3) freeze-drying the product solution obtained in the step (5), grinding into fine powder, washing with absolute ethyl alcohol, carrying out suction filtration, and then carrying out vacuum drying to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder.
2. The method for preparing the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder according to claim 1, wherein the polyvinyl alcohol in the step (1) is of a PVA1788 type or a PVA1797 type; the concentration of the PVA aqueous solution in the step (1) is 5-10wt%; the heating temperature in the step (1) is 80-90 ℃.
3. The method for preparing the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder according to claim 1, wherein the alkaline substance in the step (2) is sodium hydroxide, potassium hydroxide or lithium hydroxide monohydrate; the concentration of the comonomer mixed aqueous solution in the step (2) is 20-30wt%; the molar ratio of the alkaline substance to the acrylic acid in the step (2) is 80-90:100; the molar ratio of the acrylic acid to the acrylamide to the 2-acrylamide-2-methylpropanesulfonic acid in the step (2) is 1-5:1:1.
4. The method for preparing the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder according to claim 1, wherein the concentration of the APS aqueous solution in the step (3) is 1-5 wt%; step (3) NaHSO 3 The concentration of the aqueous solution is 1-5 wt%.
5. The method for preparing the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder according to claim 1, wherein in the step (4), APS and NaHSO are prepared 3 Is 1 in mole ratio2:1; the mass ratio of the comonomer in the APS and comonomer mixed water solution in the step (4) is 0.1-0.5:100; in the step (4), the mass ratio of the PVA to the comonomer in the comonomer mixed aqueous solution is 5-20:100.
6. The method for preparing the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder according to claim 1, wherein the heating temperature in the step (5) is 30-50 ℃; the reaction time in the step (5) is 12-24 h.
7. The method for preparing the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder according to claim 1, wherein the temperature of the vacuum drying in the step (6) is 40-60 ℃; and (3) the time of vacuum drying in the step (6) is 10-12 h.
8. A polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder prepared by the preparation method of any one of claims 1 to 7.
9. The use of the aqueous binder for a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode of claim 8 in the preparation of a silicon-carbon negative electrode of a liquid lithium ion battery.
10. The use of the aqueous binder for a polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode in the preparation of a silicon-carbon negative electrode of a liquid lithium ion battery according to claim 9, wherein the silicon-carbon negative electrode of the liquid lithium ion battery comprises: silicon-carbon composite and polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous binder; the silicon-carbon composite is a mixture of silicon-carbon active material, conductive agent SuperP and carboxymethyl cellulose water solution.
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| WO2019242318A1 (en) * | 2018-06-20 | 2019-12-26 | 深圳市贝特瑞新能源材料股份有限公司 | Waterborne binder, preparation method therefor and use thereof |
| CN111682211A (en) * | 2020-05-29 | 2020-09-18 | 华南理工大学 | Soybean protein based double-crosslinking self-healing supermolecule sulfur anode aqueous binder and preparation method and application thereof |
| CN113206252A (en) * | 2021-04-29 | 2021-08-03 | 华南理工大学 | Soybean protein-based multifunctional double-chain cross-linked sulfur cathode aqueous binder and preparation method and application thereof |
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| WO2019242318A1 (en) * | 2018-06-20 | 2019-12-26 | 深圳市贝特瑞新能源材料股份有限公司 | Waterborne binder, preparation method therefor and use thereof |
| CN111682211A (en) * | 2020-05-29 | 2020-09-18 | 华南理工大学 | Soybean protein based double-crosslinking self-healing supermolecule sulfur anode aqueous binder and preparation method and application thereof |
| CN113206252A (en) * | 2021-04-29 | 2021-08-03 | 华南理工大学 | Soybean protein-based multifunctional double-chain cross-linked sulfur cathode aqueous binder and preparation method and application thereof |
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