CN114242990A - Polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder and preparation method and application thereof - Google Patents

Polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder and preparation method and application thereof Download PDF

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CN114242990A
CN114242990A CN202111387870.5A CN202111387870A CN114242990A CN 114242990 A CN114242990 A CN 114242990A CN 202111387870 A CN202111387870 A CN 202111387870A CN 114242990 A CN114242990 A CN 114242990A
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polyvinyl alcohol
aqueous solution
interpenetrating network
negative electrode
silicon
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CN114242990B (en
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王朝阳
倪培龙
蔡思全
邓永红
郑培涛
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South China University of Technology SCUT
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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 cathode aqueous binder, and a preparation method and application thereof. The adhesive is prepared by hydrogen bond crosslinking of polyvinyl alcohol and acrylic acid-acrylamide- (2-acrylamide-2-methylpropanesulfonic acid) terpolymer. The binder 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 performance can be effectively improved, and the cycle service life of the battery can be prolonged. According to the invention, the binder with an interpenetrating network structure is obtained by the free radical copolymerization of acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid monomers in a polyvinyl alcohol aqueous solution to form hydrogen bond crosslinking. The adhesive prepared by the method has strong adhesive capacity and lithium ion affinity due to various functional groups.

Description

Polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder and preparation method and application thereof
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 cathode aqueous binder, and a preparation method and application thereof.
Background
The lithium ion battery rapidly takes a leading position in the fields of mobile electronic equipment and electric automobiles due to the advantages of high discharge voltage, large energy density, long cycle life, greenness, no pollution and the like. With the ever-increasing demand for batteries for portable electronic devices and electric vehicles, the pursuit of high energy density and long cycle life electrodes has never been interrupted. The currently commonly used lithium ion battery mainly uses a 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 high-energy density battery industry.
Silicon is a hot point of current research because of its high specific capacity (4200mAh/g), abundant reserves in earth crust and low cost. Although silicon-based materials have many excellent properties, there is a need to solve a number of problems in the practical application of lithium ion batteries. Silicon has a significant volume change (about 400%) during intercalation and deintercalation with lithium ions, which easily causes cracking of the electrode material, exposure to the active surface, and continuous decomposition of the electrolyte. In addition, mechanical breakage of the internal frame of the electrode and loss of active material accelerate the degradation of the capacity of the electrode material, resulting in a reduction in the cycle life of the battery. This disadvantage of silicon anodes has led to certain difficulties in their commercialization. The silicon and the graphite are effectively and uniformly mixed to form the silicon-carbon composite material, so that the problem caused by volume expansion is reduced while the specific capacity is improved, and the silicon-carbon composite material becomes a hot spot of 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 an interconnected structure and mechanical strength for the electrode, and maintains the electron/ion transfer in the battery cycle process. Conventional binders, such as PVDF, have poor mechanical strength and poor performance for high energy density lithium ion batteries due to their relatively low adhesion. The CMC/SBR binder, while providing good cyclability and mechanical stability to the electrode, is not uniformly distributed and SBR tends to migrate with the solvent during drying. In order to effectively improve the influence of volume change generated in the charge and discharge processes of the silicon-carbon negative electrode material on the performance of the battery, the binder needs to be designed and modified. In order to meet the requirements of green, high efficiency and high performance of the current battery electrode, the development of the lithium ion battery cathode aqueous binder with high bonding strength and elasticity is urgent.
In the literature, Acrylic Acid (AA), lithium acrylate (LiAA) and hydroxyethyl acrylate (HEA) are used as monomers, and radical graft polymerization is performed on polyvinyl alcohol (PVA) to synthesize a partially lithiated ternary graft copolymer, which has good flexibility, elasticity and bonding strength. (Liu S, Zhang L. partially modified graft copolymer with enhanced elasticity as aqueous binder for Si anode [ J ]. Journal of Applied Polymer Science,2021,138.) however, the molecular weight of the graft copolymer is limited by the molecular weight of the Polymer (polyvinyl alcohol), a Polymer with a higher molecular weight cannot be synthesized, and it is difficult to form a dense network structure. In contrast, the free radical copolymerization is directly carried out in the polymer aqueous solution, so that the process is simple and convenient to operate, the high molecular weight polymer with an interpenetrating network structure can be obtained, and the bonding strength and elasticity are further improved.
Disclosure of Invention
The invention aims to provide a polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder and a preparation method thereof, aiming at the problems that the existing silicon carbon negative electrode binder has poor binding performance and is difficult to inhibit the volume expansion of active substances.
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 liquid lithium ion battery silicon carbon negative electrode.
The adhesive provided by the invention contains a large amount of polar groups, and the cross-linking of hydrogen bonds between molecular chains of polyvinyl alcohol and allyl copolymer enables the adhesive to have an interpenetrating network structure, so that strong adhesive force can be provided, and a silicon-carbon compound is tightly adhered on a current collector.
The invention provides a polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder, which comprises the 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 cross-linking through hydrogen bonds between molecular chains.
The purpose of the invention is realized 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 cathode aqueous 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, completely dissolving by ultrasonic waves, putting the mixture into an ice-water bath, cooling to room temperature, slowly adding Acrylic Acid (AA), uniformly stirring, adding Acrylamide (AM) and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, and completely dissolving by ultrasonic waves 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) adding Ammonium Persulfate (APS) into water, and completely dissolving by ultrasonic to obtain an APS aqueous solution; mixing sodium bisulfite (NaHSO)3) Adding into water, and ultrasonic dissolving completely to obtain NaHSO3An 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 NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by 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 (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, and performing vacuum drying after suction filtration to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
Further, the polyvinyl alcohol in the step (1) is PVA1788 type or PVA1797 type; the concentration of the PVA aqueous solution in the step (1) is 5-10 wt%; 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)2O); the concentration of the comonomer mixed aqueous solution in the step (2) is 20 to 30 weight percent; the molar 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, the acrylamide and the 2-acrylamide-2-methylpropanesulfonic acid in the step (2) is 1-5: 1:1(mol: mol: mol).
Preferably, the alkaline substance in the step (2) is lithium hydroxide monohydrate (LiOH. H)2O)。
Further, the concentration of the APS aqueous solution in the step (3) is 1-5 wt%; the NaHSO in the step (3)3The concentration of the aqueous solution is 1-5 wt%.
Further, in the step (4), APS and NaHSO3The molar ratio of (A) to (B) is 1-2: 1; in the step (4), the mass ratio of the comonomers (alkaline substances, AA, AM and AMPS) in the mixed aqueous solution of the APS and the comonomers is 0.1-0.5: 100; in the step (4), the mass ratio of the comonomers (alkaline substances, AA, AM and AMPS) in the mixed aqueous solution of PVA and the comonomers 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, all the water is ultrapure water, the resistivity is more than 18.2M omega cm, and the magnetic stirring rotating speed is 400 rad/min.
The invention provides a polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder prepared by the preparation method.
The invention provides an application of a polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder in preparation of a liquid lithium ion battery silicon carbon negative electrode.
The liquid lithium ion battery silicon-carbon cathode comprises: silicon-carbon composite and polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon cathode aqueous binder; the silicon-carbon composite is a mixture of a silicon-carbon active material (SiC400, SiC450, SiC500 or SiC550), a conductive agent (Super P) and a carboxymethyl cellulose aqueous solution (CMC).
The application of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder in preparing the liquid lithium ion battery silicon carbon negative electrode comprises the following steps:
(1) adding a certain mass of silicon-carbon active material into a freezing storage tube, then adding a conductive agent (Super P) and carboxymethyl cellulose aqueous solution (CMC) into the freezing storage tube in proportion, and fully shaking up the freezing storage tube on a small-sized ball mill to obtain a silicon-carbon composite which is uniformly mixed;
(2) adding the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder into the silicon carbon composite obtained in the step (1), and fully shaking up on a small ball mill to obtain uniform silicon carbon negative electrode slurry;
(3) and (3) uniformly coating the silicon-carbon negative electrode slurry obtained in the step (2) on a current collector copper foil to obtain a pole piece to be dried, putting the pole piece to be dried into a drying oven for complete drying, and cutting the pole piece into a wafer with a certain size on a slicing machine, namely the liquid lithium ion battery silicon-carbon negative electrode pole piece.
Further, the silicon-carbon active material in the step (1) is SiC400, SiC450, SiC500 or SiC 550; the concentration of the carboxymethyl cellulose aqueous solution (CMC) in the step (1) is 1 wt%; the mass ratio of the solid contents of the silicon-carbon active material, the conductive agent (Super P) and the carboxymethyl cellulose aqueous solution (CMC) in the step (1) is 94:1.5: 0.75; the volume of the freezing tube in the step (1) is 2 mL; the rotating speed of the ball mill in the step (1) is 3000-4000 rad/min; and (2) homogenizing for 3-6 min in the step (1).
Further, the mass ratio of the solid content of the silicon-carbon composite and 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; and (3) homogenizing for 9-15 min in the step (2).
Further, the temperature for drying in the oven in the step (3) is 60 ℃; drying in the oven in the step (3) for 12-24 hours; the diameter of the round piece in the step (3) is 12 mm.
The liquid lithium ion battery silicon-carbon negative pole piece provided by the invention can be applied to the preparation of a liquid lithium ion battery. The liquid lithium ion battery includes: the lithium ion battery comprises a liquid lithium ion battery silicon-carbon negative pole piece, a polymer diaphragm, electrolyte and a metal lithium piece.
The liquid lithium ion battery prepared by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode aqueous binder has the SiC400 load of 3.76mg/cm2The first charging specific capacity is 390.840mAh/g, the first coulombic efficiency is 92.604%, after the battery is circulated for 80 circles under the current density of 0.2C, the charging specific capacity still reaches 372.383mAh/g, and the capacity retention rate is 95.278%.
The third purpose 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, an 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 disclosed by the invention.
Further, the polymer diaphragm is one of a Polyethylene (PE) single-layer diaphragm, a polypropylene (PP) single-layer diaphragm or a PP/PE/PP three-layer diaphragm, and is preferably a polypropylene (PP) single-layer diaphragm.
Further, the electrolyte component is LiPF with a concentration of 1.0M6Dissolved in Ethylene Carbonate (EC) in mass ratio: diethyl carbonate (DEC): dimethyl carbonate (DMC) was added to a mixed solvent of 1:1:1 (wt%), and 10 wt% of fluoroethylene carbonate (FEC) and 2 wt% of Vinylene Carbonate (VC) were added.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method provided by the invention takes polyvinyl alcohol, acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid as basic raw materials, and generates hydrogen bond crosslinking through the free radical copolymerization of a monomer in another polymer aqueous solution to obtain the interpenetrating network water-based binder. Compared with the existing monofunctional 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 and discharge process, and ensures effective electronic conduction.
(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 molecular chains of the polyvinyl alcohol and the acrylic acid-acrylamide- (2-acrylamide-2-methylpropanesulfonic acid) copolymer further improves the bonding strength of the bonding agent, the negative active material silicon carbon material and the conductive agent can be tightly bonded on the current collector in the charging and discharging processes, the expansion of the negative active material is effectively inhibited, the falling of the negative active material is avoided, and the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous bonding agent further prolongs the cycle life of the battery.
(3) The preparation method provided by the invention is characterized in that the aqueous binder contains a large amount of polar functional groups (-COOH, -NH)2) Improves the bonding force to silicon and copper foil, and contains sulfonic acid group (-SO)3) The polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode aqueous binder has strong affinity with lithium ions and is beneficial to the conduction of the lithium ions, and the multiplying power performance of the battery can be further improved.
(4) The preparation method provided by the invention uses water as a solvent in the whole reaction process, avoids the use of toxic organic solvents compared with traditional binders such as polyvinylidene fluoride and the like, is environment-friendly and efficient, and has low equipment cost, simplicity and easiness in operation.
Drawings
FIG. 1 is a schematic view of a peeling force testing apparatus used in examples and comparative examples of the present invention;
FIG. 2a is a graph of peel test data for silicon carbon anodes prepared from the binders described in example 4, example 6, comparative example 1, and comparative example 2;
FIG. 2b is a graph of peel test data for silicon carbon anodes 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 a graph of the AC impedance at 50% SOC after 3 cycles of activation at 0.05C for liquid lithium ion batteries made using the binders described in example 2, example 3, example 6, comparative example 1, and comparative example 2;
FIG. 3b is a graph of the actual impedance values at 50% SOC after 3 cycles of activation at 0.05C for liquid lithium ion batteries made using the binders described in example 2, example 3, example 6, comparative example 1, and comparative example 2;
FIG. 4 is a graph of rate performance data for liquid lithium ion batteries made using the binders described in examples 1, 3, 4, 6, comparative 1, and 2 after 3 cycles at 0.05C and 10 cycles at 0.1C, 0.2C, 0.5C, 1C, and 0.1C, respectively, after activation at 0.05C;
FIG. 5 is a graph of specific capacity versus voltage for charging and discharging liquid lithium ion batteries made using the binders described in example 2, example 3, and comparative example 2 at 1C;
fig. 6 is a graph of the cycle curve and coulombic efficiency 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 the embodiments of the present invention are not limited thereto. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Example 1
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous 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 (0.08mol) of lithium hydroxide monohydrate (LiOH. H)2O) is added into 153.5832g of water, ultrasonic dissolution is completed, the mixture is placed into an ice water bath to be cooled to room temperature, 7.206g (0.1mol) of Acrylic Acid (AA) is added, the mixture is stirred uniformly, after the temperature of the solution is lower than the room temperature again, 7.108g (0.1mol) of Acrylamide (AM) and 20.725g (0.1mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) are added, and ultrasonic dissolution is completed to obtain a comonomer mixed water solution with the mass fraction of 20 wt%;
(3) adding 0.1g of Ammonium Persulfate (APS) into 9.9g of water, and completely dissolving by ultrasonic to obtain a1 wt% APS aqueous solution; adding 0.1g sodium bisulfite (NaHSO)3) Adding 9.9g of water, and completely dissolving by ultrasonic to obtain 1 wt% NaHSO3An aqueous solution;
(4) 153.5832g of the aqueous PVA solution from step (1), the total comonomer mixed aqueous solution from step (2), 3.8396g of the aqueous APS solution from step (3) and 0.8754g of NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at the temperature of 30 ℃ for 24 hours to obtain a product solution;
(6) and (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, performing suction filtration, and performing vacuum drying for 10 hours at the temperature of 60 ℃ to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode 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 1 wt% carboxymethyl cellulose aqueous solution (CMC) into a 2mL freezing storage tube, and shaking for 3min in a small ball mill with the shaking speed of 3000rad/min to obtain a uniformly mixed silicon-carbon composite;
B. adding 0.7500g of polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder with the mass fraction of 3 wt% into a 2mL freezing storage tube according to the mass ratio of the solid content of the silicon carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder of 96.25:3.75, and shaking the mixture for 15min in a miniature ball mill with the 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 in a 60 ℃ oven for 12h, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
D. based on the silicon-carbon negative pole piece of the liquid lithium ion battery, lithium metal is used as a counter pole, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte component is LiPF with the concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. In the absence of water and filled with argon (H)2O<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in this example was left to stand for 24 hours for electrochemical testing. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
Example 2
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder comprises the following steps:
(1) adding 10g of PVA1797 into 90g of water, heating to 90 ℃, stirring until the PVA1797 is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution with the mass fraction of 10 wt%;
(2) adding 3.6g (0.09mol) of sodium hydroxide (NaOH) into 74.1675g of water, carrying out ultrasonic dissolution completely, putting the mixture into an ice-water bath, cooling the mixture to room temperature, adding 7.206g (0.1mol) of Acrylic Acid (AA), stirring the mixture uniformly, adding 3.554g (0.05mol) of Acrylamide (AM) and 10.3625g (0.05mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) when the temperature of the solution is lower than the room temperature again, and carrying out ultrasonic dissolution completely to obtain a comonomer mixed aqueous solution with the mass fraction of 25 wt%;
(3) adding 0.2g of Ammonium Persulfate (APS) into 9.8g of water, and completely dissolving by ultrasonic to obtain a 2 wt% APS aqueous solution; adding 0.2g sodium bisulfite (NaHSO)3) Adding 9.8g of water, and completely dissolving by ultrasonic to obtain 2 wt% NaHSO3An aqueous solution;
(4) 37.0838g of the aqueous PVA solution from step (1), the total comonomer mixed aqueous solution from step (2), 2.4723g of the aqueous APS solution from step (3) and 1.1273g of NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for reacting for 18 hours to obtain a product solution;
(6) and (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, performing suction filtration, and performing vacuum drying at 50 ℃ for 12 hours to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode aqueous binder prepared in the embodiment 2 as the binder comprises the following steps:
A. 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1 wt% carboxymethyl cellulose aqueous solution (CMC) are sequentially added into a 2mL freezing storage tube, and the mixture is shaken for 3min in a small ball mill with the shaking speed of 4000rad/min to obtain a silicon-carbon composite which is uniformly mixed;
B. adding 0.7500g of polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder with the mass fraction of 3 wt% into a 2mL freezing storage tube according to the mass ratio of the solid content of the silicon carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder of 96.25:3.75, and shaking the mixture in a miniature ball mill with the shaking speed of 4000rad/min for 9min 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 in an oven at 60 ℃ for 18h, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
D. based on the silicon-carbon negative pole piece of the liquid lithium ion battery, lithium metal is used as a counter pole, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte component is LiPF with the concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. In the absence of water and filled with argon (H)2O<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in this example was left to stand for 24 hours for electrochemical testing. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
Example 3
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder comprises the following steps:
(1) adding 10g of PVA1788 into 90g of water, heating to 80 ℃, stirring until the PVA1788 is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution with the mass fraction of 10 wt%;
(2) adding 5.7228g (0.102mol) of potassium hydroxide (KOH) into 59.5075g of water, performing ultrasonic dissolution completely, putting the mixture into an ice-water bath, cooling the mixture to room temperature, adding 8.6472g (0.12mol) of Acrylic Acid (AA), stirring the mixture uniformly, adding 2.8432g (0.04mol) of Acrylamide (AM) and 8.29g (0.04mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) when the temperature of the solution is lower than the room temperature again, and performing ultrasonic dissolution completely to obtain a comonomer mixed aqueous solution with the mass fraction of 30 wt%;
(3) adding 0.5g of Ammonium Persulfate (APS) into 9.5g of water, and completely dissolving by ultrasonic to obtain a 5 wt% APS aqueous solution; adding 0.5g sodium bisulfite (NaHSO)3) Adding 9.5g of water, and completely dissolving by ultrasonic to obtain 5 wt% NaHSO3An aqueous solution;
(4) 25.5032g of the aqueous PVA solution from step (1), the total comonomer mixed aqueous solution from step (2), 2.5503g of the aqueous APS solution from step (3) and 0.5815g of NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by 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 (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, performing suction filtration, and performing vacuum drying at 40 ℃ for 11 hours to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode aqueous binder prepared in the embodiment 3 as the binder comprises the following steps:
A. 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1 wt% carboxymethyl cellulose aqueous solution (CMC) are sequentially added into a 2mL freezing tube, and the mixture is shaken for 6min in a small ball mill with the shaking speed of 3600rad/min to obtain a silicon-carbon composite which is uniformly mixed;
B. adding 0.7500g of polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder with the mass fraction of 3 wt% into a 2mL freezing storage tube according to the mass ratio of the solid content of the silicon carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder of 96.25:3.75, and shaking the mixture for 12min in a small ball mill with the 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 in a 60 ℃ oven for 24 hours, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
D. based on the silicon-carbon negative pole piece of the liquid lithium ion battery, lithium metal is used as a counter pole, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte component is LiPF with the concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. In the absence of water and filled with argon (H)2O<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in this example was left to stand for 24 hours for electrochemical testing. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
Example 4
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder comprises the following steps:
(1) adding 8g of PVA1797 into 92g of water, heating to 85 ℃, stirring until the PVA1797 is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution with the mass fraction of 8 wt%;
(2) 4.0282g (0.096mol) of lithium hydroxide monohydrate (LiOH. H)2O) is added into 84.1012g of water, dissolved completely by ultrasonic waves, put into an ice water bath and cooled to room temperatureAdding 8.6472g (0.12mol) of Acrylic Acid (AA), uniformly stirring, adding 2.1324g (0.03mol) of Acrylamide (AM) and 6.2175g (0.03mol) 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 mixture is completely dissolved to obtain a comonomer mixed aqueous solution with the mass fraction of 20 wt%;
(3) adding 0.1g of Ammonium Persulfate (APS) into 9.9g of water, and completely dissolving by ultrasonic to obtain a1 wt% APS aqueous solution; adding 0.1g sodium bisulfite (NaHSO)3) Adding 9.9g of water, and completely dissolving by ultrasonic to obtain 1 wt% NaHSO3An aqueous solution;
(4) 13.1408g of the aqueous PVA solution from step (1), the total comonomer mixed aqueous solution from step (2), 2.1025g of the aqueous APS solution from step (3) and 0.9588g of NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for 24 hours to obtain a product solution;
(6) and (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, performing suction filtration, and performing vacuum drying for 10 hours at the temperature of 50 ℃ to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode aqueous binder prepared in the embodiment 4 as the binder comprises the following steps:
A. 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1 wt% carboxymethyl cellulose aqueous solution (CMC) are sequentially added into a 2mL freezing storage tube, and the mixture is shaken for 3min in a small ball mill with the shaking speed of 4000rad/min to obtain a silicon-carbon composite which is uniformly mixed;
B. adding 0.7500g of polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder with the mass fraction of 3 wt% into a 2mL freezing storage tube according to the mass ratio of the solid content of the silicon carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder of 96.25:3.75, and shaking the mixture in a miniature ball mill with the shaking speed of 4000rad/min for 12min 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 in an oven at 60 ℃ for 18h, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
D. based on the silicon-carbon negative pole piece of the liquid lithium ion battery, lithium metal is used as a counter pole, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte component is LiPF with the concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. In the absence of water and filled with argon (H)2O<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in this example was left to stand for 24 hours for electrochemical testing. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
Example 5
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder comprises the following steps:
(1) adding 10g of PVA1788 into 90g of water, heating to 80 ℃, stirring until the PVA1788 is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution with the mass fraction of 10 wt%;
(2) adding 6.8g (0.17mol) of sodium hydroxide (NaOH) into 97.0356g of water, performing ultrasonic dissolution completely, putting the mixture into an ice-water bath, cooling the mixture to room temperature, adding 14.412g (0.2mol) of Acrylic Acid (AA), stirring the mixture uniformly, adding 2.8432g (0.04mol) of Acrylamide (AM) and 8.29g (0.04mol) of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) after the temperature of the solution is lower than the room temperature again, and performing ultrasonic dissolution completely to obtain a comonomer mixed aqueous solution with the mass fraction of 25 wt%;
(3) adding 0.1g of Ammonium Persulfate (APS) into 9.9g of water, and completely dissolving by ultrasonic to obtain a1 wt% APS aqueous solution; adding 0.1g sodium bisulfite (NaHSO)3) Adding 9.9g of water, and completely dissolving by ultrasonic to obtain 1 wt% NaHSO3An aqueous solution;
(4) 32.3452g of the aqueous PVA solution from step (1), the total comonomer mixed aqueous solution from step (2), 6.4690g of the aqueous APS solution from step (3) and 1.4749g of NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for reacting for 18 hours to obtain a product solution;
(6) and (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, performing suction filtration, and performing vacuum drying at 60 ℃ for 11 hours to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode aqueous binder prepared in the embodiment 5 as the binder comprises the following steps:
A. 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1 wt% carboxymethyl cellulose aqueous solution (CMC) are sequentially added into a 2mL freezing storage tube, and the mixture is shaken for 6min in a small ball mill with the shaking speed of 3000rad/min to obtain a silicon-carbon composite which is uniformly mixed;
B. adding 0.7500g of polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder with the mass fraction of 3 wt% into a 2mL freezing storage tube according to the mass ratio of the solid content of the silicon carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder of 96.25:3.75, and shaking the mixture for 15min in a miniature ball mill with the 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 in a 60 ℃ oven for 24 hours, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
D. based on the silicon-carbon negative pole piece of the liquid lithium ion battery, lithium metal is used as a counter pole, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte component is LiPF with the concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. In the absence of water and filled with argon (H)2O<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in this example was left to stand for 24 hours for electrochemical testing. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
Example 6
The preparation method of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder comprises the following steps:
(1) adding 10g of PVA1788 into 90g of water, heating to 80 ℃, stirring until the PVA1788 is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution with the mass fraction of 10 wt%;
(2) 4.5317g (0.108mol) of lithium hydroxide monohydrate (LiOH. H)2O) is added into 56.7282g of water, ultrasonic dissolution is carried out completely, the mixture is placed into an ice water bath to be cooled to room temperature, 8.6472g (0.12mol) of Acrylic Acid (AA) is added, stirring is carried out evenly, and 2.8432g (0) is added when the temperature of the solution is lower than the room temperature again.04mol) Acrylamide (AM) and 8.29g (0.04mol) 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), and carrying out ultrasonic treatment until complete dissolution to obtain a comonomer mixed aqueous solution with the mass fraction of 30 wt%;
(3) adding 0.5g of Ammonium Persulfate (APS) into 9.5g of water, and completely dissolving by ultrasonic to obtain a 5 wt% APS aqueous solution; adding 0.5g sodium bisulfite (NaHSO)3) Adding 9.5g of water, and completely dissolving by ultrasonic to obtain 5 wt% NaHSO3An aqueous solution;
(4) 24.3121g of the aqueous PVA solution from step (1), the total comonomer mixed aqueous solution from step (2), 0.4862g of the aqueous APS solution from step (3) and 0.1109g of NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by argon, magnetically stirring the reaction aqueous solution obtained in the step (4) at 40 ℃ for 24 hours to obtain a product solution;
(6) and (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, performing suction filtration, and performing vacuum drying at 60 ℃ for 12 hours to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
The method for assembling the liquid lithium ion battery by using the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon cathode aqueous binder prepared in the embodiment 6 as the binder comprises the following steps:
A. 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1 wt% carboxymethyl cellulose aqueous solution (CMC) are sequentially added into a 2mL freezing tube, and the mixture is shaken for 3min in a small ball mill with the shaking speed of 3600rad/min to obtain a silicon-carbon composite which is uniformly mixed;
B. adding 0.7500g of polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder with the mass fraction of 3 wt% into a 2mL freezing storage tube according to the mass ratio of the solid content of the silicon carbon composite to the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder of 96.25:3.75, and shaking the mixture for 12min in a small ball mill with the 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 in an oven at 60 ℃ for 18h, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
D. based on the silicon-carbon negative pole piece of the liquid lithium ion battery, lithium metal is used as a counter pole, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte component is LiPF with the concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. In the absence of water and filled with argon (H)2O<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in this example was left to stand for 24 hours for electrochemical testing. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
Comparative example 1
Preparing a liquid lithium ion battery using PVA1788 as a binder:
(1) adding 10g of PVA1788 into 90g of water, heating to 80 ℃, stirring until the PVA1788 is completely dissolved, and cooling to room temperature to obtain a PVA aqueous solution with the mass fraction of 10 wt%;
(2) 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1 wt% carboxymethyl cellulose aqueous solution (CMC) are sequentially added into a 2mL freezing tube, and the mixture is shaken for 3min in a small ball mill with the shaking speed of 3600rad/min to obtain a silicon-carbon composite which is uniformly mixed;
(3) adding 0.2250g of PVA aqueous solution into a 2mL freezing storage tube according to the mass ratio of the solid contents of the silicon-carbon composite in the step (2) and the PVA aqueous solution in the step (1) being 96.25:3.75, and shaking the mixture in a small ball mill at a shaking speed of 3600rad/min for 12min to obtain uniform silicon-carbon cathode slurry;
(4) coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying in an oven at 60 ℃ for 18h, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
(5) based on the silicon-carbon negative pole piece of the liquid lithium ion battery, lithium metal is used as a counter pole, the diaphragm is a polypropylene diaphragm 2500 of Celgard company, and the electrolyte component is LiPF with the concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. Under anhydrous condition and filled with argon (H2O)<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the comparative example is used for electrochemical test after standing for 24 hours. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
Comparative example 2
Preparing a liquid lithium ion battery using the allyl copolymer as a binder:
(1) 3.3568g (0.08mol) of lithium hydroxide monohydrate (LiOH. H)2O) is added into 153.5832g of water, ultrasonic dissolution is completed, the mixture is placed into an ice water bath to be cooled to room temperature, 7.206g (0.1mol) of Acrylic Acid (AA) is added, stirring is carried out evenly, after the temperature of the solution is lower than the room temperature again, 7.108g (0.1mol) of Acrylamide (AM) and 20.725g (0.1mol) of 2-Carrying out ultrasonic treatment on acrylamide-2-methylpropanesulfonic Acid (AMPS) until the acrylamide-2-methylpropanesulfonic acid is completely dissolved to obtain a comonomer mixed aqueous solution with the mass fraction of 20 wt%;
(2) adding 0.1g of Ammonium Persulfate (APS) into 9.9g of water, and completely dissolving by ultrasonic to obtain a1 wt% APS aqueous solution; adding 0.1g sodium bisulfite (NaHSO)3) Adding 9.9g of water, and completely dissolving by ultrasonic to obtain 1 wt% NaHSO3An aqueous solution;
(3) mixing the total comonomer mixed aqueous solution of the step (1), 3.8396g of APS aqueous solution of the step (2) and 0.8754g of NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(4) after air is fully replaced by argon, magnetically stirring the reaction aqueous solution obtained in the step (3) at 40 ℃ for 24 hours to obtain a product solution;
(5) and (4) freeze-drying the product solution obtained in the step (4), grinding into fine powder, washing with absolute ethyl alcohol, carrying out suction filtration, and carrying out vacuum drying at 60 ℃ for 12h to obtain the allyl copolymer binder.
The method for assembling the liquid lithium ion battery by using the allyl copolymer binder prepared in the comparative example 2 as the binder comprises the following steps:
A. 0.5640g of SiC400 active material, 0.0090g of conductive agent (Super P) and 0.4500g of 1 wt% carboxymethyl cellulose aqueous solution (CMC) are sequentially added into a 2mL freezing storage tube, and the mixture is shaken for 3min in a small ball mill with the shaking speed of 3000rad/min to obtain a silicon-carbon composite which is uniformly mixed;
B. adding 0.7500g of 3 wt% allyl copolymer binder into a 2mL freezing storage tube according to the mass ratio of the solid content of the silicon-carbon composite to the solid content of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon cathode aqueous binder being 96.25:3.75, and shaking in a small ball mill with the shaking speed of 3000rad/min for 15min to obtain uniform silicon-carbon cathode slurry;
C. coating the silicon-carbon negative electrode slurry on a copper foil by using a scraper, drying in a 60 ℃ oven for 12h, and cutting on a slicing machine to obtain a liquid lithium ion battery silicon-carbon negative electrode piece with the diameter of 12 mm;
D. based on above-mentioned liquid lithium ion battery silicon carbon negative poleA sheet having a lithium metal as a counter electrode, a diaphragm made of polypropylene 2500 manufactured by Celgard corporation, and an electrolyte component of LiPF with a concentration of 1.0M6Dissolved in a mixed solvent in a mass ratio of EC: DEC: DMC of 1:1:1 (wt%), and 10 wt% of FEC and 2 wt% of VC were added. In the absence of water and filled with argon (H)2O<0.01ppm，O2<0.01ppm) was assembled in a glove box according to the corresponding operations to obtain a liquid lithium ion button cell.
The liquid lithium ion button cell prepared in the comparative example is used for electrochemical test after standing for 24 hours. The circulation and rate performance of the assembled liquid lithium ion button battery is tested by adopting a new Wille CT2001A battery testing system at 30 ℃, and the circulation testing conditions are as follows: the charging and discharging window is selected to be 0.01-2V, and the test is carried out under the current density of 0.2C; the multiplying power test conditions are as follows: the charging and discharging 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. Performing EIS (electrochemical impedance spectroscopy) test on the assembled liquid lithium ion button cell before circulation by using a Solartron Analytical electrochemical workstation, wherein the frequency range during the test is 106HZ～10-2HZ, amplitude 5 mV.
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 a 180 ° peel test using a peel force test apparatus as shown in fig. 1, and the test effective widths were all 1.9cm, and the results are shown in fig. 2a, fig. 2b, and fig. 2 c. As can be seen from fig. 2a and 2b, the peel strength of the silicon-carbon negative electrode sheet using the binder (allyl copolymer) described in comparative example 2 is lower than that of the silicon-carbon negative electrode sheet using the binder (PVA1788) described in comparative example 1, because polyvinyl alcohol itself has very strong binding ability as a binder. The stripping force of the silicon-carbon negative pole piece using the adhesives described in the examples 3, 4, 5 and 6 is higher than that of the silicon-carbon negative pole piece using the adhesives described in the comparative example. As can be seen from fig. 2c, the average peel force of the silicon-carbon negative electrode sheet using the adhesive described in example 6 is 3.44N/cm, which is almost 2 times the average peel force (1.83N/cm) of the silicon-carbon negative electrode sheet using the adhesive (allyl copolymer) described in comparative example 2, which shows that the polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode aqueous adhesive prepared in example has further improved adhesive capacity due to the hydrogen bond crosslinking of the molecular chain and the presence of numerous polar functional groups. The binder can tightly bind the active substance and the conductive agent on the current collector in the battery cycle process, thereby ensuring the stability of the electrode structure and improving the long-term cycle stability of the battery. The silicon-carbon negative electrode plate prepared by the adhesive in other embodiments has strong peeling force, and reference can be made to fig. 2a, fig. 2b and fig. 2 c.
Fig. 3a is a graph of the ac impedance at 50% SOC after 3 cycles of activation at 0.05C for liquid lithium ion batteries prepared using the binders described in example 2, example 3, example 6, comparative example 1, and comparative example 2. The AC impedance curve is composed of two semi-circular arcs and an inclined straight line, and the intersection point of the first semi-circular arc and the x axis corresponds to the ohmic impedance (R)s) The diameter of the first semicircle corresponds to the SEI film resistance (R)SEI) The diameter of the second semicircle corresponds to the charge transfer resistance (R)ct). Fig. 3b is a graph of the actual impedance values at 50% SOC after 3 cycles of activation at 0.05C for liquid lithium ion batteries fabricated using the binders described in examples 2, 3, 6, comparative examples 1 and 2. As can be seen from the figure, the SEI film impedance and the charge transfer impedance of the liquid lithium ion battery prepared by using the binder described in the example are lower than those of the liquid lithium ion battery prepared by using the binder described in the comparative example, which shows that the aqueous binder of the silicon-carbon negative electrode of the interpenetrating network of the polyvinyl alcohol/allyl copolymer in the example can maintain the integrity of the silicon-carbon negative electrode structure, the interpenetrating network structure and the sulfonic acid group (-SO) in the battery cycle process3) 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 described herein can also maintain the structural integrity of the silicon carbon negative electrode during battery cycling and their structural properties can aid in the transport of lithium ions, as can be seen in particular in fig. 3a andfig. 3 b.
Fig. 4 is a graph of rate performance data for liquid lithium ion batteries made using the binders described in examples 1, 3, 4, 6, 1, and 2 after 3 cycles at 0.05C and 10 cycles at 0.1C, 0.2C, 0.5C, 1C, and 0.1C, respectively, after activation at 0.05C. From fig. 4, it can be seen that the specific discharge capacity of the liquid lithium ion batteries prepared by using the binders described in examples 1, 3, 4, and 6 is higher than that of the liquid lithium ion batteries prepared by using the binders described in comparative examples 1 and 2, and particularly under the condition of high current density (0.5C, 1C), the rate performance of the liquid lithium ion batteries prepared by using the binders described in examples is excellent, which indicates that the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder in 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. Liquid lithium ion batteries prepared by the binders in other embodiments have excellent rate performance, and specific reference can be made to fig. 4.
Fig. 5 is a graph of specific capacity versus voltage for charging and discharging liquid lithium ion batteries made using the binders described in example 2, example 3, and comparative example 2 under 1C conditions. As can be seen from fig. 5, the liquid lithium ion batteries prepared by using the binders described in examples 2 and 3 respectively have specific discharge capacities of 216.45mAh/g and 260mAh/g under the condition of 1C, which is much higher than the specific discharge capacity of 91.11mAh/g of the liquid lithium ion battery prepared by using the binder described in comparative example 2, which indicates that the aqueous binder of the silicon carbon negative electrode with the interpenetrating network of the polyvinyl alcohol/allyl copolymer in the examples can effectively inhibit the expansion of the silicon carbon negative electrode under high current density, and maintain the integrity of the electrode structure, so that the battery can maintain higher specific capacity. The liquid lithium ion battery prepared by the binder in other embodiments has a higher specific discharge capacity at 1C, which can be referred to fig. 5.
Fig. 6 is a graph of the cycle curve and coulombic efficiency 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 specific charge capacities (400.1322 mAh/g, 388.1998mAh/g, 395.7251mAh/g, 388.4452mAh/g, and 390.8396mAh/g) of the liquid lithium ion batteries prepared by the binders described in examples 2, 3, 4, 5, and 6 are all higher than the first specific charge capacities (380.7542 mAh/g and 375.0647mAh/g) of the liquid lithium ion batteries prepared by the binders described in comparative examples 1 and 2. After 80 cycles of circulation at 0.2 ℃, the specific charge capacity of the liquid lithium ion battery prepared by the binder in the embodiment 6 is 372.3827mAh/g, the capacity retention rate is as high as 95.28%, and the coulombic efficiency is maintained at 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 power, can firmly bind the silicon carbon active material and the conductive agent on the current collector, and can well adapt to the huge volume change of the active material, thereby prolonging the cycle service life of the battery.
In summary, compared with the binder prepared in the comparative example, the aqueous binder of the silicon carbon negative electrode with the interpenetrating network of the polyvinyl alcohol/allyl copolymer prepared in the above embodiment has excellent bonding strength and good capability of promoting lithium ion transport, so that the binder can well adapt to the huge volume change of the active material, and the silicon carbon active material and the conductive agent are tightly bonded on the current collector to prevent the slurry from falling off. Therefore, compared with the polyvinyl alcohol binder of the comparative example 1 and the allyl copolymer binder of the comparative example 2, the specific capacity, the coulombic efficiency, the rate capability and the 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, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of a polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder is characterized by comprising 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, completely dissolving by ultrasonic, putting the mixture into an ice-water bath, cooling to room temperature, adding acrylic acid, uniformly stirring, adding acrylamide and 2-acrylamide-2-methylpropanesulfonic acid after the temperature of the solution is lower than the room temperature again, and completely dissolving by ultrasonic to obtain a comonomer mixed aqueous solution; the comonomer comprises a basic substance, acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid;
(3) adding Ammonium Persulfate (APS) into water, and completely dissolving by ultrasonic to obtain an APS aqueous solution; mixing sodium bisulfite (NaHSO)3) Adding into water, and ultrasonic dissolving completely to obtain NaHSO3An 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 NaHSO3Uniformly mixing the aqueous solution to obtain a reaction aqueous solution;
(5) after air is fully replaced by 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 (4) freeze-drying the product solution obtained in the step (5), grinding the product solution into fine powder, washing the fine powder with absolute ethyl alcohol, and performing vacuum drying after suction filtration to obtain the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode aqueous binder.
2. The preparation method of the aqueous binder of the silicon carbon cathode with the interpenetrating network of the polyvinyl alcohol/allyl copolymer as the claim 1, wherein the polyvinyl alcohol in the step (1) is PVA1788 type or PVA1797 type; the concentration of the PVA aqueous solution in the step (1) is 5-10 wt%; the heating temperature in the step (1) is 80-90 ℃.
3. The preparation method of the aqueous binder for the silicon carbon cathode of the interpenetrating network of the polyvinyl alcohol/allyl copolymer as the 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 to 30 weight percent; 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, the acrylamide and the 2-acrylamide-2-methylpropanesulfonic acid in the step (2) is 1-5: 1: 1.
4. The preparation method of the aqueous binder for the silicon carbon negative electrode with the interpenetrating network of the polyvinyl alcohol/allyl copolymer as the claim 1 is characterized in that the concentration of the APS aqueous solution in the step (3) is 1-5 wt%; the NaHSO in the step (3)3The concentration of the aqueous solution is 1-5 wt%.
5. The method for preparing the aqueous binder of the silicon carbon anode with the interpenetrating network of the polyvinyl alcohol/allyl copolymer as the claimed in claim 1, wherein the APS and the NaHSO are used in the step (4)3The molar ratio of (A) to (B) is 1-2: 1; in the step (4), the mass ratio of the comonomer in the mixed aqueous solution of the APS and the comonomer is 0.1-0.5: 100; in the step (4), the mass ratio of the PVA to the comonomer in the mixed aqueous solution is 5-20: 100.
6. The preparation method of the aqueous binder for the silicon carbon cathode of the interpenetrating network of the polyvinyl alcohol/allyl copolymer as claimed in 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 preparation method of the aqueous binder for the silicon carbon cathode of the interpenetrating network of the polyvinyl alcohol/allyl copolymer as claimed in claim 1, wherein the temperature of the vacuum drying in the step (6) is 40-60 ℃; and (4) the vacuum drying time in the step (6) is 10-12 h.
8. The 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 of polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode of claim 8 in the preparation of liquid lithium ion battery silicon carbon negative electrodes.
10. The application of the aqueous binder of the polyvinyl alcohol/allyl copolymer interpenetrating network silicon carbon negative electrode in preparing the liquid lithium ion battery silicon carbon negative electrode is characterized in that the liquid lithium ion battery silicon carbon negative electrode comprises: silicon-carbon composite and polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon cathode aqueous binder; the silicon-carbon composite is a mixture of a silicon-carbon active material, a conductive agent SuperP and a carboxymethyl cellulose aqueous solution.
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