A self-healing ion-electron integrated adhesive and a preparation method thereof

Abstract

The application provides a self-healing ion-electron integrated adhesive and a preparation method thereof. The adhesive is a triblock copolymer (PHUP) formed by copolymerization of three monomers of 2-hydroxyethyl acrylate (HEA), 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) and polyethylene glycol monomethyl ether methacrylate (PEGMA), and is formed by in-situ reaction of poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid) (PEDOT:PSS) on a negative electrode sheet of a full solid-state battery. The adhesive has both fast ion and electron conducting capacity and excellent self-repairing function, effectively improving the specific capacity and cycle stability of the full solid-state battery.

Description

Technical Field

[0001] This invention belongs to the field of battery materials technology, specifically relating to silicon-based anode materials for solid-state batteries, and more specifically to a self-healing ion-electron integrated adhesive and its preparation method. Background Technology

[0002] Currently, an increasing number of clean energy sources have been developed and applied in social production and daily life. Among them, lithium-ion batteries, with their energy density advantage, dominate electrochemical energy storage and are widely used in smart power generation, transportation, flexible wearable devices, and aerospace. However, the energy density of traditional lithium-ion batteries is approaching its theoretical limit. Furthermore, due to their tendency to grow lithium dendrites and the flammability and leakage of organic electrolytes, they can no longer meet the current demands for high safety and high energy density. Developing all-solid-state batteries is a feasible technological approach to improve battery safety. The non-volatile and non-flammable advantages of solid electrolytes make all-solid-state batteries a promising solution to safety issues. Simultaneously, the dense structure of solid electrolytes provides high strength and hardness, effectively preventing lithium dendrite penetration and thus improving battery cycle stability. Therefore, all-solid-state lithium batteries offer advantages such as good safety, high cycle stability, and low cost, making them one of the most popular development directions for next-generation lithium-ion batteries. Among various solid electrolytes, sulfide solid electrolytes can maintain close contact with electrode materials and exhibit ionic conductivity (>1 mS / cm) comparable to liquid and gel electrolytes at room temperature. -1 This gives it a significant advantage in all-solid-state batteries. However, sulfide solid electrolytes have a narrow electrochemical window (1.7–2.3V, vs. Li). + The electrode (electrolyte) has drawbacks such as easy decomposition and the two-dimensional rigid contact between the electrode and electrolyte prevents effective wetting of electrode particles like an electrolyte, leading to difficulties in ion and electron transport during cycling and significant battery polarization. Therefore, it is crucial to select and design electrodes to maintain the stability of the electrode-electrolyte interface and improve the ion and electron transport capability.

[0003] Silicon anodes are known for their high capacity (theoretical capacity 4200 mAh g). -1) Low cost, abundant reserves, environmentally friendly, non-toxic, and with a low electrochemical lithium intercalation potential (approximately 0.4V vs. Li / Li). +Silicon anodes have attracted widespread attention in recent research due to their advantages, such as the absence of lithium plating problems. Ying Shely Meng et al. reported an all-solid-state battery assembled with a micron-sized pure silicon anode, which retained 80% of its capacity after 500 cycles, revealing the great potential of silicon anodes in all-solid-state batteries. However, the large volume change (>300%) and poor conductivity of silicon anodes during cycling limit their further development. During charging, the continuous expansion of the silicon anode causes contact between silicon particles, and stress concentration at the contact sites due to compression ultimately leads to electrode failure and reduced cycle life. Current research has addressed the challenges faced by silicon anodes. Ungyu Paik et al. reported using Si nanoparticles embedded in carbon nanofibers coated with Li6PS5Cl (Si / CNF) as the anode material for ASSBs. By embedding silicon nanoparticles in the carbon nanofibers, a stable electron transport path is achieved. The Li6PS5Cl electrolyte layer coated on the Si / CNF forms a tight interface with the surrounding solid electrolyte, providing a well-networked ion transport path. HongliZhu achieved an all-solid-state lithium battery with high energy density and excellent cycle stability by using a composite material of nano-silicon, Li6PS5Cl, and conductive carbon as the negative electrode. The full cell provides a high capacity of 145 mAh / g at C / 3 and maintains stability for 1000 cycles. However, during the electrochemical reaction, the addition of carbon accelerates the decomposition of the sulfide solid electrolyte, leading to an increase in ionic / electron conduction impedance and a decrease in battery performance. At the same time, Li6PS5Cl is prone to hydrolysis in air, producing H2S gas, which affects electrochemical performance. Therefore, this electrode cannot be prepared in air, which is not conducive to large-scale production and application.

[0004] In liquid lithium metal batteries, binders play a crucial role in maintaining the integrity of the electrode structure during repeated lithium insertion and extraction. Binders can establish strong interfacial interactions with active particles through hydrogen bonds or covalent bonds, providing high adhesion and effectively mitigating crack formation and electrode structure damage, ultimately improving battery performance. Binder synthesis is simple and easy, and their mass percentage in the battery system is relatively low, making the use of polymer binders relatively cost-effective. Sufficient reports have demonstrated that well-designed polymer binders can significantly improve the cycle life of silicon-based electrodes. However, research on using binders to modify silicon anodes in sulfide-based all-solid-state batteries is lacking. Due to the poor conductivity of traditional binders, the introduction of binders in pure silicon anode systems further reduces electrode conductivity, thus affecting battery cycle performance. For Si-C-Li6PS5Cl composite anode systems, the polar functional groups of most organic solvents used to dissolve binders react with Li6PS5Cl. Therefore, the compatibility issues between solvents, binders, and Li6PS5Cl make slurry preparation very difficult. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a self-healing ion-electron integrated adhesive, its preparation method and application, so as to solve the problems of large volume change and poor conductivity of silicon anode in sulfide solid electrolytes during cycling.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] A self-healing ionic-electronic integrated adhesive, comprising component A and component B, wherein component A is a triblock copolymer of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate and polyethylene glycol monomethyl ether methacrylate, with the following molecular structural formula:

[0008]

[0009] Where n is 8; x is 35-50, y is 3-10, z is 35-50, and x, y, and z are all natural numbers;

[0010] Component B is poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid);

[0011] The adhesive is used to prepare silicon-based anodes for all-solid-state batteries.

[0012] Preferably, the mass ratio of component A to component B is (20-50):22.5.

[0013] Preferably, the adhesive is mixed with silicon powder and water, coated onto the current collector, and heated under vacuum. Components A and B in the adhesive react in situ to generate PHUP-g-PEDOT:PSS on the surface of the current collector, thus obtaining a silicon-based anode. The molecular structure of PHUP-g-PEDOT:PSS is:

[0014]

[0015] Preferably, the mass ratio of the silicon powder to the binder is (70-90):(10-30), and the solid content is 10%-40%.

[0016] Preferably, the heating temperature is 140-180℃ and the time is 3-6 hours.

[0017] A method for preparing a self-healing ion-electron integrated adhesive involves mixing component A, component B, and water, followed by ball milling to produce the adhesive.

[0018] Component A is a triblock copolymer of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate and polyethylene glycol monomethyl ether methacrylate; Component B is poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid).

[0019] Preferably, the preparation process of component A is as follows: 2-hydroxyethyl acrylate, polyethylene glycol monomethyl ether methacrylate, and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate are dissolved together in N,N-dimethylformamide to form a homogeneous solution F. The homogeneous solution F is degassed under vacuum, and then an initiator is added to form a reaction solution G. After the polymerization reaction occurs in the reaction solution G, it is cooled in an ice bath. The cooled solution is dialyzed and freeze-dried to obtain component A.

[0020] Preferably, the molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate and polyethylene glycol monomethyl ether methacrylate is (35-50):(5-10):(35-50).

[0021] Preferably, the preparation process of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate is as follows: 2-amino-4-hydroxy-6-methylpyrimidine and anhydrous dimethyl sulfoxide are mixed, stirred until completely dissolved, and then cooled to form a mixed solution C; 2-methylisocyanoethyl methacrylate is added to the mixed solution C to react and form a mixture D; the mixture D is filtered to obtain solid E; solid E is washed and dried to obtain the monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate.

[0022] Preferably, the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide is 1:(15-25), and the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to 2-methacrylate isocyanate is 1:(1-2).

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] This invention provides a self-healing ion-electron integrated adhesive, which is formed by the in-situ reaction of a triblock copolymer (PHUP) composed of three monomers—2-hydroxyethyl acrylate (HEA), 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA), and polyethylene glycol monomethyl ether methacrylate (PEGMA)—with poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) on the negative electrode of an all-solid-state battery. The 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)methyl methacrylate in this adhesive possesses dynamic quadruple hydrogen bonds, enabling highly efficient self-healing. The ether bonds abundant in polyethylene glycol monomethyl ether methacrylate provide lithium-ion transport pathways, enabling rapid ion transport. The conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) promotes electron conduction. 2-hydroxyethyl acrylate undergoes an esterification reaction with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), thereby grafting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) onto the polymer, achieving an integrated design. When applied to silicon-based anodes in all-solid-state batteries, it exhibits excellent structural and electrochemical stability, and can replace carbon and solid electrolyte powders, providing both the cycling stability of silicon anodes and an ion-electron transport pathway for all-solid-state batteries.

[0025] Furthermore, this adhesive enables the formation of a well-developed electron / ion conductive network within the silicon anode, while reducing side reactions at the electrode / electrolyte interface. Ethyl 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)methacrylate can form quadruple hydrogen bonds. This hydrogen bonding can both adapt to the stress generated by the large volume expansion of the silicon anode during cycling and repair damage and cracking of the silicon anode during cycling. The polyethylene glycol monomethyl ether methacrylate block contains a large number of ether bonds, enabling rapid Li+ conduction and forming an ion-conducting pathway. The conductive polymers poly(3,4-ethylenedioxythiophene) and poly(styrene sulfonic acid) have stable doped state structures, thus exhibiting excellent stability and conductivity, which can promote electron conduction. This adhesive can provide a three-dimensional ion-electron transport network for the silicon anode, improve the interfacial electrical contact between the silicon anode and the solid electrolyte, repair the structural damage of the silicon anode during cycling, maintain the cycling stability of the silicon anode, and allow for direct electrode fabrication in air without considering factors such as the decomposition of solid electrolyte additives. In summary, this adhesive combines rapid ion and electron conduction capabilities with excellent self-healing function, effectively improving the specific capacity and cycle stability of all-solid-state batteries.

[0026] This invention provides a method for preparing a self-healing ion-electron integrated adhesive. The preparation of this adhesive involves three steps: First, a self-healing 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate monomer is prepared. Second, a triblock copolymer is obtained by copolymerizing poly(2-hydroxyethyl acrylate) (HEA) monomer, polyethylene glycol monomethyl ether methacrylate monomer, and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate monomer. Third, the triblock copolymer is reacted in situ with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) on an electrode to obtain a self-healing ion-electron integrated negative electrode adhesive. The raw materials for this adhesive preparation are common monomers and commercially available conductive polymers. The preparation method is simple and easy to implement, suitable for large-scale preparation and industrial production.

[0027] Furthermore, PEGMA, HEA, and UPy have poor compatibility, and phase separation occurs when they are blended, resulting in poor product performance and the inability to fully utilize the function of each block. Triblock copolymerization of PEGMA, HEA, and UPy solves the interblock compatibility problem and fully utilizes the performance of the adhesive.

[0028] Furthermore, PEDOT:PSS is insoluble in water and other solvents, and can only be dispersed in water, unable to form a solution. The polymerization of PEDOT:PSS with PHUP takes place at 150°C, which exceeds the boiling point of water, thus preventing solution polymerization. Based on this, the homopolymer of PEDOT:PSS in water is thoroughly mixed with PHUP and silica powder and ball-milled to form a slurry. This slurry is then coated onto the current collector to undergo an in-situ reaction, thereby successfully grafting PEDOT:PSS onto PHUP and achieving an integrated design. Attached Figure Description

[0029] Figure 1 The infrared spectrum of the PHUP (HEA-UPy-PEGMA) triblock polymer prepared in Example 1 of this invention.

[0030] Figure 2 This is a comparison chart showing the rate performance of the half-cells assembled in Application Example 1 and Comparative Example 2.

[0031] Figure 3 Comparison of the long-cycle performance of the half-cells assembled in Application Example 1 and Comparative Example 2 at a current density of 1C.

[0032] Figure 4 This is a SEM image of application example 1 after 30 cycles.

[0033] Figure 5 This is a morphological diagram of Comparative Example 2 after 30 cycles. Detailed Implementation

[0034] The present invention will now be described in further detail with reference to the accompanying drawings:

[0035] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. The terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance. Furthermore, unless otherwise explicitly specified and limited, the terms "installed," "connected," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection or a detachable connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal connection of two elements. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0036] This invention discloses a self-healing ion-electronic-conductivity integrated negative electrode adhesive, which is composed of component A and component B. Component A is a triblock copolymer of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate, and polyethylene glycol monomethyl ether methacrylate, with a mass ratio of component A to component B of (20-50):22.5. The molecular structural formula of component A is:

[0037]

[0038] Where n is 8; x is 35-50, y is 5-10, z is 35-50, and x, y, and z are all natural numbers;

[0039] Component B is poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid).

[0040] This invention also discloses the application of a self-healing ion-electronic-conductivity integrated negative electrode adhesive in silicon negative electrodes. Component A and component B aqueous solutions are thoroughly mixed to obtain H solution. Silicon powder, H solution, and deionized water are added to a ball mill jar and thoroughly ball-milled. The milled slurry is then coated onto a copper foil current collector using a scraper and placed in a vacuum oven. Component A and component B undergo an in-situ reaction on the current collector to generate PHUP-g-PEDOT:PSS. The resulting material is then cut into electrode sheets with a diameter of [diameter missing], yielding the self-healing ion-electronic integrated adhesive and a silicon negative electrode composited with this adhesive.

[0041] The molecular structure of PHUP-g-PEDOT:PSS is as follows:

[0042]

[0043] Where m is approximately 5-15.

[0044] This invention also discloses a method for preparing a self-healing ion-electron integrated negative electrode adhesive, comprising the following steps:

[0045] Step 1: Add solid 2-amino-4-hydroxy-6-methylpyrimidine (UPy) to a flask, then add anhydrous dimethyl sulfoxide, stir until completely dissolved, and cool to form a mixed solution C. Then add ethyl isocyanate 2-methacrylate (ICEMA) to mixed solution C and stir to allow it to react fully to form a mixture D. Filter mixture D to obtain solid E. Wash and dry solid E to obtain monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate.

[0046] Step 2: 2-hydroxyethyl acrylate, polyethylene glycol monomethyl ether methacrylate, and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate are dissolved in N,N-dimethylformamide to form a homogeneous solution F in a Schlenk flask. F is then degassed under vacuum, and an initiator is added to form a reaction solution G. After polymerization, reaction solution G is cooled in an ice bath. The cooled solution is dialyzed and freeze-dried to obtain component A.

[0047] Step 3: Mix component A and component B aqueous solution thoroughly to obtain H solution. Add silicon powder, H solution and deionized water to ball milling jar and ball mill thoroughly. Apply the ball-milled slurry to copper foil current collector with a scraper and place it in a vacuum oven for in-situ reaction. Then cut it into electrode sheets with a diameter of _____ to obtain self-healing ion-electron integrated adhesive and silicon anode composite with the adhesive.

[0048] In one embodiment of the present invention, in step 1, the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide is 1:(15-25); the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to 2-methacrylate isocyanate is 1:(1-2).

[0049] In one embodiment of the present invention, in step 1, the stirring temperature in the mixed solution C is 100℃-150℃, and the reaction time is 3-4 hours.

[0050] In one embodiment of the present invention, in step 1, solid E is washed with acetone, dried at a temperature of 30°C-50°C, and dried for 3-4 hours.

[0051] In one embodiment of the present invention, in step 2, the molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate and polyethylene glycol monomethyl ether methacrylate is (35-50):(5-10):(35-50); and the mass fraction of the three monomers in the homogeneous solution F is 15%-25% by mass.

[0052] In one embodiment of the present invention, in step 2, the mass solution F is frozen solid in liquid nitrogen, evacuated for 5 minutes, then argon gas is introduced, thawed in water at room temperature, and then frozen and evacuated again. This process is repeated three times, and then the initiator is added.

[0053] In one embodiment of the present invention, in step 2, the initiator is azobisisobutyronitrile, and the amount used is 1 / 1000-1 / 500 of the total molar number of the three monomers.

[0054] In one embodiment of the present invention, in step 2, the polymerization reaction of reaction solution G is carried out at a temperature of 60°C-70°C for 12-36 hours.

[0055] In one embodiment of the present invention, in step 3, the particle size of the silicon powder is 30nm, 100nm, 500nm, 800nm ​​and 1μm, with the preferred particle sizes being 30nm and 800nm.

[0056] In one embodiment of the present invention, in step 3, the mass ratio of component A to component B is (20-50):22.5. The mass ratio of silicon powder to PHUP-g-PEDOT:PSS binder is (70-90):(10-30), and the solid content is 10%-40%.

[0057] As an optimized alternative, in step 3, the ball milling speed is 300-350 r / min, and the ball milling time is 30 min-1 h. The coating thickness is 40 μm-80 μm, preferably 50 μm-70 μm.

[0058] As an optimized alternative, in step 3, the in-situ reaction temperature is 140-180℃ and the time is 3-6h.

[0059] This invention provides a specific preparation method for a self-healing ionic electronic conductivity integrated adhesive, comprising the following steps:

[0060] Step 1: Add solid 2-amino-4-hydroxy-6-methylpyrimidine (UPy) to a flask, then add anhydrous dimethyl sulfoxide, heat to 100℃-150℃ and stir until completely dissolved, then cool to room temperature. Add ethyl isocyanate 2-methacrylate (ICEMA) to the flask and stir continuously for 3-4 hours. After the reaction is complete, filter the mixture and wash it three times with acetone. Place the solid in a vacuum oven at 30℃-50℃ and dry for 3-4 hours to obtain monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA).

[0061] Step 2: 2-Hydroxyethyl acrylate (HEA), polyethylene glycol monomethyl ether methacrylate (PEGMA), and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) are dissolved in N,N-dimethylformamide at room temperature to form a homogeneous solution in a Schlenk flask. The molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate, and polyethylene glycol monomethyl ether methacrylate is (35-50):(5-10):(35-50), and the total mass fraction of the three monomers is 15%-25%. The homogeneous solution is then frozen solid in liquid nitrogen, evacuated for 5 minutes, and then purged with argon gas. The solution is then allowed to cool at room temperature. Thaw in water, then freeze and degas, repeating three times; then add the initiator azobisisobutyronitrile (AIBN), wherein the amount of initiator is 1 / 1000-1 / 500 of the total molar amount of the three monomers N,N-dimethylformamide, 2-hydroxyethyl acrylate (HEA), polyethylene glycol monomethyl ether methacrylate (PEGMA), and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA), and polymerize at 60℃-70℃ for 12-36 hours; after the polymerization reaction, cool the product in an ice bath, dialyze the cooled solution for three days, and freeze-dry for two days to obtain the triblock copolymer P(HEA-co-UPyMA-co-PEGMA)(PHUP), which is used as a binder.

[0062] Step 3: Add the triblock copolymer PHUP to a 1.5% aqueous solution of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS), with a mass ratio of PHUP to PSS of (20-50):22.5. Stir until fully dissolved to obtain a mixed solution. Add silica powder, the mixed solution, and deionized water to the mushroom-shaped container, with a silica powder to binder mass ratio of (70-90). (10-30), with a solid content of 10%-40%, is ball-milled in a planetary ball mill for 1 hour to fully mix it and obtain a uniformly dispersed negative electrode slurry. The slurry is coated onto a copper foil current collector using an automatic coating agent with a coating thickness of 50μm-70μm. After coating, it is placed in a vacuum oven and reacted in situ at 140-180℃ for 3-6 hours. Then it is taken out and cut into electrode sheets with a diameter of 12mm. Finally, a self-healing ion-electron integrated adhesive and a silicon negative electrode composite with the adhesive are obtained.

[0063] This invention discloses a silicon-based all-solid-state battery assembled based on the aforementioned composite binder and silicon anode, comprising the following steps:

[0064] Step 1: Assembly of the all-solid-state half-cell. Transfer the prepared silicon anode sheet to an argon-filled ultra-clean glove box. Using a die with a diameter of 12mm, cut out one 150μm thick ultrathin lithium electrode and one 100μm thick indium electrode. Weigh 100mg of LPSC and grind it twice in a mortar. Pour the ground powder into the mold to evenly cover the anode sheet. Simultaneously, place the composite silicon anode sheet into the mold and press it together with the LPSC. Pre-press to 175MPa for 1 minute, then pressurize to 350MPa and hold for 5 minutes. After pressing, stack the lithium and indium sheets at the other end. Install the mold in a frame and press to 150MPa, holding for 1 minute, allowing the lithium and indium to form a lithium-indium alloy under pressure. Slowly depressurize to 60MPa and tighten the screws to complete the assembly.

[0065] Step 2, Electrochemical Testing: Electrochemical long-cycle testing and rate testing were performed using the assembled half-cell. Constant current discharge / charge testing was conducted within a voltage window of -0.61 to 0.88V (0.01 to 1.5V, Vs.Li). The theoretical capacity was set to 3500 mAh / g. Three cycles at 0.2C were used as a pre-cycle, followed by long-cycle testing at rates of 0.1C-2C. High-load composite silicon anode (>1 mg / cm³) was used. 2 Pre-cycle at 0.1C and cycle at 0.5C. Ratio testing was performed by cycling for 5 cycles at 0.1C, 0.2C, 0.4C, 0.6C, 0.8C, 1C, 2C and 0.1C respectively.

[0066] Step 3, Impedance Testing: To obtain the impedance change pattern during cycling and to reveal the energy barrier change at the interface and the kinetic effect of the binder on lithium-ion transport, EIS tests were performed on the assembled half-cells at the following points: before cycling, after 1 cycle, after 3 cycles (end of pre-cycle), after 20 cycles, after 40 cycles, after 60 cycles, and at the end of the cycle. The frequency ranged from 10kHz to 1000kHz.

[0067] The present invention will be further described in detail below with reference to embodiments:

[0068] Example 1

[0069] (1) 2 g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 50 mL of anhydrous dimethyl sulfoxide were added to a round-bottom flask at a molar ratio of 1:1.3 to 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and anhydrous dimethyl sulfoxide (ICEMA). The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide was 1:25. The mixture was heated to 140°C and stirred for 10 minutes until UPy was completely dissolved. After cooling the solution to room temperature, 2.5 g of 2-amino-4-hydroxy-6-methylpyrimidine (ICEMA) was added. The mixture was reacted at room temperature for 4 hours until a large amount of white precipitate formed. The mixture containing the white precipitate was filtered and washed three times with acetone, then dried in a vacuum oven at 40°C for 4 hours to obtain the monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA).

[0070] (2) Following the feeding of 2-hydroxyethyl acrylate (HEA), polyethylene glycol monomethyl ether methacrylate (PEGMA), and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) in a molar ratio of 50:10:50, 3.12 g of 2-hydroxyethyl acrylate (HEA), 3.63 g of polyethylene glycol monomethyl ether methacrylate (PEGMA), and 0.42 g of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) were dissolved in 30 mL of N,N-dimethylformamide at room temperature, and then... A homogeneous solution was formed in a Schlenk flask, with the three monomers comprising 20% ​​of the total mass. 43 mg of azobisisobutyronitrile (AIBN) initiator was added, with the initiator mass being 6‰ of the solute mass. The homogeneous solution was then frozen solid in liquid nitrogen, evacuated for 5 minutes, followed by purging with argon gas for 5 minutes. It was then thawed in water at room temperature, and this freezing and evacuation process was repeated three times. The reaction flask was then immersed in an oil bath at 70°C for 24 hours. After polymerization, the product was cooled in an ice-water bath to terminate the reaction. The cooled solution was purified by dialyzing in water for three days and freeze-dried for two days to obtain pure triblock copolymer P(HEA-co-UPyMA-co-PEGMA)(PHUP). Figure 1 The infrared spectrum of the PHUP (HEA-UPy-PEGMA) triblock polymer prepared in Example 1 of this invention is shown. The infrared spectrum confirms the presence of characteristic peaks for each block in PHUP, proving the successful synthesis of PHUP.

[0071] (3) Add 20 mg of triblock copolymer PHUP to 1.5 mL of an aqueous solution of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) with a solute mass ratio of 1.5% (PHUP:22.5). Stir until fully dissolved to obtain a mixed solution. Add 160 mg of 30 nm silica powder and 960 mL of the mixed solution to the mushroom box. The silicon powder and binder were mixed in a mass ratio of 80:20 and the solid content was 15%. The mixture was ball-milled in a planetary ball mill for 1 hour to obtain a uniformly dispersed negative electrode slurry. The slurry was coated onto a copper foil current collector using an automatic coating machine to a thickness of 60 μm. After coating, the slurry was placed in a vacuum oven and reacted in situ at 140 °C for 6 hours. The slurry was then removed and cut into electrode sheets with a diameter of 12 mm to obtain a silicon negative electrode of composite PHUP-g-PEDOT:PSS.

[0072] (4) Transfer the prepared silicon anode sheet to an argon-filled ultra-clean glove box. Use a die with a diameter of 12 mm to cut out one 150 μm thick ultrathin lithium sheet and one 100 μm thick indium sheet. Weigh 100 mg of LPSC and grind it twice in a mortar. Pour the ground powder into the mold to cover it evenly. At the same time, place the composite silicon anode sheet into the mold and press it together with LPSC. Press it to 175 MPa for 1 min, then press it to 350 MPa and hold it for 5 min. After pressing, stack lithium and indium sheets on the other end. Install the mold in the frame and press it to 150 MPa for 1 min, so that lithium and indium form a lithium-indium alloy under pressure. Slowly depressurize to 60 MPa and tighten the screws to complete the assembly.

[0073] (5) Electrochemical long-cycle tests and rate tests were performed using the assembled half-cells. Constant current discharge / charge tests were conducted within a voltage window of -0.61 to 0.88V (0.01 to 1.5V, Vs. Li), with the theoretical capacity set at 3500mAh / g. Three cycles at 0.2C were used as pre-cycles, followed by long-cycle tests at 1C. Rate tests were performed at 0.1C, 0.2C, 0.4C, 0.6C, 0.8C, 1C, 2C, and 0.1C for 5 cycles each. EIS tests were performed using the assembled half-cells at the following points: before cycling, after 1 cycle, after 3 cycles (end of pre-cycle), after 50 cycles, after 150 cycles, after 250 cycles, and at the end of the cycle. The frequency range was 10kHz-1000kHz. Figure 2 This is a comparison chart of the rate performance of the half-cells assembled in Example 1 and Comparative Example 2. It can be seen that Example 1 exhibits superior rate performance compared to Comparative Example 2. Figure 3 A comparison chart of the long-term cycling performance of the half-cells assembled in Example 1 and Comparative Example 2 at a current density of 1C. It can be seen that Example 1 exhibits superior cycling stability compared to Comparative Example 2. Figure 4 This is a SEM image of the application of Example 1 after 30 cycles. Figure 5 The image shows the morphology of Comparative Example 2 after 30 cycles. It can be seen that compared with Comparative Example 2, Example 1 has fewer cracks, proving that the structure has better stability.

[0074] Example 2

[0075] (1) 2 g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 50 mL of anhydrous dimethyl sulfoxide were added to a round-bottom flask at a molar ratio of 1:1.3 to 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 1:25 of anhydrous dimethyl sulfoxide. The mixture was heated to 140°C and stirred for 10 minutes until UPy was completely dissolved. After cooling the solution to room temperature, 2.5 g of 2-amino-4-hydroxy-6-methylpyrimidine (ICEMA) was added. The mixture was reacted at room temperature for 4 hours until a large amount of white precipitate formed. The mixture containing the white precipitate was filtered and washed three times with acetone, then dried in a vacuum oven at 40°C for 4 hours to obtain the monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA).

[0076] (2) Following the feeding of 2-hydroxyethyl acrylate (HEA), polyethylene glycol monomethyl ether methacrylate (PEGMA), and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) in a molar ratio of 50:10:50, 3.12 g of 2-hydroxyethyl acrylate (HEA), 3.63 g of polyethylene glycol monomethyl ether methacrylate (PEGMA), and 0.42 g of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) were dissolved in 30 mL of N,N-dimethylformamide at room temperature, and then... A homogeneous solution was formed in a Schlenk flask, with the three monomers comprising 20% ​​of the total mass. 43 mg of azobisisobutyronitrile (AIBN) initiator was added, with the initiator mass being 6‰ of the solute mass. The homogeneous solution was then frozen solid in liquid nitrogen, evacuated for 5 minutes, followed by purging with argon gas for 5 minutes. It was then thawed in water at room temperature, and this freezing and evacuation process was repeated three times. The reaction flask was then immersed in an oil bath at 70°C for 24 hours. After polymerization, the product was cooled in an ice-water bath to terminate the reaction. The cooled solution was purified by dialyzing in water for three days and freeze-dried for two days to obtain pure triblock copolymer P(HEA-co-UPyMA-co-PEGMA)(PHUP).

[0077] (3) Add 4g of acrylic acid (AA) to a 50mL round-bottom flask, add a mixed solution of 16g ​​of N,N-dimethylformamide and water (volume ratio 1:1), and then add 24mg of initiator ammonium persulfate (APS). After mixing evenly at room temperature, argon gas is introduced for degassing for 30 minutes. Then the reaction temperature is increased to 70℃ and the polymerization reaction is carried out for 4 hours to obtain polyacrylic acid (PAA). After the reaction is completed, the product is cooled in an ice-water bath to terminate the reaction. After dialysis with water for three days and freeze-drying for 48 hours, sponge-like polyacrylic acid (PAA) solid is obtained.

[0078] (4) Add 40 mg of triblock copolymer PHUP to 1.5 mL of an aqueous solution of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) with a solute mass ratio of 1.5% (PHUP:22.5). Stir until fully dissolved to obtain a mixed solution. Add 160 mg of 30 nm silica powder, 480 mg of the mixed solution, 20 mg of solid polyacrylic acid (PAA), and deionized water to the mushroom box. Water 673mg, silicon powder, PHUP-g-PEDOT:PSS and polyacrylic acid (PAA) in a mass ratio of 80:10:10, solid content 15%, were ball-milled in a planetary ball mill for 1 hour to ensure thorough mixing and obtain a uniformly dispersed negative electrode slurry. The slurry was coated onto a copper foil current collector using an automatic coating machine to a thickness of 60μm. After coating, the slurry was placed in a vacuum oven and reacted in situ at 140℃ for 6 hours. The slurry was then removed and cut into electrode sheets with a diameter of 12mm to obtain a silicon negative electrode with composite PHUP-g-PEDOT:PSS.

[0079] (5) Transfer the prepared silicon anode sheet to an argon-filled ultra-clean glove box. Use a die with a diameter of 12 mm to cut out one 150 μm thick ultrathin lithium sheet and one 100 μm thick indium sheet. Weigh 100 mg of LPSC and grind it twice in a mortar. Pour the ground powder into the mold and cover it evenly. At the same time, place the composite silicon anode sheet into the mold and press it together with LPSC. Press it to 175 MPa for 1 min, then press it to 350 MPa and hold it for 5 min. After pressing, stack lithium and indium sheets on the other end. Install the mold in the frame and press it to 150 MPa for 1 min, so that lithium and indium form a lithium-indium alloy under pressure. Slowly depressurize to 60 MPa and tighten the screws to complete the assembly.

[0080] (6) Electrochemical long-cycle tests and rate tests were performed using the assembled half-cells. Constant current discharge / charge tests were conducted within a voltage window of -0.61 to 0.88V (0.01 to 1.5V, Vs. Li), with the theoretical capacity set at 3500mAh / g. Three cycles at 0.2C were used as pre-cycles, followed by long-cycle tests at 1C. Rate tests were performed at 0.1C, 0.2C, 0.4C, 0.6C, 0.8C, 1C, 2C, and 0.1C for 5 cycles each. EIS tests were performed using the assembled half-cells at the following points: before cycling, after 1 cycle, after 3 cycles (end of pre-cycle), after 50 cycles, after 150 cycles, after 250 cycles, and at the end of the cycle. The frequency range was 10kHz-1000kHz.

[0081] Example 3

[0082] (1) 2 g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 50 mL of anhydrous dimethyl sulfoxide were added to a round-bottom flask at a molar ratio of 1:1.3 to 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 1:25 of anhydrous dimethyl sulfoxide. The mixture was heated to 140°C and stirred for 10 minutes until UPy was completely dissolved. After cooling the solution to room temperature, 2.5 g of 2-amino-4-hydroxy-6-methylpyrimidine (ICEMA) was added. The mixture was reacted at room temperature for 4 hours until a large amount of white precipitate formed. The mixture containing the white precipitate was filtered and washed three times with acetone, then dried in a vacuum oven at 40°C for 4 hours to obtain the monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA).

[0083] (2) Following the feeding of 2-hydroxyethyl acrylate (HEA), polyethylene glycol monomethyl ether methacrylate (PEGMA), and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) in a molar ratio of 50:10:50, 3.12 g of 2-hydroxyethyl acrylate (HEA), 3.63 g of polyethylene glycol monomethyl ether methacrylate (PEGMA), and 0.42 g of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) were dissolved in 30 mL of N,N-dimethylformamide at room temperature, and then... A homogeneous solution was formed in a Schlenk flask, with the three monomers comprising 20% ​​of the total mass. 43 mg of azobisisobutyronitrile (AIBN) initiator was added, with the initiator mass being 6‰ of the solute mass. The homogeneous solution was then frozen solid in liquid nitrogen, evacuated for 5 minutes, followed by purging with argon gas for 5 minutes. It was then thawed in water at room temperature, and this freezing and evacuation process was repeated three times. The reaction flask was then immersed in an oil bath at 70°C for 24 hours. After polymerization, the product was cooled in an ice-water bath to terminate the reaction. The cooled solution was purified by dialyzing in water for three days and freeze-dried for two days to obtain pure triblock copolymer P(HEA-co-UPyMA-co-PEGMA)(PHUP).

[0084] (3) Add 40 mg of triblock copolymer PHUP to 1.5 mL of an aqueous solution of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) with a solute mass ratio of 1.5% (PHUP:22.5). Stir until fully dissolved to obtain a mixed solution. Add 160 mg of 30 nm silicon powder and 960 mL of the mixed solution to the mushroom box. The silicon powder and binder were mixed in a mass ratio of 80:20 and the solid content was 15%. The mixture was ball-milled in a planetary ball mill for 1 hour to obtain a uniformly dispersed negative electrode slurry. The slurry was coated onto a copper foil current collector using an automatic coating machine to a thickness of 70 μm. After coating, the slurry was placed in a vacuum oven and reacted in situ at 140 °C for 6 hours. The slurry was then removed and cut into electrode sheets with a diameter of 12 mm to obtain a silicon negative electrode of composite PHUP-g-PEDOT:PSS.

[0085] (4) Transfer the prepared silicon anode sheet to an argon-filled ultra-clean glove box. Use a die with a diameter of 12 mm to cut out one 150 μm thick ultrathin lithium sheet and one 100 μm thick indium sheet. Weigh 100 mg of LPSC and grind it twice in a mortar. Pour the ground powder into the mold to cover it evenly. At the same time, place the composite silicon anode sheet into the mold and press it together with LPSC. Press it to 175 MPa for 1 min, then press it to 350 MPa and hold it for 5 min. After pressing, stack lithium and indium sheets on the other end. Install the mold in the frame and press it to 150 MPa for 1 min, so that lithium and indium form a lithium-indium alloy under pressure. Slowly depressurize to 60 MPa and tighten the screws to complete the assembly.

[0086] (5) Electrochemical long-cycle test and rate test were performed using the assembled half-cell. Constant current discharge / charge test was performed in a voltage window of -0.61 to 0.88V (0.01 to 1.5V, Vs.Li). The theoretical capacity was set to 3500mAh / g. Three cycles at 0.1C were used as pre-cycles, and then long-cycle test was performed at 0.5C.

[0087] Example 4 (1)

[0089] The reaction mixture was prepared according to a molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) to ethyl isocyanate 2-methacrylate (ICEMA) of 1:1.3. 2 g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 50 mL of anhydrous dimethyl sulfoxide were added to a round-bottom flask. The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide was 1:25. The mixture was heated to 140°C and stirred for 10 minutes until UPy was completely dissolved. After cooling the solution to room temperature, 2.5 g of ethyl isocyanate 2-methacrylate (ICEMA) was added. The mixture was reacted at room temperature for 4 hours until a large amount of white precipitate formed. The mixture containing the white precipitate was filtered and washed three times with acetone, then dried in a vacuum oven at 40°C for 4 hours to obtain the monomer ethyl 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)methacrylate (UPyMA).

[0090] (2) Following the feeding of 2-hydroxyethyl acrylate (HEA), polyethylene glycol monomethyl ether methacrylate (PEGMA), and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) in a molar ratio of 50:10:50, 3.12 g of 2-hydroxyethyl acrylate (HEA), 3.63 g of polyethylene glycol monomethyl ether methacrylate (PEGMA), and 0.42 g of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) were dissolved in 30 mL of N,N-dimethylformamide at room temperature, and then... A homogeneous solution was formed in a Schlenk flask, with the three monomers comprising 20% ​​of the total mass. 43 mg of azobisisobutyronitrile (AIBN) initiator was added, with the initiator mass being 6‰ of the solute mass. The homogeneous solution was then frozen solid in liquid nitrogen, evacuated for 5 minutes, followed by purging with argon gas for 5 minutes. It was then thawed in water at room temperature, and this freezing and evacuation process was repeated three times. The reaction flask was then immersed in an oil bath at 70°C for 24 hours. After polymerization, the product was cooled in an ice-water bath to terminate the reaction. The cooled solution was purified by dialyzing in water for three days and freeze-dried for two days to obtain pure triblock copolymer P(HEA-co-UPyMA-co-PEGMA)(PHUP).

[0091] (3) Add 40 mg of triblock copolymer PHUP to 1.5 mL of an aqueous solution of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) with a solute mass ratio of 1.5% (PHUP:22.5). Stir until fully dissolved to obtain a mixed solution. Add 180 mg of 800 nm silica powder and 480 mg of the mixed solution to the mushroom box. The silicon powder and PHUP-g-PEDOT:PSS were mixed in a mass ratio of 90:10 and the solid content was 30%. The mixture was ball-milled in a planetary ball mill for 1 hour to obtain a uniformly dispersed negative electrode slurry. The slurry was coated onto a copper foil current collector using an automatic coating machine to a thickness of 40 μm. After coating, the slurry was placed in a vacuum oven and reacted in situ at 140°C for 6 hours. The slurry was then removed and cut into electrode sheets with a diameter of 12 mm to obtain a silicon negative electrode of composite PHUP-g-PEDOT:PSS.

[0092] The prepared composite silicon anode was assembled into a silicon-based all-solid-state battery for testing, and all steps were the same as in Example 1.

[0093] Example 5

[0094] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the particle size of the silicon powder used for slurry preparation is changed to 100 nm.

[0095] Example 6

[0096] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the solid-state battery negative electrode binder are the same as in Example 4, except that the particle size of the silicon powder used for slurry preparation is changed to 500 nm.

[0097] Example 7

[0098] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the solid-state battery negative electrode binder are the same as in Example 4, except that the particle size of the silicon powder used for slurry preparation is changed to 1 μm.

[0099] Example 8

[0100] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 3, except that the coating thickness is changed to 80 μm.

[0101] Example 9

[0102] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1. The difference is that the electrochemical long cycle rate is changed to 0.2C pre-cycle for 3 cycles followed by 2C long cycle.

[0103] Example 10

[0104] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of PHUP to poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is 30:22.5.

[0105] Example 11

[0106] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of PHUP to poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is 50:22.5.

[0107] Example 12

[0108] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of PHUP to poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is 25:22.5.

[0109] Example 13

[0110] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of PHUP to poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is 35:22.5.

[0111] Example 14

[0112] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of PHUP to poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is 20:22.5.

[0113] Example 15

[0114] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate, and polyethylene glycol monomethyl ether methacrylate is 35:10:35.

[0115] Example 16

[0116] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate, and polyethylene glycol monomethyl ether methacrylate is 40:10:40.

[0117] Example 17

[0118] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate, and polyethylene glycol monomethyl ether methacrylate is 35:5:35.

[0119] Example 18

[0120] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate, and polyethylene glycol monomethyl ether methacrylate is 35:8:35.

[0121] Example 19

[0122] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the in-situ reaction temperature is 150°C and the reaction time is 6 hours.

[0123] Example 20

[0124] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the in-situ reaction temperature is 160°C and the reaction time is 5 hours.

[0125] Example 21

[0126] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the in-situ reaction temperature is 170°C and the reaction time is 4 hours.

[0127] Example 22

[0128] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the in-situ reaction temperature is 180°C and the reaction time is 3 hours.

[0129] Example 23

[0130] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide is 1:20, and the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to 2-methacrylate isocyanate is 1:1.5.

[0131] Example 24

[0132] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide is 1:15, and the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to 2-methacrylate isocyanate is 1:1.

[0133] Example 25

[0134] The preparation method, reaction conditions, purification method, electrode preparation, and battery assembly and testing of the all-solid-state battery negative electrode binder are the same as in Example 1, except that the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide is 1:25, and the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to 2-methacrylate isocyanate is 1:2.

[0135] Comparative Example 1

[0136] (1) 2 g of 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 50 mL of anhydrous dimethyl sulfoxide were added to a round-bottom flask at a molar ratio of 1:1.3 to 2-amino-4-hydroxy-6-methylpyrimidine (UPy) and 1:25 of anhydrous dimethyl sulfoxide. The mixture was heated to 140°C and stirred for 10 minutes until UPy was completely dissolved. After cooling the solution to room temperature, 2.5 g of 2-amino-4-hydroxy-6-methylpyrimidine (ICEMA) was added. The mixture was reacted at room temperature for 4 hours until a large amount of white precipitate formed. The mixture containing the white precipitate was filtered and washed three times with acetone, then dried in a vacuum oven at 40°C for 4 hours to obtain the monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA).

[0137] (2) Following the feeding of 2-hydroxyethyl acrylate (HEA), polyethylene glycol monomethyl ether methacrylate (PEGMA), and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) in a molar ratio of 50:10:50, 3.12 g of 2-hydroxyethyl acrylate (HEA), 3.63 g of polyethylene glycol monomethyl ether methacrylate (PEGMA), and 0.42 g of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate (UPyMA) were dissolved in 30 mL of N,N-dimethylformamide at room temperature, and then... A homogeneous solution was formed in a Schlenk flask, with the three monomers comprising 20% ​​of the total mass. 43 mg of azobisisobutyronitrile (AIBN) initiator was added, with the initiator mass being 6‰ of the solute mass. The homogeneous solution was then frozen solid in liquid nitrogen, evacuated for 5 minutes, followed by purging with argon gas for 5 minutes. It was then thawed in water at room temperature, and this freezing and evacuation process was repeated three times. The reaction flask was then immersed in an oil bath at 70°C for 24 hours. After polymerization, the product was cooled in an ice-water bath to terminate the reaction. The cooled solution was purified by dialyzing in water for three days and freeze-dried for two days to obtain pure triblock copolymer P(HEA-co-UPyMA-co-PEGMA)(PHUP).

[0138] (3) Add 160mg of 30nm silicon powder, 40mg of PHUP solid and 1133mg of deionized water to the mushroom box. The mass ratio of silicon powder to PHUP is 80:20 and the solid content is 15%. Ball mill in a planetary ball mill for 1 hour to mix them thoroughly and obtain a uniformly dispersed negative electrode slurry. Use an automatic coating machine to coat the slurry onto the copper foil current collector with a coating thickness of 60μm. After coating, put it into a vacuum oven and dry it at 80℃ for 6 hours. Then take it out and cut it into electrode sheets with a diameter of 12mm to obtain a silicon negative electrode with composite PHUP.

[0139] The prepared composite silicon anode was assembled into a silicon-based all-solid-state battery for testing, and all steps were the same as in Example 1.

[0140] Comparative Example 2

[0141] Add 200mg of 30nm silicon powder and 800mg of deionized water to a mushroom-shaped container, with a solid content of 20%. Ball mill the mixture in a planetary ball mill for 1 hour to ensure thorough mixing and obtain a uniformly dispersed negative electrode slurry. Use an automatic coating machine to coat the slurry onto a copper foil current collector with a coating thickness of 60μm. After coating, place the slurry in a vacuum oven and dry it at 80℃ for 6 hours. Remove the slurry and cut it into electrode sheets with a diameter of 12mm to obtain a pure silicon negative electrode.

[0142] The prepared pure silicon anode was used to assemble a silicon-based all-solid-state battery for testing, and all steps were the same as in Example 1.

[0143] Comparative Example 3

[0144] 160 mg of 30 nm silicon powder, 40 mg of solid polyacrylic acid (PAA), and 1133 mg of deionized water were added to a mushroom-shaped container. The mass ratio of silicon powder to PAA was 80:20, and the solid content was 15%. The mixture was ball-milled in a planetary ball mill for 1 hour to ensure thorough mixing and obtain a uniformly dispersed negative electrode slurry. The slurry was coated onto a copper foil current collector using an automatic coating machine to a thickness of 60 μm. After coating, the slurry was placed in a vacuum oven and dried at 80 °C for 6 hours. The dried slurry was then removed and cut into electrode sheets with a diameter of 12 mm to obtain a silicon negative electrode with composite PAA.

[0145] The prepared composite silicon anode was assembled into a silicon-based all-solid-state battery for testing, and all steps were the same as in Example 1.

[0146] Comparative Example 4

[0147] 160 mg of 30 nm silicon powder, 800 mg of 2% sodium carboxymethyl cellulose (CMC) solution, and 313 mg of deionized water were added to a mushroom-shaped container. The mixture was then milled in a planetary ball mill at 350 r / min for 1 hour to ensure thorough mixing. The ball mill jar was then removed, and 60 mg of 40% styrene-butadiene rubber (SBR) solution was added. The mixture was then milled in a planetary ball mill at 200 r / min for 1 hour to ensure thorough mixing, resulting in a uniformly dispersed negative electrode slurry. The mass ratio of silicon powder to CMC / SBR was 80:20, and the solid content was 15%. The slurry was coated onto a copper foil current collector using an automatic coating machine to a thickness of 60 μm. After coating, the slurry was placed in a vacuum oven and dried at 80 °C for 6 hours. The dried slurry was then cut into electrode sheets with a diameter of 12 mm to obtain a silicon negative electrode composite CMC / SBR.

[0148] The prepared composite silicon anode was assembled into a silicon-based all-solid-state battery for testing, and all steps were the same as in Example 1.

[0149] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A self-healing ionic-electronic integrated adhesive, characterized in that, Composed of component A and component B, wherein component A is a triblock copolymer of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate and polyethylene glycol monomethyl ether methacrylate, with the following molecular structural formula: Where n is 8; x is 35-50, y is 3-10, z is 35-50, and x, y, and z are all natural numbers; Component B is poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid). The mass ratio of component A to component B is (20-50):22.5; The adhesive is used to prepare a silicon-based anode for all-solid-state batteries; the adhesive is formed by the in-situ reaction of component A and component B on the anode sheet of the all-solid-state battery.

2. The self-healing ion-electron integrated adhesive according to claim 1, characterized in that, The adhesive is used to mix with silicon powder and water, coat it onto the current collector, and heat it in a vacuum environment. Components A and B in the adhesive react in situ to generate PHUP-g-PEDOT:PSS on the surface of the current collector, thus obtaining a silicon-based anode. The molecular structural formula of PHUP-g-PEDOT:PSS is: 。 3. The self-healing ion-electron integrated adhesive according to claim 2, characterized in that, The mass ratio of silicon powder to binder is (70-90):(10-30), and the solid content is 10%-40%.

4. The self-healing ion-electron integrated adhesive according to claim 2, characterized in that, The heating temperature is 140-180℃, and the time is 3-6 hours.

5. A method for preparing the self-healing ion-electron integrated adhesive according to claim 1, characterized in that, Components A, B, and water were mixed and ball-milled to produce an adhesive. Component A is a triblock copolymer of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate and polyethylene glycol monomethyl ether methacrylate; Component B is poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid).

6. The method for preparing a self-healing ion-electron integrated adhesive according to claim 5, characterized in that, The preparation process of component A is as follows: 2-hydroxyethyl acrylate, polyethylene glycol monomethyl ether methacrylate, and 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate are dissolved together in N,N-dimethylformamide to form a homogeneous solution F. The homogeneous solution F is degassed under vacuum, and then an initiator is added to form a reaction solution G. After the polymerization reaction occurs in the reaction solution G, it is cooled in an ice bath. The cooled solution is dialyzed and freeze-dried to obtain component A.

7. The method for preparing a self-healing ion-electron integrated adhesive according to claim 6, characterized in that, The molar ratio of 2-hydroxyethyl acrylate, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido) ethyl methacrylate and polyethylene glycol monomethyl ether methacrylate is (35-50):(5-10):(35-50).

8. The method for preparing a self-healing ion-electron integrated adhesive according to claim 5, characterized in that, The preparation process of 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate is as follows: 2-amino-4-hydroxy-6-methylpyrimidine and anhydrous dimethyl sulfoxide are mixed, stirred until completely dissolved, and then cooled to form a mixed solution C; 2-methylisocyanoethyl methacrylate is added to the mixed solution C to react and form a mixture D; the mixture D is filtered to obtain solid E; solid E is washed and dried to obtain the monomer 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate.

9. The method for preparing a self-healing ion-electron integrated adhesive according to claim 8, characterized in that, The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine to anhydrous dimethyl sulfoxide is 1:(15-25), and the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to 2-methacrylate isocyanate is 1:(1-2).

Images