Polymer solid electrolyte battery with hydrogen bond structure and preparation method thereof

Abstract

The invention discloses a polymer solid electrolyte battery with a hydrogen bond structure and a preparation method thereof, and relates to a solid electrolyte and a preparation method thereof. Comprising the following steps: preparation of an electrode plate, preparation of a precursor solvent of the solid electrolyte, assembly of the battery and in-situ polymerization of the solid electrolyte. On the basis of a cross-linked polymer system, a small molecular polymer rich in polar groups is innovatively introduced. Strong electronegative atoms (such as N, O, F and the like) contained in the micromolecule polymer and active hydrogen on a polymer chain form a hydrogen bond structure by virtue of a mutual attraction mechanism between positive and negative potential groups. Through the mediation effect of hydrogen bonds, micromolecules and a polymer main chain are further crosslinked, so that not only is the stability of the polymer electrolyte enhanced, but also an additional channel is opened up for the transmission of lithium ions. The solid electrolyte prepared by the method enables the solid-state battery to have the characteristics of high rate performance, high safety, high energy density and the like, and has a commercial scale application prospect.

Description

Technical Field

[0001] The invention relates to a solid electrolyte and a preparation method thereof, and in particular to a solid electrolyte battery with high-efficiency ion conduction based on a hydrogen bond structure and a preparation method thereof. Background Art

[0002] With the development of new energy technologies, lithium metal anodes have become increasingly popular due to their high theoretical specific capacity (3860 mAh g -1) and extremely low potential (-3.04 V vs standard hydrogen electrode). However, the further application of lithium metal anode is hindered by problems such as decomposition, leakage and explosion of liquid electrolyte. Since solid electrolytes have high mechanical modulus, thermal stability and non-flammability, they can not only inhibit the growth of lithium dendrites, but also improve the energy density of batteries. Therefore, solid electrolytes are considered to be the development direction of next-generation battery technology. Among various types of solid electrolytes, polymer solid electrolytes have attracted attention due to their low manufacturing cost, non-toxicity and good toughness. However, the ionic conductivity of polymer solid electrolytes is low and it is difficult to meet the requirements of practical applications. In addition, complex interfacial reactions will occur between polymer solid electrolytes and electrodes, which will increase the interfacial resistance of the battery and affect the cycle stability of the battery. In order to optimize the interfacial contact of solid-state batteries and improve the ion conduction in the electrolyte, scientists have done a lot of research and proposed strategies such as optimizing the concentration of lithium salts and using cross-linked polymers. The dielectric constant of a polymer is an important parameter for evaluating the ability of a polymer to dissociate lithium salts. The higher the dielectric constant, the stronger the ability to dissociate lithium salts. As Zhang et al. proposed in the article "Heterojunction-accelerating lithium salt dissociation in polymer solid electrolytes" on page 2307263 of Volume 33 of Advanced Functional Materials in 2023, the introduction of ceramic fillers with dielectric polarity and Lewis acid-base sites in the electrolyte substrate can promote the degree of lithium salt dissociation, increase the lithium ion concentration in the electrolyte, and achieve efficient lithium ion transmission. Huang et al. proposed in the article "Multisite crosslinked poly(ether-urethane)-based polymer eectrolytes for high-voltage solid-state lithium metal batteries" on page 2409269 of Volume 36 of Advanced Materials in 2024 that a metal organic framework with amino modification is introduced into the polymer framework as a multi-site crosslinking node, so that the electrolyte has rich polar sites such as ether / ketone / oxygen, which improves the efficient transport of lithium ions. However, due to the significant interaction between lithium ions and crosslinking sites, the dissociation and transmission of lithium ions are hindered, which in turn affects the charge and discharge performance of the battery. Therefore, in order to achieve fast transfer kinetics, good compatibility between lithium ions and migration sites is required in polymer electrolytes; secondly, the active hydrogen contained in the cross-linked polymer system can trigger reactions such as polymer chain breakage and rearrangement, thereby reducing polymer stability. In addition, the cross-linked polymer and the method of optimizing the lithium salt concentration make the negative electrode interface unstable.This leads to increased polarization inside the battery, and even induces dendrite growth during the cycle, causing the battery to short-circuit. Therefore, redesigning the polymer molecular structure and developing polymer electrolytes with high ion conductivity and efficient electrochemical reactions are of great significance for achieving high-performance solid-state lithium metal batteries. Summary of the invention

[0003] The purpose of the present invention is to provide a polymer solid electrolyte battery with a hydrogen bond structure in view of the above problems, which has a solid polymer electrolyte with high ion conductivity and efficient electrochemical reaction. The present invention is based on a cross-linked polymer system and innovatively introduces a small molecule polymer rich in polar groups. The strongly electronegative atoms (such as N, O, F, etc.) contained in the small molecule polymer can form a hydrogen bond structure with the active hydrogen on the polymer chain by virtue of the mutual attraction mechanism between the positive and negative potential groups. Based on the mutual attraction mechanism between the positive and negative potential groups, a hydrogen bond structure is formed with the active hydrogen on the polymer chain. Through the mediation of hydrogen bonds, the small molecules and the polymer main chain are further cross-linked, which not only enhances the stability of the polymer electrolyte, making it have a decomposition resistance voltage of 4.4-4.7 V, but also opens up additional channels for the transmission of lithium ions. In addition, the introduced small molecules have multiple functional advantages. On the one hand, it can significantly promote the dissociation of lithium salts, thereby effectively increasing the concentration of lithium ions in the system, achieving high ionic conductivity, and presenting a (5-10)×10 -4 S cm -1 On the other hand, the small molecule actively participates in the construction process of the negative electrode interface layer, forming a solid electrolyte interface layer rich in inorganic components, which helps to form a stable negative electrode interface and ensures that the electrochemical reaction can be carried out efficiently and stably. The solid electrolyte prepared with it can give solid-state batteries the characteristics of high rate performance, high safety, high energy density, etc., showing broad prospects in the field of commercial-scale applications.

[0004] Another object of the present invention is to provide a method for preparing a polymer solid electrolyte battery with a hydrogen bond structure.

[0005] The purpose of the invention is achieved through the following technical solutions.

[0006] A polymer solid electrolyte battery with a hydrogen bond structure, characterized in that it is prepared by a method comprising the following steps: Step 1: Preparation of electrode plates: Preparation of button electrode plates, using chemical vapor deposition and spraying method to prepare composite electrodes, forming composite electrodes with carbon nanotubes coated with active substances, the selection of positive electrode active material includes but is not limited to lithium cobalt oxide (LCO), lithium iron phosphate (LFP), lithium nickel cobalt manganese oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, etc.; the selection of lithium battery negative electrode active material includes but is not limited to metallic lithium, metallic lithium alloy, silicon or silicon-carbon composite material, lithium titanate, etc.; the active material loading is 4-20 mg cm -2 ; Use a punching machine to punch the composite electrode. The positive electrode is a circular electrode with a diameter of 12-16 mm. The lithium battery negative electrode is punched into a circular electrode with a diameter of 14-19 mm; the diaphragm is punched into a circular electrode with a diameter of 16-20 mm; Preparation of soft-pack battery electrodes: Use a knife and a ruler to cut the composite positive electrode into a size of (50-100) mm × (20-80) mm, leaving 6-10 mm for the welding ear position; cut the negative electrode into a size of (60-100) mm × (30-80) mm, leaving 5-10 mm for the welding ear position. After the electrode is prepared, put it in a 50 ° C vacuum drying oven and use it after drying for 4-8 hours. After use, put it back in the drying oven for storage.

[0007] Step 2, configuration of the precursor solvent of the solid electrolyte: the solid electrolyte monomers used include but are not limited to trans-2-methyl-2-butenoic acid propyl ester, polyethylene glycol dimethacrylate (PEGDMA), trimethylolpropane trimethacrylate (TMPTMA), poly (1-naphthyl methacrylate), etc.; the initiator includes but is not limited to benzoyl peroxide and azobisisobutyronitrile (AIBN), etc.; the plasticizer includes but is not limited to ethylene carbonate (EC), diethyl carbonate, dimethyl carbonate (DMC), etc.; the lithium salt includes but is not limited to lithium bistrifluoromethanesulfonyl imide (LiTFSI), lithium hexafluorophosphate, lithium bisoxalatoborate, lithium difluorooxalatoborate, lithium bisdifluorosulfonyl imide, lithium perchlorate, lithium hexafluoroarsenate, etc.; the additives include but are not limited to fluoroethylene carbonate (FEC), bisfluoroethylene carbonate, maleimide, trifluoro-1-(2-furanyl)-1,3-butanedione, etc. First, two plasticizers and lithium salts are selected, and the plasticizers are mixed in a volume ratio of (1:1)-(5:1) to prepare a 0.5-3 M lithium salt solution. Then, 0.5-2% of initiator powder is added to the lithium salt solution. Two solid electrolyte monomers are selected, and the molar ratio is (1:1)-(5:1), and the mixed monomer solution is obtained after uniform mixing. The lithium salt solution and the mixed monomer solution are uniformly mixed in a mass ratio of 5-20% to obtain a precursor solution. Subsequently, 5-20% of the mass ratio of the additive reagent is added to the precursor solution, and the solid electrolyte solution is obtained after uniform mixing.

[0008] Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode, separator, positive electrode, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution in step 2. -1 The positive electrode, negative electrode and separator cut and dried in step 1 are assembled. Before assembly, the pole tabs are welded to the reserved position of the pole piece and encapsulated with aluminum plastic film to obtain a soft pack battery. All preparation processes are carried out in a glove box (H 2 O≤0.1 ppm; O 2 The prepared battery was placed in a constant temperature drying oven at 40-70 °C for 1-5 h to obtain a polymer solid electrolyte battery with a hydrogen bond structure.

[0009] A method for preparing a polymer solid electrolyte battery with a hydrogen bond structure, characterized in that it comprises the following steps: Step 1: Preparation of electrode plates: Preparation of button electrode plates, using chemical vapor deposition and spraying method to prepare composite electrodes, forming composite electrodes with carbon nanotubes coated with active substances, the selection of positive electrode active material includes but is not limited to lithium cobalt oxide (LCO), lithium iron phosphate (LFP), lithium nickel cobalt manganese oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, etc.; the selection of lithium battery negative electrode active material includes but is not limited to metallic lithium, metallic lithium alloy, silicon or silicon-carbon composite material, lithium titanate, etc.; the active material loading is 4-20 mg cm -2 ; Use a punching machine to punch the composite electrode. The positive electrode is a circular electrode with a diameter of 12-16 mm, and the negative electrode is punched into a circular electrode with a diameter of 14-19 mm; punch the diaphragm into a circular electrode with a diameter of 16-20 mm; Preparation of soft-pack battery electrodes: Use a knife and a ruler to cut the composite positive electrode into a size of (50-100) mm × (20-80) mm, leaving 6-10 mm for the welding ear position; cut the negative electrode into a size of (60-100) mm × (30-80) mm, leaving 5-10 mm for the welding ear position. After the electrode is prepared, put it in a 50 ° C vacuum drying oven and use it after drying for 4-8 hours. After use, put it back into the drying oven for storage.

[0010] Step 2, configuration of the precursor solvent of the solid electrolyte: the solid electrolyte monomers used include but are not limited to trans-2-methyl-2-butenoic acid propyl ester, polyethylene glycol dimethacrylate (PEGDMA), trimethylolpropane trimethacrylate (TMPTMA), poly (1-naphthyl methacrylate), etc.; the initiator includes but is not limited to benzoyl peroxide and azobisisobutyronitrile (AIBN), etc.; the plasticizer includes but is not limited to ethylene carbonate (EC), diethyl carbonate, dimethyl carbonate (DMC), etc.; the lithium salt includes but is not limited to lithium bistrifluoromethanesulfonyl imide (LiTFSI), lithium hexafluorophosphate, lithium bisoxalatoborate, lithium difluorooxalatoborate, lithium bisdifluorosulfonyl imide, lithium perchlorate, lithium hexafluoroarsenate, etc.; the additives include but are not limited to fluoroethylene carbonate (FEC), bisfluoroethylene carbonate, maleimide, trifluoro-1-(2-furanyl)-1,3-butanedione, etc. First, two plasticizers and lithium salts are selected, and the plasticizers are mixed in a volume ratio of (1:1)-(5:1) to prepare a 0.5-3 M lithium salt solution. Then, 0.5-2% of initiator powder is added to the lithium salt solution. Two solid electrolyte monomers are selected, and the molar ratio is (1:1)-(5:1), and the mixed monomer solution is obtained after uniform mixing. The lithium salt solution and the mixed monomer solution are uniformly mixed in a mass ratio of 5-20% to obtain a precursor solution. Subsequently, 5-20% of the mass ratio of the additive reagent is added to the precursor solution, and the solid electrolyte solution is obtained after uniform mixing.

[0011] Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode, separator, positive electrode, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution in step 2. -1 The positive electrode, negative electrode and separator cut and dried in step 1 are assembled. Before assembly, the pole tabs are welded to the reserved position of the pole piece and encapsulated with aluminum plastic film to obtain a soft pack battery. All preparation processes are carried out in a glove box (H 2 O≤0.1 ppm; O 2 The prepared battery was placed in a constant temperature drying oven at 40-70 °C for 1-5 h to obtain a polymer solid electrolyte battery with a hydrogen bond structure.

[0012] The battery performance prepared above was tested in an electrochemical test cabinet. The solid electrolyte prepared according to the above steps showed a (5-10)×10 -4S cm -1 The ion conductivity of the symmetrical battery prepared according to the above steps is 0.25-1 mA cm -2 Current density, 0.25-1 mAh cm -2 The prepared half-cell has a capacity of 140-150 mAh g at a rate of 0.5C. -1 High discharge capacity. It can still work normally at a high rate of 3-5 C and has a capacity of 130-100 mAh g -1 The discharge capacity of the electrode can be stably cycled for 800-1500 cycles. -2 The assembled half-cell has stable cycle performance, a Coulomb efficiency of 99.8-99.9%, and a surface capacity of 2-3 mAh cm -2 The lithium metal soft-pack battery assembled with composite electrodes can maintain stable voltage and current output after cutting and needle puncture tests.

[0013] The present invention has the following beneficial effects: In the research field of solid-state battery technology, optimizing interfacial contact and improving the internal ionic conductivity of the electrolyte have always been the core points. In previous studies, to achieve this goal, the conventional strategy was to introduce multi-chain organic matter with cross-linking fulcrums and optimize the lithium salt concentration to improve the interface performance and ion conductivity of solid-state batteries. However, there is a strong interaction between lithium ions and cross-linking sites, which seriously hinders the dissociation and transmission process of lithium ions, and thus has a great impact on the charge and discharge performance of the battery. In addition, the cross-linked polymer and the method of optimizing the lithium salt concentration make the negative electrode interface unstable, which seriously affects the application of solid-state polymer batteries. Different from traditional methods, the present invention focuses on the unique advantages of small molecule additives. These small molecule additives can not only rely on their own strong electronegative atoms (such as N, O, F, etc.), and the mutual attraction mechanism between positive and negative potential groups, to form hydrogen bond structures with the polymer main chain, open up new channels for lithium ion transmission, but also actively participate in the construction of the negative electrode interface, significantly improving the interface compatibility between the solid electrolyte and the negative electrode. Therefore, the development of this new type of small molecule cross-linked solid electrolyte material is of great significance. The present invention adopts the technical solution of in-situ polymerization of solid electrolyte inside the battery, and is committed to constructing a fast lithium ion transmission channel, increasing the lithium ion concentration inside the solid-state battery, and stabilizing the negative electrode interface, thereby preparing an integrated solid-state battery with high rate performance and high safety performance. Specifically, the present invention has the following significant advantages: First, the present invention proposes a simple method to construct a polymerized integrated solid-state lithium battery with multiple branches, and the polymer chain is cross-linked with a small molecule through a hydrogen bond structure, wherein the small molecule with rich polar functional groups not only provides an additional transmission path for the transmission of lithium ions, improves the lithium ion conductivity, but also its mutual attraction with the polymer chain effectively inhibits the polymer decomposition caused by active hydrogen on the polymer main chain; second, the introduction of polar small molecules promotes the dissociation degree of lithium salts, increases the lithium ion concentration inside the polymer electrolyte, and improves the lithium ion conduction efficiency; third, free anions and excess small molecules construct a solid electrolyte interface layer rich in inorganic components, which enhances the stability of the negative electrode interface, and realizes efficient electrochemical transmission and excellent cycle life. In summary, the present invention realizes an integrated solid-state lithium metal battery with high ion conduction, efficient electrochemical reaction and long cycle life. It provides a new path for developing high-performance solid-state batteries. DETAILED DESCRIPTION

[0014] The following is a detailed description of an embodiment of the present invention: This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and process are given, but the protection scope of the present invention is not limited to the following embodiment. Example 1.

[0015] Step 1: Preparation of electrode plates: Button electrode plates are prepared by chemical vapor deposition and spraying to form a composite electrode with carbon nanotubes encapsulating active materials. The positive electrode active material is lithium iron phosphate (LFP); the negative electrode active material is lithium metal; the active material loading is 5 mg cm -2 ; Use a punching machine to punch the composite electrode. The positive electrode is a circular electrode with a diameter of 12 mm. The negative electrode is punched into a circular electrode with a diameter of 14 mm. Punch the diaphragm into a circular electrode with a diameter of 15.6 mm. Preparation of soft-pack battery electrode: Use a knife and a ruler to cut the composite positive electrode into a size of 50 mm × 20 mm, leaving 6 mm for the welding ear position; cut the negative electrode into a size of 60 mm × 30 mm, leaving 5 mm for the welding ear position, and the size of the middle diaphragm is 70 mm × 40 mm. After the electrode is prepared, put it in a 50℃ vacuum drying oven. It can be used after drying for 8 hours. After use, put it back in the drying oven for storage.

[0016] Step 2, configuration of solid electrolyte solution: solid electrolyte monomers PEGDMA and TMPTMA are used; AIBN is selected as the initiator; EC and DMC are selected as the plasticizer; LiTFSI is selected as the lithium salt; FEC is selected as the additive. First, the plasticizer is used to prepare a lithium salt solution of 0.5 M LiTFSI at a volume ratio of 1:1. Then, 0.5% of AIBN initiator powder is added to the lithium salt solution. PEGDMA and TMPTMA solid electrolyte monomers are evenly mixed at a molar ratio of 3:1 to obtain a mixed monomer solution, and the lithium salt solution and the mixed monomer solution are evenly mixed at a mass ratio of 15% to obtain a precursor solution. Subsequently, 10% of the mass ratio of FEC reagent is added to the precursor solution, and mixed evenly to obtain a solid electrolyte solution.

[0017] Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 10 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode sheet, separator, positive electrode sheet, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 10 μL mg of the solid electrolyte solution in step 2. -1 The positive electrode, negative electrode and separator cut and dried in step 1 are assembled. Before assembly, the pole tabs are welded to the reserved position of the pole piece and encapsulated with aluminum plastic film to obtain a soft pack battery. All preparation processes are carried out in a glove box (H 2 O≤0.1 ppm; O 2The prepared battery was placed in a 70 ℃ constant temperature drying oven for 5 h to obtain a polymer solid electrolyte battery with a CH…FC hydrogen bond structure.

[0018] In this embodiment, an impedance test (EIS) was performed on the above battery. The initial charge transfer resistance of the button half-cell was 118.4 Ω. After 100 charge and discharge cycles, the charge transfer resistance of the button half-cell was 25.85 Ω. The prepared button half-cell was cycled between 2.5-4 V at a rate of 3 C and had a capacity of 123 mAh g -1 The discharge capacity of the soft-pack battery is 143.1 mAh g at a rate of 0.5 C. -1 , as the current density increases, the soft-pack battery can still maintain a high charge and discharge capacity. Example 2.

[0019] Step 1: Preparation of electrode plates: Button electrode plates are prepared by chemical vapor deposition and spraying to form a composite electrode with carbon nanotubes encapsulating active materials. The positive electrode active material is lithium cobalt oxide (LCO); the negative electrode active material is lithium metal; the active material loading is 6 mg cm -2 ; Use a punching machine to punch the composite electrode. The positive electrode is a circular electrode with a diameter of 12 mm. The negative electrode is punched into a circular electrode with a diameter of 15 mm. Punch the diaphragm into a circular electrode with a diameter of 16 mm. Preparation of soft-pack battery electrode: Use a knife and a ruler to cut the composite positive electrode into a size of 80 mm × 60 mm, leaving 8 mm for the welding ear position; Cut the negative electrode into a size of 90 mm × 70 mm, leaving 8 mm for the welding ear position, and the size of the middle diaphragm is 100 mm × 75 mm. After the electrode is prepared, put it in a 50 ℃ vacuum drying oven. It can be used after drying for 8 hours. After use, put it back in the drying oven for storage.

[0020] Step 2, the preparation of the precursor solvent of the solid electrolyte: the solid electrolyte monomers used are PEGDMA and trans-2-methyl-2-butenoic acid propyl ester; the initiator is AIBN; the plasticizer is EC and DMC; the lithium salt is lithium hexafluorophosphate; the additive is trifluoro-1-(2-furanyl)-1,3-butanedione. First, the plasticizer is prepared into a lithium salt solution of 0.5 M lithium hexafluorophosphate at a volume ratio of 2:1. Then, 0.8% AIBN initiator powder is added to the lithium salt solution. PEGDMA and trans-2-methyl-2-butenoic acid propyl ester solid electrolyte monomers are mixed evenly at a molar ratio of 2:1 to obtain a mixed monomer solution, and the lithium salt solution and the mixed monomer solution are mixed evenly at a mass ratio of 15% to obtain a precursor solution. Subsequently, 10% of the mass ratio of trifluoro-1-(2-furanyl)-1,3-butanedione reagent is added to the precursor solution, and mixed evenly to obtain a solid electrolyte solution.

[0021] Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 10 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode, separator, positive electrode, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 10 μL mg of the solid electrolyte solution in step 2. -1 The positive electrode, negative electrode and separator cut and dried in step 1 are assembled. Before assembly, the pole tabs are welded to the reserved position of the pole piece and encapsulated with aluminum plastic film to obtain a soft pack battery. All preparation processes are carried out in a glove box (H 2 O≤0.1 ppm; O 2 The prepared battery was placed in a 70 ℃ constant temperature drying oven for 5 h to obtain a polymer solid electrolyte with a CH…FC hydrogen bond structure.

[0022] In this embodiment, an impedance test (EIS) was performed on the above battery. The initial charge transfer resistance of the button half-cell was 104.5 Ω, and the charge transfer resistance of the button half-cell after 100 charge and discharge cycles was 35.5 Ω. The prepared soft pack battery was cycled between 3-4.4 V at a rate of 1 C and had a capacity of 170 mAh g -1 The discharge specific capacity can be stably cycled for 100 cycles, and with the increase of the number of cycles, the battery charge and discharge curve has no obvious change, the charge and discharge polarization voltage and discharge capacity remain stable, and it has good electrochemical reversibility. Example 3.

[0023] Step 1: Preparation of electrode plates: Button electrode plates are prepared by using chemical vapor deposition and spraying to form a composite electrode with carbon nanotubes encapsulating active materials. The positive electrode active material is lithium iron phosphate (LFP); the negative electrode active material is lithium metal; the active material loading is 13 mg cm -2 ; Use a punching machine to punch the composite electrode. The positive electrode is a circular electrode with a diameter of 14 mm. The negative electrode is punched into a circular electrode with a diameter of 15 mm. The diaphragm is punched into a circular electrode with a diameter of 16 mm. Preparation of soft-pack battery electrode: Use a knife and a ruler to cut the composite positive electrode into a size of 60 mm × 60 mm, leaving 7 mm for the welding ear position; Cut the negative electrode into a size of 70 mm × 70 mm, leaving 7 mm for the welding ear position, and the size of the middle diaphragm is 80 mm × 80 mm. After the electrode is prepared, put it in a 50℃ vacuum drying oven. It can be used after drying for 8 hours. After use, put it back in the drying oven for storage.

[0024] Step 2, the preparation of the precursor solvent of the solid electrolyte: the solid electrolyte monomers used are PEGDMA and poly (1-naphthyl methacrylate) solid electrolyte monomers; the initiator is AIBN; the plasticizer is EC and DMC; the lithium salt is LiTFSI; the additive is difluoroethylene carbonate. First, the plasticizer is used to prepare a lithium salt solution of 3 M LiTFSI at a volume ratio of 3:1. Then, 0.5% of AIBN initiator powder is added to the lithium salt solution. PEGDMA and poly (1-naphthyl methacrylate) solid electrolyte monomers are uniformly mixed at a molar ratio of 3:1 to obtain a mixed monomer solution, and the lithium salt solution and the mixed monomer solution are uniformly mixed at a mass ratio of 15% to obtain a precursor solution. Subsequently, 10% of the mass ratio of difluoroethylene carbonate reagent is added to the precursor solution, and mixed uniformly to obtain a solid electrolyte solution.

[0025] Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 7 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode, separator, positive electrode, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 7 μL mg of the solid electrolyte solution in step 2. -1 The positive electrode, negative electrode and separator cut and dried in step 1 are assembled. Before assembly, the pole tabs are welded to the reserved position of the pole piece and encapsulated with aluminum plastic film to obtain a soft pack battery. All preparation processes are carried out in a glove box (H 2O≤0.1 ppm; O 2 The prepared battery was placed in a 70 ℃ constant temperature drying oven for 5 h to obtain a polymer solid electrolyte battery with a CH…FC hydrogen bond structure.

[0026] In this embodiment, the above-mentioned battery was subjected to a cyclic voltammetry test (CV). The CV curve of the button half-cell shows a high degree of consistency as the number of cycles increases. Secondly, from the CV curve of the third cycle, it can be seen that the polarization voltage of the button half-cell is 0.28V, which reflects the rapid reaction kinetics inside the battery, so that the battery has a smaller polarization voltage, thereby giving the battery a high initial capacity. In addition, the button half-cell has a higher peak current (1.449 mA), indicating that the interface ion concentration of the lithium negative electrode / solid electrolyte is high, and the electrochemical charge and discharge response is fast, which is beneficial to improving the battery rate performance. The prepared soft-pack battery cycles between 2.5-4 V at a rate of 1 C and has a capacity of 135 mAh g -1 The discharge specific capacity can be stably cycled for 200 cycles, and with the increase of the number of cycles, the battery charge and discharge curve has no obvious change, the charge and discharge polarization voltage and discharge capacity remain stable, and it has good electrochemical reversibility. Example 4.

[0027] Step 1: Preparation of electrode plates: Button electrode plates are prepared by chemical vapor deposition and spraying to form a composite electrode with carbon nanotubes encapsulating active materials. The positive electrode active material is lithium iron phosphate (LFP); the negative electrode active material is lithium metal; the active material loading is 5 mg cm -2 ; Use a punching machine to punch the composite electrode. The positive electrode is a circular electrode with a diameter of 14 mm. The negative electrode is punched into a circular electrode with a diameter of 15 mm. The diaphragm is punched into a circular electrode with a diameter of 16 mm. Preparation of soft-pack battery electrode: Use a knife and a ruler to cut the composite positive electrode into a size of 80×70 mm, leaving 6 mm for the welding ear position; cut the metal lithium negative electrode into a size of 90×80 mm, leaving 5 mm for the welding ear position; the middle diaphragm is cut into a size of 100×90 mm. After the electrode is prepared, put it in a 50℃ vacuum drying oven. It can be used after drying for 6 hours. After use, put it back in the drying oven for storage.

[0028] Step 2, the preparation of the precursor solvent of the solid electrolyte: the solid electrolyte monomers used are PEGDMA and poly (1-naphthyl methacrylate) solid electrolyte monomers; the initiator is AIBN; the plasticizer is EC and DMC; the lithium salt is LiTFSI; the additive is FEC. First, the plasticizer is used to prepare a lithium salt solution of 3 M LiTFSI at a volume ratio of 5:1. Then, 0.5% AIBN initiator powder is added to the lithium salt solution. PEGDMA and poly (1-naphthyl methacrylate) solid electrolyte monomers are uniformly mixed at a molar ratio of 3:1 to obtain a mixed monomer solution, and the lithium salt solution and the mixed monomer solution are uniformly mixed at a mass ratio of 15% to obtain a precursor solution. Subsequently, 10% of the mass ratio of FEC reagent is added to the precursor solution, and the solid electrolyte solution is obtained by mixing evenly.

[0029] Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 7 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode, separator, positive electrode, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 10 μL mg of the solid electrolyte solution in step 2. -1 The positive electrode, negative electrode and separator cut and dried in step 1 are assembled. Before assembly, the pole tabs are welded to the reserved position of the pole piece and encapsulated with aluminum plastic film to obtain a soft pack battery. All preparation processes are carried out in a glove box (H 2 O≤0.1 ppm; O 2 The prepared battery was placed in a 70 ℃ constant temperature drying oven for 5 h to obtain a polymer solid electrolyte battery with a CH…FC hydrogen bond structure.

[0030] In this embodiment, the initial charge transfer resistance of the prepared button half-cell is 120.5Ω, and the charge transfer resistance of the button half-cell after 100 charge and discharge cycles is 40.7Ω. The soft pack battery is cycled between 2.5-4 V at a rate of 0.5 C and has a capacity of 145 mAh g -1 The discharge specific capacity can be stably cycled for 150 cycles, and with the increase of the number of cycles, the charge and discharge platform is smooth and long, the charge and discharge polarization voltage is 93 mV, and the capacity retention rate is 94.6% after 150 cycles. The soft-pack battery does not catch fire during the scissors cutting process and can maintain a stable voltage and current output. Example 5.

[0031] Step 1: Preparation of electrode plates: Button electrode plates are prepared by chemical vapor deposition and spraying to form a composite electrode with carbon nanotubes encapsulating active materials. The positive electrode active material is lithium iron phosphate (LFP); the negative electrode active material is lithium metal; the active material loading is 15 mg cm -2 ; Use a punching machine to punch the composite electrode. The positive electrode is a circular electrode with a diameter of 15 mm. The negative electrode is punched into a circular electrode with a diameter of 16 mm. Punch the diaphragm into a circular electrode with a diameter of 17 mm. Preparation of soft-pack battery electrode: Use a knife and a ruler to cut the composite positive electrode into a size of 70 mm × 50 mm, leaving 8 mm for the welding ear position; cut the negative electrode into a size of 80 mm × 70 mm, leaving 7 mm for the welding ear position. The size of the middle diaphragm is 85 mm × 75 mm. After the electrode is prepared, put it in a 50℃ vacuum drying oven. It can be used after drying for 8 hours. After use, put it back in the drying oven for storage.

[0032] Step 2, the preparation of the precursor solvent of the solid electrolyte: the solid electrolyte monomers used are trans-2-methyl-2-butenoic acid propyl ester and PEGDMA; the initiator is AIBN; the plasticizer is EC and DMC; the lithium salt is LiTFSI; the additive is maleimide. First, the plasticizer is used to prepare a lithium salt solution of 1 M LiTFSI at a volume ratio of 4:1. Then, 0.5% of AIBN initiator powder is added to the lithium salt solution. The trans-2-methyl-2-butenoic acid propyl ester and PEGDMA solid electrolyte monomers are uniformly mixed at a molar ratio of 3:1 to obtain a mixed monomer solution, and the lithium salt solution and the mixed monomer solution are uniformly mixed at a mass ratio of 15% to obtain a precursor solution. Subsequently, 10% of the mass ratio of maleimide reagent is added to the precursor solution, and the solid electrolyte solution is uniformly obtained by mixing.

[0033] Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 5 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode sheet, separator, positive electrode sheet, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 5 μL mg of the solid electrolyte solution in step 2. -1 The positive electrode, negative electrode and separator cut and dried in step 1 are assembled. Before assembly, the pole tabs are welded to the reserved position of the pole piece and encapsulated with aluminum plastic film to obtain a soft pack battery. All preparation processes are carried out in a glove box (H 2 O≤0.1 ppm; O2 The prepared battery was placed in a 70 ℃ constant temperature drying oven for 5 h to obtain a polymer solid electrolyte battery with a CH…O=C hydrogen bond structure.

[0034] In this embodiment, the prepared button half-cell is cycled between 2.5-4 V at a rate of 5 C, and the button half-cell has a capacity of 110 mAh g -1 The discharge capacity of the soft-pack battery is 144.1 mAh g at a rate of 0.5 C at 45 °C. -1 , and can stably cycle 100 times, and with the increase of the number of cycles, the battery charge and discharge curve has no obvious change, the charge and discharge polarization voltage and discharge capacity remain stable, and it has good electrochemical reversibility and temperature stability.

Claims

1. A polymer solid electrolyte battery with a hydrogen bond structure, characterized in that: Prepared by a method comprising the following steps: Step 1: Preparation of electrode sheet: Preparation of button electrode sheet, using chemical vapor deposition and spraying method to prepare composite electrode, forming a composite electrode of carbon nanotubes coated with active material, with an active material loading of 4-20 mg cm -2 ; Use a punching machine to punch the composite electrode, the positive electrode is a circular electrode with a diameter of 12-16 mm; punch the lithium battery negative electrode into a circular electrode with a diameter of 14-19 mm; punch the diaphragm into a circular electrode with a diameter of 16-20 mm; Preparation of soft-pack battery electrode: use a knife and a ruler to cut the composite positive electrode into a size of 50-100mm×20-80mm, leaving 6-10 mm for the welding ear position; cut the negative electrode into a size of 60-100mm×30-80mm, leaving 5-10 mm for the welding ear position; after the electrode is prepared, put it in a 50℃ vacuum drying oven, dry it for 4-8 hours before use, and put it back in the drying oven for storage after use; Step 2, preparation of a precursor solvent for a solid electrolyte: selecting two plasticizers and a lithium salt, and mixing the plasticizers at a volume ratio of 1:1-5:1 to prepare a 0.5-3 M lithium salt solution; then adding 0.5-2% by mass of an initiator powder to the lithium salt solution, selecting two solid electrolyte monomers, mixing them at a molar ratio of 1:1-5:1 to obtain a mixed monomer solution, and mixing the lithium salt solution and the mixed monomer solution at a mass ratio of 5-20% to obtain a precursor solution, and then adding 5-20% by mass of an additive reagent to the precursor solution, and mixing them to obtain a solid electrolyte solution; Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode, separator, positive electrode, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution in step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1, weld the pole ear at the reserved position of the pole piece before assembly, and use aluminum plastic film to encapsulate to obtain a soft pack battery. All preparation processes are carried out in a glove box under argon atmosphere. The obtained battery is placed in a constant temperature drying oven at 40-70 ℃ for 1-5 hours to obtain a polymer solid electrolyte battery with a hydrogen bond structure.

2. The polymer solid electrolyte battery with a hydrogen bond structure according to claim 1, characterized in that: The positive electrode active material selected in step one includes lithium cobalt oxide, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium manganese oxide, and lithium nickel cobalt aluminum oxide. The lithium battery negative electrode active material in step one is one or more of the following: metallic lithium, metallic lithium alloy, silicon or silicon-carbon composite material, and lithium titanate.

3. The polymer solid electrolyte battery with a hydrogen bond structure according to claim 1, characterized in that: The solid electrolyte monomers used in the step 2 include trans-2-methyl-2-butenoic acid propyl ester, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and poly (1-naphthyl methacrylate); the initiator includes benzoyl peroxide and azobisisobutyronitrile; the plasticizer includes ethylene carbonate, diethyl carbonate, and dimethyl carbonate; the lithium salt includes lithium bistrifluoromethanesulfonyl imide, lithium hexafluorophosphate, lithium bisoxalatoborate, lithium difluorooxalatoborate, lithium bisdifluorosulfonyl imide, lithium perchlorate, and lithium hexafluoroarsenate; the additive includes fluoroethylene carbonate, bisfluoroethylene carbonate, maleimide, and trifluoro-1-(2-furanyl)-1,3-butanedione.

4. The polymer solid electrolyte battery with a hydrogen bond structure according to claim 1, characterized in that: In step 3, H2O≤0.1 ppm; O2≤0.1 ppm in the glove box.

5. A method for preparing a polymer solid electrolyte battery with a hydrogen bond structure, characterized in that: The following steps are involved: Step 1: Preparation of electrode sheet: Preparation of button electrode sheet, using chemical vapor deposition and spraying method to prepare composite electrode, forming a composite electrode of carbon nanotubes coated with active material, with an active material loading of 4-20 mg cm -2 ; Use a punching machine to punch the composite electrode, the positive electrode is a circular electrode with a diameter of 12-16 mm; punch the lithium battery negative electrode into a circular electrode with a diameter of 14-19 mm; punch the diaphragm into a circular electrode with a diameter of 16-20 mm; Preparation of soft-pack battery electrode: use a knife and a ruler to cut the composite positive electrode into a size of 50-100mm×20-80mm, leaving 6-10 mm for the welding ear position; cut the negative electrode into a size of 60-100mm×30-80mm, leaving 5-10 mm for the welding ear position; after the electrode is prepared, put it in a 50℃ vacuum drying oven, dry it for 4-8 hours before use, and put it back in the drying oven for storage after use; Step 2, preparation of a precursor solvent for a solid electrolyte: select two plasticizers and a lithium salt, and prepare a 0.5-3 M lithium salt solution by mixing the plasticizers at a volume ratio of 1:1-5:1; then add 0.5-2% by mass of an initiator powder to the lithium salt solution, select two solid electrolyte monomers, and mix them evenly at a molar ratio of 1:1-5:1 to obtain a mixed monomer solution, and mix the lithium salt solution and the mixed monomer solution evenly at a mass ratio of 5-20% to obtain a precursor solution. Then, add 5-20% by mass of an additive reagent to the precursor solution, and mix evenly to obtain a solid electrolyte solution; Step 3: Battery assembly and solid electrolyte in-situ polymerization: Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution from step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1. When assembling, first place the negative electrode shell on the platform, then put the negative electrode, separator, positive electrode, solid electrolyte solution, gasket, and shrapnel in turn, and finally cover the positive electrode shell. Use a button battery packaging machine to package to obtain a button half-cell. The assembly process of the soft pack battery is the same as that of the button half-cell. Use a pipette to pick up 2-10 μL mg of the solid electrolyte solution in step 2. -1 , assemble the positive electrode, negative electrode and separator cut and dried in step 1, weld the pole ear at the reserved position of the pole piece before assembly, and use aluminum plastic film to package to obtain a soft pack battery. All preparation processes are carried out in a glove box under argon atmosphere. The prepared battery is heated to 40-70 o C constant temperature drying oven for 1-5h to obtain a polymer solid electrolyte battery with a hydrogen bond structure.

6. The method for preparing a polymer solid electrolyte battery with a hydrogen bond structure according to claim 5, characterized in that: The positive electrode active material selected in step one includes lithium cobalt oxide, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium manganese oxide, and lithium nickel cobalt aluminum oxide. The lithium battery negative electrode active material in step one is one or more of the following: metallic lithium, metallic lithium alloy, silicon or silicon-carbon composite material, and lithium titanate.

7. The method for preparing a polymer solid electrolyte battery with a hydrogen bond structure according to claim 5, characterized in that: The solid electrolyte monomers used in the step 2 include trans-2-methyl-2-butenoic acid propyl ester, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and poly (1-naphthyl methacrylate); the initiator includes benzoyl peroxide and azobisisobutyronitrile; the plasticizer includes ethylene carbonate, diethyl carbonate, and dimethyl carbonate; the lithium salt includes lithium bistrifluoromethanesulfonyl imide, lithium hexafluorophosphate, lithium bisoxalatoborate, lithium difluorooxalatoborate, lithium bisdifluorosulfonyl imide, lithium perchlorate, and lithium hexafluoroarsenate; the additives include fluoroethylene carbonate and bisfluoroethylene carbonate, maleimide, and trifluoro-1-(2-furanyl)-1,3-butanedione.

8. The method for preparing a polymer solid electrolyte battery with a hydrogen bond structure according to claim 5, characterized in that: In step 3, H2O≤0.1 ppm; O2≤0.1 ppm in the glove box.