A topological structure all-solid-state polymer electrolyte and a preparation method and application thereof

Abstract

The application belongs to the technical field of battery electrolyte, and discloses a topological structure all-solid-state polymer electrolyte and a preparation method and application thereof. The topological structure all-solid-state polymer electrolyte comprises, in percentage by mass, 10-80% of a topological structure all-solid-state polymer matrix, 0-60% of a porous support material, and 10-70% of a lithium salt; the topological structure all-solid-state polymer matrix is a hyperbranched, monocyclic or polycyclic topological structure polymer formed by self-polymerization and cross-linking of a polymer precursor comprising two segment structures of polyether and urethane methacrylate. The topological structure all-solid-state polymer electrolyte has good film-forming performance, a wide electrochemical window (0-4.7 V vs. Li / Li + ), and can be applied in battery systems such as high-voltage lithium metal batteries, high-specific-energy lithium metal batteries and solid-state lithium metal batteries, and has good compatibility with lithium metal negative electrodes, and exhibits excellent stability and safety.

Description

Technical Field

[0001] This invention belongs to the field of battery electrolyte technology, specifically relating to a topologically structured all-solid-state polymer electrolyte, its preparation method, and its application. Background Technology

[0002] Growing market demand is driving lithium battery research towards higher energy density and performance, while the energy density and performance of traditional lithium-ion batteries are far from meeting the expanding market demand. Therefore, lithium metal batteries, with their energy density exceeding 3860 mAh g / g, are gaining popularity. -1 The theoretical specific capacity and low electrochemical potential below -3V vs SCE of lithium metal batteries have once again come into focus. However, currently commercially available lithium metal batteries often use flammable liquid carbonate electrolytes, and their inherent instability easily leads to safety hazards such as fire and explosion. To simultaneously improve the safety and energy density of lithium metal batteries, the academic community has proposed a series of optimization measures, including replacing the electrolyte solvent and using inorganic solid electrolytes or solid polymer electrolytes to replace liquid electrolytes. Among these, using solid polymer electrolytes to replace liquid electrolytes to achieve all-solid-state lithium metal batteries is an effective method.

[0003] All-solid-state polymer electrolytes have attracted widespread attention from industry due to their high processability, energy density, interfacial compatibility, and better safety. Invention patent CN110416603A discloses a method for preparing and applying a modified vinyl oxide solid polymer electrolyte, which exhibits high electrochemical and cycling stability. However, vinyl oxide polymer electrolytes have poor compatibility with the cathode, a narrow electrochemical window, and are prone to degradation of vinyl oxide and performance degradation of lithium metal batteries during cycling. Compared to more traditional vinyl oxide solid polymer electrolytes and polycarbonate-based solid polymer electrolytes, polyether-based solid electrolytes have higher room-temperature ionic conductivity and higher cycling stability, showing greater application potential. For example, CN111653828A discloses a method for preparing and applying a polydioxolane-based polymer solid electrolyte, but the solid electrolyte prepared by this method has poor film-forming properties, low oxidation stability, and poor cycle stability of the assembled battery, still posing a certain risk of thermal runaway. Polymers with specific topological structures have better film-forming properties and are more conducive to the dissociation of lithium salts and the migration of positive carriers, showing potential for use as lithium battery electrolytes. However, current topological polymer electrolytes still face a series of problems, such as poor film-forming properties, weak ability to dissociate and transport lithium ions, and narrow electrochemical windows. Therefore, developing all-solid-state topological polymer electrolytes with higher stability and better electrochemical performance for the commercial application of high-safety and high-energy-density lithium metal batteries is of great significance. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to address the shortcomings of the existing technology by providing a topological structure all-solid-state polymer electrolyte, its preparation method and application. The electrolyte has good film-forming properties, a wide electrochemical window, and good compatibility with lithium metal anodes. It can be applied to battery systems such as high-voltage lithium metal batteries, high-energy-density lithium metal batteries, and solid-state lithium metal batteries.

[0005] To address the technical problems proposed in this invention, this invention provides a topologically structured all-solid-state polymer electrolyte, comprising, by mass percentage: 10-80% topologically structured all-solid-state polymer matrix, 0-60% porous support material, and 10-70% lithium salt.

[0006] Preferably, the topologically structured all-solid polymer electrolyte comprises, by mass percentage: 20-60% topologically structured all-solid polymer matrix, 10-60% porous support material, and 20-50% lithium salt.

[0007] In the above scheme, the topologically structured all-solid polymer matrix is ​​a hyperbranched, monocyclic, or polycyclic topologically structured polymer formed by the self-polymerization and crosslinking of polymer precursors including two segmental structures: polyether and urea methacrylate.

[0008] Furthermore, the structural formula of the polymerization precursor is:

[0009]

[0010] In the formula, R is selected from One of them, where n is an integer from 1 to 1000.

[0011] In the above scheme, the porous support material is one of polyethylene terephthalate film, cellulose nonwoven film, polypropylene nonwoven film, glass fiber nonwoven film, seaweed fiber nonwoven film, polyethylene nonwoven film, aramid nonwoven film, polysulfone amide nonwoven film, and polyimide nonwoven film.

[0012] In the above scheme, the lithium salt is one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium bis(oxalateborate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium di(fluorooxalateborate)borate (LiDFOB), and lithium trifluoromethanesulfonate (CF3SO3Li).

[0013] This invention also provides a method for preparing a topologically structured all-solid-state polymer electrolyte, comprising the following steps:

[0014] 1) Under an inert atmosphere at room temperature, aluminum trifluoromethanesulfonate was added to an oxygen-containing heterocyclic compound, and the reaction was stirred. The reaction solution gradually solidified to obtain a solid polymer.

[0015] 2) Under an inert atmosphere of an ice bath, the solid polymer was added to anhydrous dichloromethane, followed by the sequential addition of triethylamine and isocyanate methacrylate. After stirring and reacting, a flocculent product precipitated in anhydrous diethyl ether to obtain the polymerization precursor.

[0016] 3) Under an inert atmosphere at room temperature, the polymerization precursor was dissolved in N,N-dimethylformamide, azobisisobutyronitrile was added, the mixture was heated and stirred, and the solid product was precipitated in anhydrous diethyl ether and dried to obtain the topologically structured all-solid polymer matrix.

[0017] 4) Dissolve the topologically structured all-solid polymer matrix and lithium salt in a solvent, mix them evenly, and then drop-coat them onto a porous support material or directly form a self-supporting film. After vacuum drying, the topologically structured all-solid polymer electrolyte is obtained.

[0018] In the above scheme, the oxygen-containing heterocyclic compound is one of 1,3-dioxolane, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, trioxymethylene, and oxetane.

[0019] In the above scheme, the mass ratio of aluminum trifluoromethanesulfonate to the volume ratio of the oxygen-containing heterocyclic compound is (0.01~0.1) g: 10 mL.

[0020] In the above scheme, the stirring rate in step 1) is 100-300 r / min, and the reaction time is 3-24 h.

[0021] In the above scheme, the mass ratio of the solid polymer to the volume ratio of anhydrous dichloromethane is 1g:(10~100)mL.

[0022] In the above scheme, the mass ratio of the solid polymer, triethylamine, and isocyanate methacrylate is 1:(0.01-0.1):(0.5-5).

[0023] In the above scheme, the stirring rate in step 2) is 100-300 r / min, and the reaction time is 3-24 h.

[0024] In the above scheme, the volume of anhydrous diethyl ether in step 2) is 0.1 to 10 times the volume of anhydrous dichloromethane.

[0025] In the above scheme, the mass ratio of the polymerization precursor to the volume ratio of N,N-dimethylformamide is 1g:(10~100)mL.

[0026] In the above scheme, the mass ratio of the polymerization precursor to azobisisobutyronitrile is 1:(0.005~0.1g).

[0027] In the above scheme, the heating temperature in step 3) is 40-100℃, and the reaction time is 3-24h.

[0028] In the above scheme, the volume of anhydrous diethyl ether in step 3) is 0.1 to 10 times the volume of anhydrous dichloromethane in step 2).

[0029] In the above scheme, the drying temperature in step 3) is 30-120℃.

[0030] In the above scheme, the solvent is one of tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone.

[0031] In the above scheme, the volume ratio of the solvent to the mass ratio of the lithium salt is (5-30) mL: 1 g.

[0032] In the above scheme, the temperature of vacuum drying is 40-120℃.

[0033] This invention also provides an application of a topologically structured all-solid-state polymer electrolyte, which is used to prepare all-solid-state lithium metal batteries.

[0034] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0035] 1) This invention breaks through the morphological limitations of traditional polyether-based all-solid polymer electrolytes and prepares a polyether-based all-solid polymer electrolyte with a topological structure. Based on the high lithium-ion transport capability brought about by the intrinsic weak coordination of polyether-based all-solid polymer electrolytes, its electrochemical performance and battery cycle performance are further improved through reasonable topological structure design.

[0036] 2) The all-solid-state polymer electrolyte of this invention exhibits excellent film-forming properties (ultra-thin, with a thickness of 5–20 micrometers) and a wide electrochemical window (0–4.7V vs. Li / Li). + It can be applied to battery systems such as high-voltage lithium metal batteries, high-energy-density lithium metal batteries, and solid-state lithium metal batteries. When applied, it can form an SEI film at the interface between the positive electrode and the lithium metal / electrolyte, and has good compatibility with the lithium metal negative electrode, improving the stability of the electrode / electrolyte interface and inhibiting the growth of lithium dendrites, thereby significantly improving safety performance.

[0037] 3) The lithium-lithium symmetric battery assembled using the all-solid-state polymer electrolyte with the topology of this invention can achieve a speed of 0.1 mA / cm². -2 It can cycle stably for over 3000 hours at a current density; a full cell using lithium metal as the negative electrode, lithium iron phosphate as the positive electrode, and an all-solid-state polymer electrolyte with this topology can achieve a current density of 0.5C (1C = 170mAh g / L). -1After cycling for 400 cycles at a current density of 0.5, it still retains 99% of its capacity, demonstrating excellent cycle stability. Attached Figure Description

[0038] Figure 1 This is a physical image of the all-solid-state polymer electrolyte with the topological structure of Embodiment 1 of the present invention.

[0039] Figure 2 The linear sweep voltammetry curves of the all-solid-state polymer electrolyte with the topological structure of Example 1 of the present invention are shown.

[0040] Figure 3 The lithium-lithium symmetric battery assembled with an all-solid-state polymer electrolyte of the topological structure in Example 1 of this invention operates at a current density of 0.1 mA cm⁻¹. -2 Long-cycle performance diagram at 60℃.

[0041] Figure 4 The full cell assembled with the all-solid-state polymer electrolyte of the topological structure in Example 1 of this invention was tested at 0.5C (1C = 170 mAh g). -1 Cyclic performance diagram at 60°C under current density. Detailed Implementation

[0042] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0043] Example 1

[0044] A topologically structured all-solid-state polymer electrolyte comprises, by mass percentage: 50% topologically structured all-solid-state polymer matrix, 10% polyethylene terephthalate film, and 40% LiTFSI.

[0045] The preparation method of the above-mentioned all-solid-state polymer electrolyte with the above-mentioned topological structure includes the following steps:

[0046] 1) Under a nitrogen protective atmosphere at room temperature, 0.1 g of aluminum trifluoromethanesulfonate was added to 10 mL of 1,3-dioxolane and stirred at 200 r / min for 6 h. The reaction solution was then solidified to obtain a solid polymer.

[0047] 2) Under the protection of nitrogen in an ice bath, 10g of solid polymer was added to 100mL of anhydrous dichloromethane, followed by the addition of 0.1g of triethylamine and 10g of isocyanate methacrylate. After stirring at 250r / min for 6h, flocculent products were precipitated in 20mL of anhydrous diethyl ether to obtain the polymerization precursor.

[0048] 3) Under a nitrogen protective atmosphere at room temperature, 5g of the polymerization precursor was dissolved in 100mL of N,N-dimethylformamide, 0.05g of azobisisobutyronitrile was added, the mixture was heated to 60℃, stirred at 180r / min for 6h, and then a solid product was precipitated in 20mL of anhydrous diethyl ether and dried at 60℃ to obtain a topologically structured all-solid polymer matrix.

[0049] 4) Dissolve 0.5g of topologically structured all-solid polymer matrix and 0.4g of LiTFSI in 5mL of N,N-dimethylformamide, mix evenly, and then drop-coat onto 0.1g of polyethylene terephthalate film. After vacuum drying at 80℃, the topologically structured all-solid polymer electrolyte is obtained.

[0050] The structural formula of the polymerization precursor prepared in this embodiment is:

[0051]

[0052] The all-solid polymer matrix with a topological structure prepared in this embodiment has a monocyclic topological structure, and its structural formula is as follows:

[0053]

[0054] A physical image of the all-solid-state polymer electrolyte with the topological structure prepared in this embodiment is shown below. Figure 1 The prepared colorless and transparent electrolyte membrane possesses ultra-thin thickness and superior mechanical properties. Electrochemical window testing was performed on the topologically structured all-solid-state polymer electrolyte prepared in this embodiment. The testing method was as follows: a coin cell was constructed using a stainless steel inert electrode as the working electrode and a lithium sheet as the counter electrode. Under room temperature conditions, the test voltage range was 0–6 V, and the test was conducted using an EC-lab electrochemical workstation at a scan rate of 1 mV / s. The test results are shown in [Figure number missing]. Figure 2 As can be seen from the figure, the electrolyte has a voltage range of 0-4.7V (vs. Li / Li). + The electrochemical window of the electrolyte with the topological structure indicates that it has high electrochemical stability and the potential to operate at high voltages.

[0055] The all-solid-state polymer electrolyte with the topological structure prepared in this embodiment was used to assemble a lithium-lithium symmetric battery. Specifically, the prepared all-solid-state polymer electrolyte and lithium metal sheets were sequentially placed into a 2016 coin cell casing, with a loading rate of 50 kg / cm². 2 Pressure encapsulation, after assembly, at 60°C with a pressure of 0.1 mA cm -2 Symmetrical battery tests were conducted using a current density that was charged for 1 hour and then discharged for 1 hour. The test results are shown in […]. Figure 3 As can be seen from the figure, the assembled lithium-lithium symmetric battery can cycle stably for more than 3000 hours, which shows that it has extremely high lithium stability and can be perfectly applied to lithium metal batteries.

[0056] The topological structure of the all-solid-state polymer electrolyte prepared in this embodiment is used to assemble an all-solid-state lithium metal battery. The specific method is as follows: Polyvinylidene fluoride (PVDF) with a concentration of 0.1–1.5 mol / L is dissolved in N-methylpyrrolidone. PVDF, conductive carbon black (such as Kolmogorov-Sachs black, acetylene black, or SuperP), and lithium iron phosphate active material are mixed at a mass ratio of 10:10:80 and ground for at least 1 hour. The resulting positive electrode slurry is uniformly coated onto aluminum foil or carbon-coated aluminum foil, dried in a vacuum oven at 60–120°C, rolled, punched, and stored in a glove box for later use. Lithium metal foil is purchased and stored in a glove box for later use. The prepared all-solid-state polymer electrolyte, lithium metal sheet, and positive electrode sheet are sequentially placed into a 2016 coin cell casing, and then pressed at 50 kg / cm². 2 Pressure encapsulation, followed by assembly and sterilization at 60°C at 0.5C (1C = 170mAh g). -1 After constant current charging to 4V, the voltage was discharged to 2.5V for long-cycle charge-discharge testing. The test results are shown in [link to test results]. Figure 4 As can be seen from the figure, the assembled full cell can cycle stably for more than 400 cycles, indicating that the topological structure of the all-solid-state polymer electrolyte prepared in this embodiment has high cycle stability and can be used in all-solid-state lithium metal batteries.

[0057] Example 2

[0058] A topologically structured all-solid-state polymer electrolyte comprises, by mass percentage: 60% topologically structured all-solid-state polymer matrix and 40% lithium bis(fluorosulfonyl)imide.

[0059] The preparation method of the above-mentioned all-solid-state polymer electrolyte with the above-mentioned topological structure includes the following steps:

[0060] 1) Under a nitrogen protective atmosphere at room temperature, 0.17 g of aluminum trifluoromethanesulfonate was added to 20 mL of 1,4-dioxane and stirred at 250 r / min for 10 h. The reaction solution was then solidified to obtain a solid polymer.

[0061] 2) Under the protection of nitrogen in an ice bath, 5g of solid polymer was added to 50mL of anhydrous dichloromethane, followed by the addition of 0.05g of triethylamine and 20g of isocyanate methacrylate. After stirring at 200r / min for 10h, flocculent products were precipitated in 50mL of anhydrous diethyl ether to obtain the polymerization precursor.

[0062] 3) Under a nitrogen protective atmosphere at room temperature, 1g of the polymerization precursor was dissolved in 100mL of N,N-dimethylformamide, 0.01g of azobisisobutyronitrile was added, the mixture was heated to 50℃, stirred at 250r / min for 8h, and then a solid product was precipitated in 50mL of anhydrous diethyl ether and dried at 70℃ to obtain a topologically structured all-solid polymer matrix.

[0063] 4) Dissolve 0.6g of the topologically structured all-solid polymer matrix and 0.4g of LiFSI in 10mL of tetrahydrofuran. After mixing evenly, drop-coat the mixture into a film and dry it under vacuum at 750℃ to obtain the topologically structured all-solid polymer electrolyte.

[0064] The structural formula of the polymerization precursor prepared in this embodiment is:

[0065]

[0066] The all-solid polymer matrix with a topological structure prepared in this embodiment has a polycyclic topological structure, and its structural formula is as follows:

[0067]

[0068] Example 3

[0069] A topologically structured all-solid-state polymer electrolyte comprises, by mass percentage: 10% topologically structured all-solid-state polymer matrix, 60% cellulose nonwoven membrane, and 30% lithium difluorooxalate borate.

[0070] The preparation method of the above-mentioned all-solid-state polymer electrolyte with the above-mentioned topological structure includes the following steps:

[0071] 1) Under a nitrogen protective atmosphere at room temperature, 0.03 g of aluminum trifluoromethanesulfonate was added to 15 mL of tetrahydrofuran and stirred at 180 r / min for 8 h. The reaction solution was then solidified to obtain a solid polymer.

[0072] 2) Under the protection of nitrogen in an ice bath, 8g of solid polymer was added to 80mL of anhydrous dichloromethane, followed by the addition of 0.1g of triethylamine and 8g of isocyanate methacrylate. After stirring at 230r / min for 8h, flocculent products were precipitated in 200mL of anhydrous diethyl ether to obtain the polymerization precursor.

[0073] 3) Under a nitrogen protective atmosphere at room temperature, 6g of the polymerization precursor was dissolved in 100mL of N,N-dimethylformamide, 0.06g of azobisisobutyronitrile was added, the mixture was heated to 80℃, stirred at 180r / min for 9h, and then a solid product was precipitated in 200mL of anhydrous diethyl ether and dried at 80℃ to obtain a topologically structured all-solid polymer matrix.

[0074] 4) Dissolve 0.1g of topologically structured all-solid polymer matrix and 0.3g of lithium difluorooxalate borate in 4mL of acetonitrile, mix evenly, and then drop-coat onto 0.6g of cellulose nonwoven membrane. After vacuum drying at 70℃, the topologically structured all-solid polymer electrolyte is obtained.

[0075] The structural formula of the polymerization precursor prepared in this embodiment is:

[0076]

[0077] The all-solid polymer matrix with a topological structure prepared in this embodiment has a monocyclic topological structure, and its structural formula is as follows:

[0078]

[0079] Example 4

[0080] A topologically structured all-solid-state polymer electrolyte comprises, by mass percentage: 80% topologically structured all-solid-state polymer matrix, 10% polypropylene nonwoven membrane, and 10% lithium hexafluorophosphate.

[0081] The preparation method of the above-mentioned all-solid-state polymer electrolyte with the above-mentioned topological structure includes the following steps:

[0082] 1) Under a nitrogen protective atmosphere at room temperature, 0.11 g of aluminum trifluoromethanesulfonate was added to 50 mL of tetrahydropyran and stirred at 300 r / min for 9 h. The reaction solution was then solidified to obtain a solid polymer.

[0083] 2) Under the protection of nitrogen in an ice bath, 7g of solid polymer was added to 110mL of anhydrous dichloromethane, followed by the addition of 0.5g of triethylamine and 9g of isocyanate methacrylate. After stirring at 230r / min for 7h, flocculent products were precipitated in 120mL of anhydrous diethyl ether to obtain the polymerization precursor.

[0084] 3) Under a nitrogen protective atmosphere at room temperature, 4g of the polymerization precursor was dissolved in 110mL of N,N-dimethylformamide, 0.07g of azobisisobutyronitrile was added, the mixture was heated to 70℃, stirred at 280r / min for 9h, and then a solid product was precipitated in 120mL of anhydrous diethyl ether and dried at 70℃ to obtain a topologically structured all-solid polymer matrix.

[0085] 4) Dissolve 0.8g of topologically structured all-solid polymer matrix and 0.1g of lithium hexafluorophosphate in 3mL of N-methylpyrrolidone, mix evenly, and then drop-coat it onto 0.1g of polypropylene nonwoven membrane. After vacuum drying at 60℃, the topologically structured all-solid polymer electrolyte is obtained.

[0086] The structural formula of the polymerization precursor prepared in this embodiment is:

[0087]

[0088] The all-solid polymer matrix with a topological structure prepared in this embodiment has a polycyclic topological structure, and its structural formula is as follows:

[0089]

[0090] Example 5

[0091] A topologically structured all-solid-state polymer electrolyte comprises, by mass percentage: 40% topologically structured all-solid-state polymer matrix, 10% polyarylsulfonamide nonwoven membrane, and 50% lithium bis(oxalato)borate.

[0092] The preparation method of the above-mentioned all-solid-state polymer electrolyte with the above-mentioned topological structure includes the following steps:

[0093] 1) Under a nitrogen protective atmosphere at room temperature, 0.19 g of aluminum trifluoromethanesulfonate was added to 30 mL of trioxymethane and stirred at 230 r / min for 5 h. The reaction solution was then solidified to obtain a solid polymer.

[0094] 2) Under the protection of nitrogen in an ice bath, 6g of solid polymer was added to 120mL of anhydrous dichloromethane, followed by the addition of 0.15g of triethylamine and 7g of isocyanate methacrylate. After stirring at 200r / min for 7h, flocculent products precipitated in 120mL of anhydrous diethyl ether to obtain the polymerization precursor.

[0095] 3) Under a nitrogen protective atmosphere at room temperature, 10g of the polymerization precursor was dissolved in 120mL of N,N-dimethylformamide, 0.1g of azobisisobutyronitrile was added, the mixture was heated to 90℃, stirred at 200r / min for 10h, and then a solid product was precipitated in 120mL of anhydrous diethyl ether and dried at 90℃ to obtain a topologically structured all-solid polymer matrix.

[0096] 4) Dissolve 0.5g of topologically structured all-solid polymer matrix and 0.4g of lithium bis(oxalato)borate in 10mL of N,N-dimethylformamide. After mixing evenly, drop-coat the mixture onto 0.1g of poly(arylsulfonamide) nonwoven membrane. After vacuum drying at 90℃, the topologically structured all-solid polymer electrolyte is obtained.

[0097] The structural formula of the polymerization precursor prepared in this embodiment is:

[0098]

[0099] The all-solid polymer matrix with a topological structure prepared in this embodiment has a polycyclic topological structure, and its structural formula is as follows:

[0100]

[0101] Example 6

[0102] A topologically structured all-solid-state polymer electrolyte comprises, by mass percentage: 40% topologically structured all-solid-state polymer matrix, 10% polyethylene nonwoven membrane, and 50% lithium perchlorate.

[0103] The preparation method of the above-mentioned all-solid-state polymer electrolyte with the above-mentioned topological structure includes the following steps:

[0104] 1) Under a nitrogen protective atmosphere at room temperature, 0.2 g of aluminum trifluoromethanesulfonate was added to 20 mL of oxetane and stirred at 300 r / min for 8 h. The reaction solution was then solidified to obtain a solid polymer.

[0105] 2) Under the protection of nitrogen in an ice bath, 8g of solid polymer was added to 130mL of anhydrous dichloromethane, followed by the addition of 0.15g of triethylamine and 12g of isocyanate methacrylate. After stirring at 200r / min for 8h, flocculent products were precipitated in 50mL of anhydrous diethyl ether to obtain the polymerization precursor.

[0106] 3) Under a nitrogen protective atmosphere at room temperature, 6g of the polymerization precursor was dissolved in 70mL of N,N-dimethylformamide, 0.2g of azobisisobutyronitrile was added, the mixture was heated to 50℃, stirred at 280r / min for 8h, and then a solid product was precipitated in 50mL of anhydrous diethyl ether and dried at 50℃ to obtain a topologically structured all-solid polymer matrix.

[0107] 4) Dissolve 0.5g of topologically structured all-solid polymer matrix and 0.4g of lithium perchlorate in 10mL of N-methylpyrrolidone, mix evenly, and then drop-coat it onto 0.1g of polyethylene nonwoven film. After vacuum drying at 70℃, the topologically structured all-solid polymer electrolyte is obtained.

[0108] The structural formula of the polymerization precursor prepared in this embodiment is:

[0109]

[0110] The all-solid polymer matrix with a topological structure prepared in this embodiment has a hyperbranched topological structure, and its structural formula is as follows:

[0111]

[0112] The above embodiments are merely examples for clear illustration and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations, and any obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A topologically structured all-solid-state polymer electrolyte, characterized in that, The product comprises, by weight percentage: 10-80% topologically structured all-solid-state polymer matrix, 0-60% porous support material, and 10-70% lithium salt; the topologically structured all-solid-state polymer matrix is ​​a hyperbranched, monocyclic, or polycyclic topologically structured polymer formed by self-polymerization and crosslinking of a polymerization precursor comprising two segmental structures: polyether and urea methacrylate; the structural formula of the polymerization precursor is: In the formula, R is selected from , , , , , One of them, where n is an integer from 1 to 1000.

2. The all-solid-state polymer electrolyte with the topological structure according to claim 1, characterized in that, The porous support material is one of polyethylene terephthalate film, cellulose nonwoven film, polypropylene nonwoven film, glass fiber nonwoven film, seaweed fiber nonwoven film, polyethylene nonwoven film, aramid nonwoven film, polyarylsulfonamide nonwoven film, and polyimide nonwoven film; the lithium salt is one or more of lithium bis(trifluoromethanesulfonyl)imide, lithium perchlorate, lithium hexafluorophosphate, lithium bis(oxalateborate), lithium bis(fluorosulfonyl)imide, lithium di(fluorooxalateborate), and lithium trifluoromethanesulfonate.

3. A method for preparing the all-solid-state polymer electrolyte with the topological structure as described in claim 1, characterized in that, Includes the following steps: 1) Under an inert atmosphere at room temperature, aluminum trifluoromethanesulfonate was added to an oxygen-containing heterocyclic compound, and the reaction was stirred. The reaction solution gradually solidified to obtain a solid polymer. 2) Under an inert atmosphere of an ice bath, the solid polymer was added to anhydrous dichloromethane, followed by the sequential addition of triethylamine and isocyanate methacrylate. After stirring and reacting, a flocculent product precipitated in anhydrous diethyl ether to obtain the polymerization precursor. 3) Under an inert atmosphere at room temperature, the polymerization precursor was dissolved in N,N-dimethylformamide, azobisisobutyronitrile was added, the reaction was heated and stirred, and a solid product was precipitated in anhydrous diethyl ether. After drying, a topologically structured all-solid polymer matrix was obtained. 4) Dissolve the topologically structured all-solid polymer matrix and lithium salt in a solvent, mix them evenly, and then drop-coat them onto a porous support material or directly form a self-supporting film. After vacuum drying, the topologically structured all-solid polymer electrolyte is obtained.

4. The method for preparing the all-solid-state polymer electrolyte with the topological structure according to claim 3, characterized in that, The oxygen-containing heterocyclic compound is one of 1,3-dioxolane, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, trioxymethylene, and oxobutane.

5. The method for preparing the all-solid-state polymer electrolyte with the topological structure according to claim 3, characterized in that, In step 1), the mass ratio of aluminum trifluoromethanesulfonate to the volume ratio of the oxygen-containing heterocyclic compound is (0.01~0.1) g: 10 mL, and the reaction time is 3~24 h.

6. The method for preparing the all-solid-state polymer electrolyte with the topological structure according to claim 3, characterized in that, In step 2), the mass ratio of the solid polymer to the volume of anhydrous dichloromethane is 1 g: (10~100) mL, the mass ratio of the solid polymer, triethylamine, and isocyanate methacrylate is 1: (0.01~0.1): (0.5~5), and the reaction time is 3~24 h.

7. The method for preparing the all-solid-state polymer electrolyte with the topological structure according to claim 3, characterized in that, In step 3), the mass ratio of the polymerization precursor to the volume of N,N-dimethylformamide is 1 g: (10~100) mL, the mass ratio of the polymerization precursor to azobisisobutyronitrile is 1: (0.005~0.1), the heating temperature is 40~100℃, and the reaction time is 3~24 h.

8. The method for preparing the all-solid-state polymer electrolyte with the topological structure according to claim 3, characterized in that, The solvent is one of tetrahydrofuran, acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; the volume ratio of the solvent to the mass ratio of the lithium salt is (5~30) mL:1g; and the vacuum drying temperature is 40~120℃.

9. The application of a topologically structured all-solid-state polymer electrolyte as described in any one of claims 1-2 or a topologically structured all-solid-state polymer electrolyte prepared by the preparation method described in any one of claims 3-8 in an all-solid-state lithium metal battery.

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