A quasi-solid-state alkali-ion battery super-crosslinked polymer-based electrolyte, and a preparation method and application thereof

Abstract

The present application relates to providing a kind of quasi-solid-state alkali-ion battery hypercrosslinked polymer-based electrolyte, including 100 weight parts hypercrosslinked polymer and 50~200 weight parts alkali-ion battery electrolyte;Wherein, alkali-ion battery electrolyte is dispersed in hypercrosslinked polymer;The monomer of hypercrosslinked polymer is selected from benzene, toluene, xylene, chloromethyl benzene, biphenyl, 4,4'‑dimethyl biphenyl and 4,4'‑ dichloromethyl biphenyl;The average pore size of hypercrosslinked polymer is 1~10 nm, and the thickness of hypercrosslinked polymer is 100‑300 μm.The quasi-solid-state alkali-ion battery hypercrosslinked polymer-based electrolyte prepared by the present application has the advantages of wide use condition, high mechanical strength, good cycle performance and stable electrochemical performance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of battery materials, and particularly relates to a quasi-solid-state alkali-ion battery super-crosslinked polymer-based electrolyte as well as a preparation method and application thereof. BACKGROUND

[0002] Overexploitation and utilization of non-renewable resources such as petroleum, coal and natural gas will make them quickly reach the end of exhaustion. Ultimately, it will affect the survival and development of human beings. The massive use of these fossil energy sources will also cause environmental pollution to intensify and destroy the living environment of human beings. However, in today's rapid economic development, human beings have an increasingly high demand for energy, and the use of these non-renewable resources is also increasing year by year. Therefore, in order to realize the sustainable development of society, finding substitutes for these non-renewable resources has become a problem that must be solved by human beings at present. The energy storage methods that have been developed by people at present include flywheel energy storage, compressed air energy storage, pumped storage, supercapacitor energy storage and battery energy storage. Among them, battery energy storage mainly utilizes the oxidation-reduction reaction between the positive and negative electrode materials to realize the mutual conversion of chemical energy and electrical energy. Due to high conversion efficiency and the ability to better meet the application requirements in different environments and different sizes, battery energy storage has currently attracted widespread attention. Energy storage batteries mainly include nickel-hydrogen batteries, lead-acid batteries, flow batteries and alkali metal ion batteries. Among them, alkali metal ion batteries including lithium ion batteries and sodium ion batteries have obvious advantages in many energy storage batteries due to their high energy density, good cycle performance, no memory effect and environmental friendliness.

[0003] Electrolyte, as the medium for ion transmission between the positive and negative electrodes, plays an important role in the battery system. At present, in alkali metal ion batteries, liquid electrolyte is mainly used. Non-aqueous liquid electrolyte is mainly composed of organic solvents and potassium salt. Although the organic solvent has strong ion conductivity, it is volatile and flammable, which leads to potential safety hazards such as easy ignition and explosion of the battery during use. Therefore, it is urgent to develop a new type of solid-state electrolyte. An ideal solid-state electrolyte should have high room temperature ionic conductivity, wide electrochemical stability window, excellent stability and excellent mechanical properties. The core of the solid-state battery is the solid-state electrolyte. In recent years, the research on solid-state batteries has mainly focused on the development of solid-state electrolytes with excellent performance. SUMMARY

[0004] Therefore, the present application aims to provide a quasi-solid-state alkali-ion battery super-crosslinked polymer-based electrolyte as well as a preparation method and application thereof.

[0005] The first aspect of the present application relates to providing a quasi-solid-state alkali-ion battery super-crosslinked polymer-based electrolyte, comprising

[0006] 100 parts by weight of super-crosslinked polymer, and

[0007] 50-200 parts by weight, preferably 50-150 parts by weight, more preferably 70-150 parts by weight, more preferably 100-150 parts by weight of alkali-ion battery electrolyte;

[0008] wherein,

[0009] the alkali-ion battery electrolyte is dispersed in the super-crosslinked polymer;

[0010] the monomer of the super-crosslinked polymer is selected from the group consisting of benzene, toluene, xylene, chloromethylbenzene, biphenyl, 4,4'-dimethylbiphenyl and 4,4'- dichloromethylbiphenyl, preferably selected from the group consisting of benzene, toluene, xylene, biphenyl and 4,4'-dimethylbiphenyl, more preferably selected from the group consisting of benzene and biphenyl;

[0011] the average pore size of the super-crosslinked polymer is 1-10 nm, preferably 1-8 nm, more preferably 2-5 nm,

[0012] the thickness of the super-crosslinked polymer is 100-300 μm, preferably 150-300 μm, more preferably 150-250 μm.

[0013] The second aspect of the present application relates to a method for preparing the quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte of the present application, comprising the following steps:

[0014] i) allowing the aromatic compound and the crosslinking agent to undergo a crosslinking reaction in the presence of a catalyst to obtain a super-crosslinked polymer;

[0015] ii) allowing the super-crosslinked polymer to be shaped and dried to obtain a super-crosslinked polymer-based film;

[0016] iii) dispersing the alkali-ion battery electrolyte into the super-crosslinked polymer-based film by infiltration to obtain the quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte;

[0017] wherein,

[0018] the weight ratio of the super-crosslinked polymer-based film and the alkali-ion battery electrolyte dispersed in the film is 1:(0.5-2), preferably 1:(0.5-1.5), more preferably 1:(0.7-1.5), more preferably 1:(1-1.5);

[0019] the aromatic compound is selected from the group consisting of benzene, toluene, xylene, chloromethylbenzene, biphenyl, 4,4'-dimethylbiphenyl and 4,4'-dichloromethylbiphenyl, preferably selected from the group consisting of benzene, toluene, xylene, biphenyl and 4,4'-dimethylbiphenyl, more preferably selected from the group consisting of benzene and biphenyl;

[0020] the average pore size of the super-crosslinked polymer is 1-10 nm, preferably 1-8 nm, more preferably 2-5 nm;

[0021] The thickness of the supercrosslinked polymer film is 100-300 pm, preferably 150-300 pm, more preferably 150-250 pm.

[0022] A third aspect of the present application relates to the use of the quasi-solid-state alkali-ion battery supercrosslinked polymer-based electrolyte of the present application in a secondary battery.

[0023] The present application has the following beneficial effects:

[0024] The present application provides a quasi-solid-state alkali-ion battery supercrosslinked polymer-based electrolyte. The electrolyte combines the advantages of solid-state electrolytes and liquid-state electrolytes, improving the overall performance. The quasi-solid-state alkali-ion battery supercrosslinked polymer-based electrolyte prepared by the present application has readily available raw materials and lower toxicity. Moreover, the preparation process of the present application is simple, low in cost, and easy to implement. The quasi-solid-state alkali-ion battery supercrosslinked polymer-based electrolyte prepared by the present application has the advantages of wide use conditions, high mechanical strength, good cycle performance, and stable electrochemical performance. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 is a schematic diagram of the micro-morphology of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0026] Figure 2 is a specific surface area test result graph of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0027] Figure 3 is an average pore size test result graph of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0028] Figure 4 is a linear voltammetry scan test and cyclic voltammetry test result graph of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0029] Figure 5 is a constant current charge and discharge test result graph of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0030] Figure 6 is a schematic diagram of the micro-morphology of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0031] Figure 7 is a specific surface area test result graph of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0032] Figure 8 is an average pore size test result graph of the quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte;

[0033] Figure 9Linear voltammetry test results of the super-crosslinked polymer-based electrolyte for quasi-solid-state sodium-ion batteries;

[0034] Figure 10 Galvanostatic charge-discharge test results of the super-crosslinked polymer-based electrolyte for quasi-solid-state sodium-ion batteries;

[0035] Figure 11 Micro-morphology diagram of the super-crosslinked polymer-based electrolyte membrane for quasi-solid-state potassium-ion batteries;

[0036] Figure 12 Galvanostatic charge-discharge test results of the super-crosslinked polymer-based electrolyte for quasi-solid-state potassium-ion batteries. DETAILED DESCRIPTION

[0037] Hereinafter, the present application will be described in more detail.

[0038] The term "comprising", "comprises" and "comprised of" as used herein are synonymous with "including", "includes" or "containing", "contains", and are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0039] The ranges disclosed herein are defined by the lower and upper limits of the range, given that the range is defined by selecting a lower limit and an upper limit, the selected lower limit and upper limit define the boundaries of the particular range. The ranges defined in this manner can be inclusive or exclusive of the end values, and can be arbitrarily combined, i.e. any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if a minimum range value of 1 and 2 is listed, and if a maximum range value of 3, 4 and 5 is listed, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise stated, a numerical range "a-b" indicates a shorthand manner of describing all the individual real combinations between "a" and "b", wherein "a" and "b" are both real numbers. For example, the numerical range "0-5" indicates that all the real numbers between "0" and "5" have been listed herein, "0-5" is just a shorthand manner of describing these numerical combinations. In addition, when it is stated that a parameter is an integer ≥ 2, it is equivalent to disclose that the parameter is, for example, integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0040] If not specifically stated, all the embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions.

[0041] If not specifically stated, all the technical features and optional technical features of the present application can be combined with each other to form new technical solutions.

[0042] If not otherwise specified, all steps of the present application can be performed sequentially, randomly or simultaneously. For example, the method comprising steps (a) and (b) means that the method can comprise steps (a) and (b) sequentially, or steps (b) and (a) sequentially, or steps (a) and (b) simultaneously. For example, the method comprising step (c) means that step (c) can be added to the method in any order. For example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0043] If not otherwise specified, the terms mentioned in the present application have the same meaning as generally understood by the person skilled in the art.

[0044] If not otherwise specified, the operations mentioned in the present application are performed at room temperature and under normal pressure.

[0045] If not otherwise specified, the operations mentioned in the present application can be performed by means known to the person skilled in the art.

[0046] If not otherwise specified, the equipment, devices, instruments, parts, materials, agents, etc. mentioned in the present application can be obtained by means known to the person skilled in the art.

[0047] If not otherwise specified, the indexes mentioned in the present application, such as specific surface area, pore size, etc. can be measured by means known to the person skilled in the art.

[0048] The term “quasi-solid state” mentioned in the present application refers to a special physical state of electrolyte, which is between the traditional liquid electrolyte and the all-solid-state electrolyte. Specifically, it refers to the main body of the electrolyte being composed of solid-state materials (such as super-crosslinked polymers), but possibly containing a small amount of liquid components (such as liquid electrolytes). These liquid components are “locked” in the three-dimensional network of the polymer and do not flow freely. The electrolyte as a whole exhibits solid state (no flow) on the macroscopic level, but may have a local liquid-like ion transport environment on the microscopic level, combining the stability of solid state and the high ionic conductivity of liquid state. The quasi-solid-state electrolyte of the present application is easier to form close contact with the electrode than the all-solid-state electrolyte, reducing the interface impedance; compared with the liquid electrolyte, it avoids the risk of liquid leakage, improving the safety.

[0049] According to one aspect of the present application, the present application provides a quasi-solid-state alkaline ion battery super-crosslinked polymer-based electrolyte, comprising 100 parts by weight of super-crosslinked polymer, and 50-200 parts by weight of alkaline ion battery electrolyte. Wherein the alkaline ion battery electrolyte is dispersed in the super-crosslinked polymer.

[0050] Without being bound by any theory, the inventors surprisingly found that alkali-ion battery electrolyte is adsorbed within the framework of the porous hypercrosslinked polymer (i.e. solid electrolyte) through nano-sized pores. By utilizing intermolecular forces such as hydrogen bonding and dipole-dipole interactions, solvent molecules and anion groups are anchored on the pore channels inside the hypercrosslinked polymer material, thus restricting their movement. This behavior not only reduces the solvent attack on the electrode materials, but also allows the alkali metal ions in the solid electrolyte to migrate rapidly in a pseudo-liquid environment. Meanwhile, the rigid hypercrosslinked polymer guarantees the overall stability of the electrolyte under extreme environments, not only suppressing the growth of dendrites, but also improving the oxidation resistance and service life of the solid-state electrolyte.

[0051] In one embodiment of the present application, the hypercrosslinked polymer-based electrolyte of the quasi-solid alkali-ion battery of the present application comprises 50-200 parts by weight of alkali-ion battery electrolyte, preferably 50-170 parts by weight, more preferably 50-160 parts by weight, more preferably 50-150, or preferably 70-200 parts by weight, more preferably 70-170 parts by weight, more preferably 70-160 parts by weight, more preferably 70-150 parts by weight, more preferably 90-150 parts by weight, more preferably 100-150 parts by weight, more preferably 120-150 parts by weight, more preferably 120-135 parts by weight, or 135-150 parts by weight of alkali-ion battery electrolyte. Thereby, better and balanced molding properties, mechanical strength, cycle performance and electrochemical performance can be obtained.

[0052] The specific surface area of the hypercrosslinked polymer is 600-1400 cm 2 / g, preferably 700-1300 cm 2 / g, more preferably 800-1200 cm 2 / g, more preferably 900-1100 cm 2 / g. Thereby, better and balanced molding properties, mechanical strength, cycle performance and electrochemical performance can be obtained.

[0053] The average pore size of the hypercrosslinked polymer is 1-10 nm, preferably 1-8 nm, more preferably 2-5 nm, more preferably 2.5-4.5 nm. Without being bound by any theory, the inventors surprisingly found that the above specific surface area and / or pore size provides sufficient free movement space for ions, reduces the steric hindrance of ions during migration, and the continuous pore channels are conducive to maintaining the high activity of ions and improving the ionic conductivity. Thereby, better and balanced molding properties, mechanical strength, cycle performance and electrochemical performance can be obtained.

[0054] The thickness of the supercrosslinked polymer-based electrolyte of the quasi-solid alkali-ion battery of the present application is 100-300 pm, preferably 150-300 pm, more preferably 150-250 pm, more preferably 150-220 pm, more preferably 180-220 pm, more preferably 200 pm. Without being bound by any theory, the inventors surprisingly found that as the thickness of the electrolyte increases, the bulk resistance of the electrolyte itself increases, which causes the ionic conductivity to decrease, thus being detrimental to the ion migration. Correspondingly, the decrease of the thickness of the electrolyte causes the ionic conductivity to increase, but at the same time causes the mechanical properties of the electrolyte to decrease, thus weakening the inhibition of sodium dendrite growth and being detrimental to the long cycle performance of the battery. Based on the above finding, the inventors further found that the use of the above thicknesses can achieve better and balanced molding properties, mechanical strength, cycle performance and electrochemical performance.

[0055] The monomer of the supercrosslinked polymer of the present application is an aromatic compound, which can be selected from, for example, benzene, toluene, xylene, chloromethylbenzene, biphenyl, 4,4'-dimethylbiphenyl and 4,4'- dichloromethylbiphenyl, etc., preferably from benzene, toluene, xylene, biphenyl and 4,4'- dimethylbiphenyl, more preferably from benzene and biphenyl.

[0056] In one embodiment of the present application, the monomer of the supercrosslinked polymer of the present application is selected from benzene and biphenyl. Thereby, better and balanced molding properties, mechanical strength, cycle performance and electrochemical performance can be achieved.

[0057] The base ion battery electrolyte used in the present application can be classified in various ways. For example, according to the type of battery to be used, the base ion battery electrolyte can include lithium ion battery electrolyte, sodium ion battery electrolyte and potassium ion battery electrolyte. In one embodiment of the present application, the base ion battery electrolyte of the present application can be selected from lithium ion battery electrolyte, sodium ion battery electrolyte and potassium ion battery electrolyte. Among them, the lithium ion battery electrolyte can be selected from, for example, lithium hexafluorophosphate (LiPF6), lithium bisfluorosulfonylimide (LiFSI) and lithium bis-trifluoromethanesulfonylimide (LiTFSI) solution; the sodium ion battery electrolyte can be selected from, for example, sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4) and sodium bisfluorosulfonylimide (NaFSI) solution; the potassium ion battery electrolyte can be selected from, for example, potassium hexafluorophosphate (KPF6), potassium bisfluorosulfonylimide (KFSI) and potassium bis-trifluoromethanesulfonylimide (KTFSI) solution. The solvent of the base ion battery electrolyte of the present application can be selected from, for example, carbonates, ethers and mixtures thereof, the carbonates can include, for example, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and the like; the ethers can include, for example, ethylene glycol dimethyl ether (DME) and diethylene glycol dimethyl ether (DEGDME) and the like. The base ion battery electrolyte of the present application can also include additives, such as film-forming aids, flame retardants and overcharge protection agents and the like.

[0058] In a preferred embodiment of the present application, the base ion battery electrolyte of the present application is selected from sodium ion battery electrolyte and potassium ion battery electrolyte. Among them, the sodium ion battery electrolyte is preferably selected from sodium hexafluorophosphate solution, sodium perchlorate solution and mixtures thereof, and the solvent of the sodium ion battery electrolyte is preferably selected from ethylene carbonate, diethyl carbonate and mixtures thereof. The potassium ion battery electrolyte is preferably selected from potassium hexafluorophosphate, and the solvent of the potassium ion battery electrolyte is preferably selected from ethylene carbonate, diethyl carbonate and mixtures thereof. More preferably, the solvent of the sodium ion battery electrolyte and the potassium ion battery electrolyte is a mixture of ethylene carbonate and diethyl carbonate, and further preferably, the volume ratio of ethylene carbonate and diethyl carbonate in the mixture is 1:1. In this way, better cycle performance and electrochemical performance can be obtained, and thus better balance of excellent forming performance, high mechanical strength, good cycle performance and stable electrochemical performance and the like can be achieved.

[0059] In one embodiment of the present application, the alkali-ion battery electrolyte of the present application can be obtained in a commercially available form, for example, can be purchased from Suzhou Duoduo Chemical Technology Co., Ltd., and the trade name can be, for example, LB-002 (composition: 1M LiPF6in DMC:EC:EMC=1:1:1 Vol%), LB-008 (composition: 1M LiPF6in DEC:EC=1:1 Vol%), NP-001 (composition: 1M NaPF6in DEC:EC=1:1 Vol%), NS-001 (composition: 1M NaCF3SO3in DIGLYME=100 Vol%), NC-008 (composition: 1M NaClO4in DEC:EC=1:1 Vol%), KP-001 (composition: 0.8M KPF6in EC:PC=1:1 Vol%), or KP-044 (composition: 1M KFSI in DEC:EC=1:1 Vol%).

[0060] The quasi-solid-state alkali-ion battery hypercrosslinked polymer-based electrolyte of the present application can further comprise a binder, which can be known to those skilled in the art. The binder can be selected from, for example, polyethylene oxide (PEO), polyvinylidene-hexafluoropropylene (PVDF-HFP), polyacrylonitrile (PAN), polyurethane (PU), polybutadiene (PB), polytetrafluoroethylene (PTFE), and mixtures thereof.

[0061] In one embodiment of the present application, the binder is polytetrafluoroethylene. Thereby, better molding performance and mechanical strength can be obtained, and in turn, better balance of excellent molding performance, high mechanical strength, good cycle performance, and stable electrochemical performance, and the like.

[0062] In one embodiment of the present application, the quasi-solid-state alkali-ion battery hypercrosslinked polymer-based electrolyte of the present application can further comprise 10-20 parts by weight, preferably 11-20 parts by weight, more preferably 11-15 parts by weight, more preferably 11-13 parts by weight of the binder. Thereby, better molding performance and mechanical strength can be obtained, and in turn, better balance of excellent molding performance, high mechanical strength, good cycle performance, and stable electrochemical performance, and the like.

[0063] According to another aspect of the present application, the present application also provides a method for preparing the quasi-solid-state alkali-ion battery hypercrosslinked polymer-based electrolyte of the present application, comprising the following steps:

[0064] i) allowing the aromatic compound and the crosslinking agent to undergo a crosslinking reaction in the presence of a catalyst to obtain a hypercrosslinked polymer;

[0065] ii) allowing the hypercrosslinked polymer to be molded and dried to obtain a hypercrosslinked polymer-based film;

[0066] iii) dispersing the alkali-ion battery electrolyte into the supercrosslinked polymer-based film by infiltration to obtain a quasi-solid alkali-ion battery supercrosslinked polymer-based electrolyte;

[0067] wherein,

[0068] the weight ratio of the supercrosslinked polymer-based film and the alkali-ion battery electrolyte dispersed in the film is 1 : (0.5-2), preferably 1 : (0.5-1.5), more preferably 1 : (0.7-1.5), more preferably 1 : (1-1.5);

[0069] the aromatic compound is selected from the group consisting of benzene, toluene, xylene, chloromethylbenzene, biphenyl, 4,4'-dimethylbiphenyl and 4,4'- dichloromethylbiphenyl, preferably from the group consisting of benzene, toluene, xylene, biphenyl and 4,4'-dimethylbiphenyl, more preferably from the group consisting of benzene and biphenyl;

[0070] the average pore size of the supercrosslinked polymer is 1-10 nm, preferably 1-8 nm, more preferably 2-5 nm;

[0071] the thickness of the supercrosslinked polymer film is 100-300 pm, preferably 150-300 pm, more preferably 150-250 pm.

[0072] the aromatic compound employed in the process of the present application is a monomer of a supercrosslinked polymer as defined herein.

[0073] the alkali-ion battery electrolyte employed in the process of the present application is as defined herein.

[0074] the crosslinking agent employed in the process of the present application can be known to the person skilled in the art. The crosslinking agent can be selected from the group consisting of, for example, trimethylorthoformate (TMOF), trimethylorthoacetate (TMOA), p-dimethoxybenzene (DMB), trichlorotriazine, triethylorthoacetate (TEOA), triisopropylorthoformate (TIPO), tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and dimethoxymethane (FDA), preferably from the group consisting of tetramethoxysilane, tetraethoxysilane and dimethoxymethane. In one embodiment of the present application, the crosslinking agent is dimethoxymethane.

[0075] the catalyst employed in the process of the present application can be known to the person skilled in the art. The catalyst can be selected from the group consisting of, for example, sulfuric acid, p-toluenesulfonic acid (PTSA), molybdenum pentachloride (MoCl5), aluminum trichloride (AlCl3), iron trichloride (FeCl3) and zinc chloride (ZnCl2), preferably from the group consisting of molybdenum pentachloride, aluminum trichloride, iron trichloride and zinc chloride. In one embodiment of the present application, the catalyst is iron trichloride.

[0076] In one embodiment of the present application, the weight ratio of the aromatic compound to the cross-linking agent is 1 : (2.7-4.4), preferably 1 : (3-4).

[0077] In one embodiment of the present application, the weight ratio of the cross-linking agent to the catalyst is 1 : (0.8-1.2), preferably 1 : 1.

[0078] In one embodiment of the present application, the weight ratio of the aromatic compound to the catalyst is 1 : (2.7-4.4), preferably 1 : (3-4).

[0079] In one embodiment of the present application, the weight ratio of the aromatic compound, the cross-linking agent and the catalyst is 1 : (2.7-4.4) : (2.7-4.4), preferably 1 : (3-4) : (3-4). Thereby, the specific surface area of the hypercrosslinked polymer of the present application is 600-1400 cm 2 / g, preferably 700-1300 cm 2 / g, more preferably 800-1200 cm 2 / g, more preferably 900-1100 cm 2 / g; and the average pore size is 1-10 nm, preferably 1-8 nm, more preferably 2-5 nm, more preferably 2.5-4.5 nm, to obtain better and balanced molding properties, mechanical strength, cycle performance and electrochemical performance.

[0080] The reactants of the present application can be dissolved in solvents known to those skilled in the art to perform the cross-linking reaction. The solvents can be selected from, for example, dichloromethane, dichloroethane and nitromethane. In one embodiment of the present application, the solvent is dichloroethane.

[0081] The cross-linking reaction of the present application can be performed under reaction conditions known to those skilled in the art. In one embodiment of the present application, the reaction conditions of the cross-linking reaction are reaction under an inert gas (e.g. nitrogen, argon, etc.); the reaction temperature is 60-100°C, preferably 70-90°C, more preferably 75-85°C, more preferably 80°C; and the reaction time is 18-30 hours, preferably 20-28 hours, more preferably 22-26 hours, more preferably 24 hours. Thereby, better and balanced molding properties, mechanical strength, cycle performance and electrochemical performance can be obtained.

[0082] The forming and drying process employed in the present application can be performed in a manner known to those skilled in the art. In one embodiment of the present application, the forming can be, for example, rolling, so that the thickness of the supercrosslinked polymer-based film of the present application reaches 100-300 μm, preferably 150-300 μm, more preferably 150-250 μm, more preferably 150-220 μm, more preferably 180-220 μm, more preferably 200 μm, thereby achieving better forming performance and mechanical strength, and further better balancing the properties of excellent forming performance, high mechanical strength, good cycle performance, and stable electrochemical performance. The drying can be, for example, vacuum drying, for example, drying at an absolute atmospheric pressure of less than 0.012 Mpa, preferably less than 0.0115 Mpa, more preferably less than 0.0114 Mpa; the drying temperature can be, for example, 80-95 °C, preferably 85-90 °C; the drying time can be, for example, 18-30 hours, preferably 20-28 hours, more preferably 22-26 hours, more preferably 24 hours, so that sufficient drying can be achieved, thereby achieving better forming performance and mechanical strength, and further better balancing the properties of excellent forming performance, high mechanical strength, good cycle performance, and stable electrochemical performance.

[0083] The infiltration process employed in the present application can be performed in a manner known to those skilled in the art. For example, the alkali-ion battery electrolyte is added dropwise on the surface of the supercrosslinked polymer-based film of the present application in small amounts and multiple times, and the alkali-ion battery electrolyte infiltrated on the surface of the film is absorbed into the porous structure inside the film by capillary action.

[0084] In one embodiment of the present application, the weight ratio of the supercrosslinked polymer-based film and the alkali-ion battery electrolyte dispersed in the film is 1:(0.5-2), preferably 1:(0.5-1.7), more preferably 1:(0.5-1.6), more preferably 1:(0.5-1.5), or preferably 1:(0.7-2), more preferably 1:(0.7-1.7), more preferably 1:(0.7-1.6), more preferably 1:(0.7-1.5), more preferably 1:(0.9-1.5), more preferably 1:(1-1.5), more preferably 1:(1.2-1.5), more preferably 1:(1.2-1.35), or 1:(1.35-1.5). Thereby, better and balanced forming performance, mechanical strength, cycle performance, and electrochemical performance can be achieved.

[0085] In one embodiment of the present application, the method of the present application further comprises adding a binder to the hypercrosslinked polymer before performing the shaping. Wherein the binder used is as defined herein. The weight ratio of the hypercrosslinked polymer and the binder is 1:(0.1~0.2), preferably 1:(0.11~0.2), more preferably 1:(0.11~0.15), more preferably 1:(0.11~0.13). Thereby, excellent shaping and performance and mechanical strength can be obtained, and in turn, better balance of excellent shaping performance, high mechanical strength, good cycling performance, and stable electrochemical performance, and the like.

[0086] According to another aspect of the present application, the present application also provides a use of the quasi-solid-state alkali-ion battery hypercrosslinked polymer-based electrolyte of the present application in a secondary battery.

[0087] Example

[0088] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to examples. It should be understood that the specific examples described herein are only used to explain the present application, but not to limit the present application.

[0089] The reagents or instruments used are not marked with the manufacturer, and are all conventional commercial products commonly used in the art, or can be prepared by those skilled in the art. In the examples of the present application, unless otherwise specified, all operations are performed at room temperature and under normal pressure. Unless otherwise specified, the content and percentage in the context of the present application are based on weight.

[0090] Example 1

[0091] The hypercrosslinked polymer is prepared by one-step "Friedel-Crafts" reaction, and a crosslinked network structure is woven by an external crosslinking agent dimethoxymethane (FDA) and a benzene monomer building block, forming a microporous hypercrosslinked polymer.

[0092] External crosslinking agent dimethoxymethane (FDA) and benzene monomer reacted under anhydrous FeCl3 catalysis and nitrogen protection. The ratio of benzene monomer:external crosslinking agent dimethoxymethane (FDA):anhydrous FeCl3 was 1 (0.03 mol; 2.34 g):3 (0.09 mol; 6.85 g):3 (0.09 mol; 14.60 g). All reactants were dissolved in 200 g of dichloroethane and heated to 80 °C for 24 hours to complete the condensation reaction. The resulting solid product was washed multiple times with methanol, water, dichloromethane, and acetone. The resulting solid powder was dried in a vacuum drying oven at 70 °C for 24 hours to obtain the hypercrosslinked polymer. A 200 μm thick supercrosslinked polymer-based electrolyte membrane was obtained by uniformly mixing 0.1 g of concentrated polytetrafluoroethylene dispersion with 0.8 g of phenyl supercrosslinked polymer through grinding and physical rolling. The membrane was then dried in a vacuum drying oven at 85–90 °C for 24 h at a gauge pressure of -0.09 MPa (approximately equivalent to atmospheric pressure 0.011325 MPa). The membrane was then cut into 16 mm diameter films, each weighing 0.1 g. A quasi-solid-state sodium-ion battery supercrosslinked polymer-based electrolyte membrane was obtained by adsorbing 0.12 g of commercial sodium-ion battery electrolyte (1 M NaClO4 in DEC:EC = 1:1 Vol %, Suzhou Duoduo Chemical Technology Co., Ltd., trade name NC-008) onto the porous supercrosslinked polymer film through wetting (i.e., adding small amounts of electrolyte dropwise onto the film surface).

[0093] The microstructure of the hypercrosslinked polymer-based electrolyte membrane (i.e., the hypercrosslinked polymer-based electrolyte membrane) for the quasi-solid-state sodium-ion battery is as follows: Figure 1 As shown. By Figure 1 It is known that the prepared quasi-solid-state sodium-ion battery hypercrosslinked polymer-based electrolyte has a porous structure. The rigid hypercrosslinked polymer network framework can improve the mechanical strength of the electrolyte. This porous structure can effectively adsorb organic solvent molecules in the electrolyte, restrict the movement of anionic groups in the electrolyte, and reduce the negative impact of interfering with sodium ion migration.

[0094] The prepared hypercrosslinked polymer-based electrolyte membrane was subjected to nitrogen adsorption-desorption tests at 77 K liquid nitrogen. The test results are as follows: Figure 2 and Figure 3 As shown. From Figure 2 and Figure 3 It can be seen that the specific surface area of ​​this sample is 921.62 cm². 2 / g, with an average pore size of 4.47nm.

[0095] A test cell using stainless steel as the working electrode, assembled with this quasi-solid-state electrolyte, was subjected to linear voltammetry and cyclic voltammetry tests at room temperature using a CHI600E electrochemical workstation. The results are as follows:Figure 4 As shown by Figure 4 the LSV curve of the prepared electrolyte, it can be seen that the plating / delamination potential in the curve is stable, and there is no oxidation peak except the plating / delamination potential before 4.5 V, which indicates that the prepared electrolyte has good electrochemical stability and can be matched with the positive electrode material with a charging voltage below 4.5 V.

[0096] The quasi-solid sodium-ion CR2032 type button cell assembled by using the quasi-solid electrolyte was subjected to constant current charge and discharge test at room temperature by using a LAND battery test system, and the test results are shown in Figure 5 . As shown by Figure 5 , the quasi-solid sodium-ion secondary battery assembled based on the electrolyte prepared in Example 1 has good cycle stability and can effectively improve the cycle life of the quasi-solid sodium-ion battery.

[0097] Example 2

[0098] The hypercrosslinked polymer is prepared by one-step "Friedel-Crafts" reaction, and a crosslinked network structure is woven by an external crosslinking agent dimethoxymethane (FDA) and a biphenyl monomer building block to form a microporous hypercrosslinked polymer.

[0099] The external crosslinking agent dimethoxymethane (FDA) and the biphenyl monomer are reacted under the catalysis of anhydrous FeCl3 and nitrogen protection, and the molar ratio of the biphenyl monomer: the external crosslinking agent dimethoxymethane (FDA): anhydrous FeCl3 is 1 (0.03 mol; 4.63 g): 4 (0.12 mol; 9.13 g): 4 (0.12 mol; 19.46 g). After all the reactants are dissolved in 300 g of dichloroethane and heated to 80°C for 24 hours, the condensation reaction is completed. The obtained product solid product is washed with methanol, water, dichloromethane and acetone for multiple times, and the obtained solid powder is dried in a vacuum drying oven at 70°C for 24 hours to obtain the hypercrosslinked polymer. 0.1 g of polytetrafluoroethylene concentrated dispersion is uniformly mixed with 0.8 g of biphenyl-based hypercrosslinked polymer by grinding, and then a hypercrosslinked polymer-based electrolyte membrane with a thickness of 200 μm is obtained by physical rolling. The membrane is dried in a vacuum drying oven at 85-90°C for 24 hours at a gauge pressure of -0.09 MPa (approximately equivalent to an absolute atmospheric pressure of 0.011325 Mpa), cut into a thin film with a diameter of 16 mm, and weighed to have a mass of 0.09 g. A quasi-solid sodium-ion battery hypercrosslinked polymer-based electrolyte membrane is obtained by adsorbing 0.12 g of commercial sodium-ion battery electrolyte (1 M NaPF6 in DEC:EC=1:1 Vol %, Suzhou Duoduo Chemical Technology Co., Ltd., product name NP-001) in the porous structure of the hypercrosslinked polymer thin film by infiltration (i.e., the electrolyte is added on the surface of the thin film in small amounts and multiple times).

[0100] The micro-morphology of the quasi-solid-state sodium-ion battery super-crosslinked polymer-based electrolyte film is shown in Figure 6 As can be seen from Figure 6 , the prepared quasi-solid-state sodium-ion battery super-crosslinked polymer-based electrolyte has a porous structure, and the rigid super-crosslinked polymer network framework can improve the mechanical strength of the electrolyte. This porous structure can effectively adsorb organic solvent molecules in the electrolyte, limit the movement of anion groups in the electrolyte, and reduce the negative impact on the migration of sodium ions.

[0101] The prepared super-crosslinked polymer-based electrolyte film was subjected to nitrogen adsorption / desorption test under 77K liquid nitrogen condition, and the test results are shown in Figure 7 and Figure 8 As can be seen from Figure 7 and Figure 8 , the specific surface area of the sample is 1103.28 cm 2 / g, and the average pore size is 2.88 nm.

[0102] The stainless steel test battery assembled with the quasi-solid-state electrolyte was subjected to linear voltammetry scanning test and cyclic voltammetry test at room temperature using CHI600E electrochemical workstation, and the test results are shown in Figure 9 As can be seen from the LSV curve graph of Figure 9 , it can be seen that the plating / detaching potential in the curve is stable, and there is no oxidation peak except the plating / detaching potential before 4.5 V, which indicates that the prepared electrolyte has good electrochemical stability and can be matched with the positive electrode material with a charging voltage below 4.5 V.

[0103] The quasi-solid-state sodium-ion CR2032 type button cell assembled with the quasi-solid-state electrolyte was subjected to constant current charge / discharge test at room temperature using LAND battery test system, and the test results are shown in Figure 10 . As can be seen from Figure 10 , the quasi-solid-state sodium-ion secondary battery assembled based on the electrolyte prepared in Example 2 has good cycle stability and can effectively improve the cycle life of the quasi-solid-state sodium-ion battery.

[0104] Example 3

[0105] The super-crosslinked polymer was prepared by one-step "Fu-Ke" reaction, and the crosslinked network structure was woven by external crosslinking agent dimethoxymethane (FDA) and benzene monomer building blocks to form microporous super-crosslinked polymer.

[0106] The external crosslinking agent dimethoxymethane (FDA) and benzene monomer were reacted under the catalysis of anhydrous FeCl3 and protection of argon, benzene monomer: external crosslinking agent dimethoxymethane (FDA): anhydrous FeCl3 = 1 (0.03 mol; 2.34 g): 3 (0.09 mol; 6.85 g): 3 (0.09 mol; 14.60 g), all the reactants were dissolved in 210 g of dichloroethane and heated to 80°C for 24 hours to complete the condensation reaction. The obtained product solid product was washed with methanol, water, dichloromethane, acetone several times, and the obtained solid powder was dried in a vacuum drying oven at 70°C for 24h to obtain a hypercrosslinked polymer. 0.1 g of polytetrafluoroethylene concentrated dispersion was mixed with 0.7 g of phenyl hypercrosslinked polymer by grinding, and then a hypercrosslinked polymer-based electrolyte membrane with a thickness of 200 μm was obtained by physical rolling. The membrane was dried in a vacuum drying oven at 85-90°C for 24h under a pressure of -0.09 Mpa (approximately equivalent to 0.011325 Mpa of absolute atmospheric pressure), cut into a film with a diameter of 16 mm, and weighed to have a mass of 0.1 g. A quasi-solid-state potassium ion battery hypercrosslinked polymer-based electrolyte membrane was obtained by adsorbing 0.15 g of a commercial potassium ion battery electrolyte (0.8 M KPF6 in EC:PC = 1:1 Vol %, Suzhou Duoduo Chemical Technology Co., Ltd., product name KP-001) in the porous structure of the hypercrosslinked polymer membrane by soaking (i.e., adding a small amount of electrolyte on the surface of the membrane several times).

[0107] The micro-morphology of the quasi-solid-state potassium ion battery hypercrosslinked polymer-based electrolyte membrane is shown in Figure 11 As can be seen from Figure 11 , the prepared quasi-solid-state potassium ion battery hypercrosslinked polymer-based electrolyte has a porous structure, and the rigid hypercrosslinked polymer network framework can improve the mechanical strength of the electrolyte. This porous structure can effectively adsorb the organic solvent molecules in the electrolyte, limit the movement of anion groups in the electrolyte, and reduce the negative impact on the migration of potassium ions.

[0108] The quasi-solid-state potassium ion CR2032 type button cell assembled using the quasi-solid-state electrolyte was subjected to constant current charge and discharge test at room temperature using a LAND battery test system, and the test results are shown in Figure 12 As can be seen from Figure 12 , the quasi-solid-state potassium ion secondary battery assembled based on the electrolyte prepared in Example 3 has good cycle stability, which can effectively improve the cycle life of the quasi-solid-state potassium ion battery.

[0109] Comparative Example 1

[0110] A quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte was prepared according to the method described in Example 1, except that the mass of the alkali-ion battery electrolyte absorbed by the porous structure of the super-crosslinked polymer thin film was 0.09 g.

[0111] Comparative Example 2

[0112] A quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte was prepared according to the method described in Example 1, except that the mass of the alkali-ion battery electrolyte absorbed by the porous structure of the super-crosslinked polymer thin film was 0.15 g.

[0113] Comparative Example 3

[0114] A quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte was prepared according to the method described in Example 2, except that the mass of the alkali-ion battery electrolyte absorbed by the porous structure of the super-crosslinked polymer thin film was 0.09 g.

[0115] Comparative Example 4

[0116] A quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte was prepared according to the method described in Example 2, except that the mass of the alkali-ion battery electrolyte absorbed by the porous structure of the super-crosslinked polymer thin film was 0.145 g.

[0117] Comparative Example 5

[0118] A quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte was prepared according to the method described in Example 3, except that the mass of the alkali-ion battery electrolyte absorbed by the porous structure of the super-crosslinked polymer thin film was 0.07 g.

[0119] Comparative Example 6

[0120] A quasi-solid alkali-ion battery super-crosslinked polymer-based electrolyte was prepared according to the method described in Example 3, except that the mass of the alkali-ion battery electrolyte absorbed by the porous structure of the super-crosslinked polymer thin film was 0.17 g.

[0121] The preparation and performance parameters of Examples 1-3 and Comparative Examples 1-6 are compared in Table 1 below:

[0122] Table 1:

[0123]

[0124] Comparative Example 7

[0125] The preparation of the quasi-solid-state alkali metal ion battery super-crosslinked polymer-based electrolyte was carried out according to the method described in Example 1, except that the thickness of the super-crosslinked polymer film was 300 μm.

[0126] Comparative Example 8

[0127] The preparation of the quasi-solid-state alkali metal ion battery super-crosslinked polymer-based electrolyte was carried out according to the method described in Example 1, except that the thickness of the super-crosslinked polymer film was 150 μm.

[0128] The preparation and performance parameters of Example 1 and Comparative Examples 7 and 8 are compared in the following Table 2:

[0129] Table 2:

[0130]

[0131] In summary: the quasi-solid-state alkali metal ion battery super-crosslinked polymer-based electrolyte prepared by the present application has raw materials that are easy to obtain and low toxicity, and the preparation process of the present application is simple, low in cost and easy to implement. The quasi-solid-state alkali metal ion battery super-crosslinked polymer-based electrolyte prepared by the present application has the advantages of wide use conditions, high mechanical strength, good cycle performance, stable electrochemical performance and the like, and can be applied in secondary solid-state alkali metal ion batteries.

Claims

1. A quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte, comprising: 100 parts by weight of hypercrosslinked polymer, and 120-135 parts by weight of alkaline ion battery electrolyte; in, The electrolyte for alkaline ion batteries is dispersed within a hypercrosslinked polymer, and the electrolyte is adsorbed within the porous hypercrosslinked polymer framework through nanoscale pores. The monomers of the hypercrosslinked polymer are selected from benzene, toluene, xylene, chloromethylbenzene, biphenyl, 4,4'-dimethylbiphenyl and 4,4'-dichloromethylbiphenyl; The average pore size of the hypercrosslinked polymer is 1~10 nm. The thickness of the hypercrosslinked polymer is 180-220 μm.

2. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 1, wherein, The monomers of the hypercrosslinked polymer are selected from benzene, toluene, xylene, biphenyl and 4,4'-dimethylbiphenyl.

3. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 2, wherein, The monomers of the hypercrosslinked polymer are selected from benzene and biphenyl.

4. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 1, wherein, The average pore size of the hypercrosslinked polymer is 1~8 nm.

5. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 4, wherein, The average pore size of the hypercrosslinked polymer is 2~5 nm.

6. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 1, wherein, The electrolyte for alkaline ion batteries is selected from lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide and lithium bis(trifluoromethanesulfonyl)imide solutions, sodium hexafluorophosphate, sodium perchlorate and sodium bis(fluorosulfonyl)imide solutions, potassium hexafluorophosphate, potassium bis(fluorosulfonyl)imide and potassium bis(trifluoromethanesulfonyl)imide solutions.

7. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 6, wherein, The electrolyte for alkaline ion batteries is selected from sodium hexafluorophosphate solution, sodium perchlorate solution, and potassium hexafluorophosphate solution.

8. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 1, wherein, The specific surface area of ​​hypercrosslinked polymers is 600–1400 cm². 2 / g.

9. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 8, wherein, The specific surface area of ​​hypercrosslinked polymers is 700–1300 cm². 2 / g.

10. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 9, wherein, The specific surface area of ​​the hypercrosslinked polymer is 800~1200 cm². 2 / g.

11. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 1, further comprising 10-20 parts by weight of binder. The adhesive is selected from polyethylene oxide, polyvinylidene chloride-hexafluoropropylene, polyacrylonitrile, polyurethane, polybutadiene, and polytetrafluoroethylene.

12. The quasi-solid-state alkaline ion battery supercrosslinked polymer-based electrolyte according to claim 1, further comprising 11 to 20 parts by weight of binder.

13. The quasi-solid-state alkaline ion battery supercrosslinked polymer-based electrolyte according to claim 1, further comprising 11-15 parts by weight of binder.

14. The quasi-solid-state alkaline ion battery supercrosslinked polymer-based electrolyte according to claim 1, further comprising 11 to 13 parts by weight of binder.

15. The quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to claim 11, wherein the binder is selected from polytetrafluoroethylene.

16. A method for preparing the quasi-solid-state alkaline ion battery supercrosslinked polymer-based electrolyte according to any one of claims 1-15, comprising the following steps: i) A crosslinking reaction is carried out between aromatic compounds and crosslinking agents in the presence of a catalyst to obtain a hypercrosslinked polymer; ii) The hypercrosslinked polymer is molded and dried to obtain a hypercrosslinked polymer-based film; iii) The alkaline ion battery electrolyte is dispersed into the super-crosslinked polymer-based film by wetting to obtain the quasi-solid-state alkaline ion battery super-crosslinked polymer-based electrolyte; in, The weight ratio of the hypercrosslinked polymer-based film to the alkaline ion battery electrolyte dispersed in the film is 1:(1.2~1.35); The aromatic compounds are selected from benzene, toluene, xylene, chloromethylbenzene, biphenyl, 4,4'-dimethylbiphenyl and 4,4'-dichloromethylbiphenyl; The average pore size of the hypercrosslinked polymer is 1~10 nm; The thickness of the hypercrosslinked polymer film is 180-220 μm.

17. The method according to claim 16, wherein, The aromatic compounds are selected from benzene, toluene, xylene, biphenyl and 4,4'-dimethylbiphenyl.

18. The method according to claim 17, wherein, Aromatic compounds are selected from benzene and biphenyl.

19. The method of claim 16, wherein, The average pore size of the hypercrosslinked polymer is 1~8 nm.

20. The method according to claim 19, wherein, The average pore size of the hypercrosslinked polymer is 2~5 nm.

21. The method according to claim 16, wherein, The electrolyte for alkaline ion batteries is as described in claim 6 or 7.

22. The method according to claim 16, wherein, The specific surface area of ​​hypercrosslinked polymers is 600–1400 cm². 2 / g.

23. The method according to claim 22, wherein, The specific surface area of ​​hypercrosslinked polymers is 700–1300 cm². 2 / g.

24. The method according to claim 23, wherein, The specific surface area of ​​the hypercrosslinked polymer is 800~1200 cm². 2 / g.

25. The method of claim 16, further comprising adding an adhesive to the hypercrosslinked polymer prior to molding, wherein, The weight ratio of the hypercrosslinked polymer to the adhesive is 1:(0.1~0.2); The adhesive is as described in claim 11 or 15.

26. The method of claim 25, wherein, The weight ratio of the hypercrosslinked polymer to the adhesive is 1:(0.11~0.2).

27. The method according to claim 26, wherein, The weight ratio of the hypercrosslinked polymer to the adhesive is 1:(0.11~0.15).

28. The method according to claim 27, wherein, The weight ratio of the hypercrosslinked polymer to the adhesive is 1:(0.11~0.13).

29. The method according to claim 16, wherein, The crosslinking agent is selected from tetramethoxysilane, tetraethoxysilane, and dimethoxymethane; The catalysts are selected from molybdenum pentachloride, aluminum trichloride, ferric trichloride, and zinc chloride; The weight ratio of aromatic compounds to crosslinking agents is 1:(2.7-4.4); The weight ratio of crosslinking agent to catalyst is 1:(0.8-1.2).

30. The method according to claim 29, wherein, The crosslinking agent is selected from dimethoxymethane.

31. The method according to claim 29, wherein, The catalyst was selected from ferric chloride.

32. The application of the quasi-solid-state alkaline ion battery hypercrosslinked polymer-based electrolyte according to any one of claims 1-15 in secondary batteries.

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