Pyrrole polymer electrolyte film in energy storage lithium battery and preparation method and application thereof

Abstract

The application discloses a pyrrole polymer electrolyte film in an energy storage lithium battery and a preparation method and application thereof, and belongs to the polymer electrolyte field. The method comprises the following steps: reacting 1-methyl pyrrolidine and bromine n-butane to prepare 1-methyl-1-butyl pyrrolidine bromide; preparing 1-methyl-1-butyl pyrrolidine difluoromethane sulfonimide salt ionic liquid by mixing the 1-methyl-1-butyl pyrrolidine bromide and lithium difluoromethane sulfonimide; mixing 1-methyl-1-butyl pyrrolidine difluoromethane sulfonimide salt ionic liquid, polyethylene glycol methyl ether methacrylate, acrylonitrile, lithium bistrifluoromethanesulfonimide, divinylbenzene and benzoin ethyl ether uniformly, coating and curing to obtain a pyrrole ionic liquid polymer electrolyte film. The application combines the molecular configuration of the pyrrolidine-based ionic liquid and the topological structure of the polymer network, realizes triple optimization of ion transmission-mechanical strength-interface stability.

Description

Technical Field

[0001] This invention relates to the field of polymer electrolyte technology, specifically to a pyrrole polymer electrolyte membrane for energy storage lithium batteries, its preparation method, and its application. Background Technology

[0002] With the increasing demands for battery safety in new energy vehicles and intelligent energy storage systems, traditional liquid electrolytes are gradually failing to meet the requirements due to their flammability and leakage. Solid polymer electrolytes (SPEs) have become a research hotspot due to their non-flammability and flexible processing characteristics. However, existing SPE systems still face significant challenges: rigid polymers, such as polyacrylonitrile (PAN), while exhibiting excellent film-forming properties, suffer from highly ordered molecular chain arrangements that restrict lithium-ion migration channels, resulting in room-temperature conductivity far below practical application requirements. While copolymerization modification strategies involving the introduction of flexible segments can improve chain mobility, such as the introduction of polyethylene glycol monomethyl ether acrylate (PEGMEMA), this approach often comes at the cost of sacrificing mechanical properties, leading to a significant decrease in material mechanical strength. More seriously, the physical contact interface between the polymer electrolyte and the electrode is prone to forming micron-sized voids, causing uneven lithium-ion distribution, accelerating lithium dendrite growth, and severely threatening battery cycle life. Although the use of inorganic filler doping or complex structural design can alleviate the above problems to some extent, the blockage of conduction paths caused by filler agglomeration and the high process cost make these solutions difficult to apply on a large scale.

[0003] To overcome the performance bottlenecks of solid-state electrolytes, ionic liquids (ILs) have become a key breakthrough due to their unique physicochemical properties. ILs not only possess a wide electrochemical window and high thermal stability, but their liquid-like ion transport characteristics can significantly improve the ionic conductivity of electrolyte systems. ILs containing fluorosulfonamide anions can further induce the formation of a stable solid-electrolyte interface (SEI) at the electrode interface, effectively suppressing dendrite growth, such as with FSI. - Anions. However, there are inherent contradictions in the composite of traditional ILs with polymer matrices: while imidazole ILs can enhance interfacial compatibility, their cations easily compete with lithium ions for migration, resulting in a low lithium ion transference number; pyrrolidine ILs, although having better oxidative stability, have poor compatibility with polar polymer matrices and are prone to phase separation after long-term cycling, leading to conductivity decay and mechanical property deterioration. These contradictions make it difficult to simultaneously improve the performance of IL composite systems. Summary of the Invention

[0004] This invention addresses the bottleneck problems of low ionic conductivity and high interfacial impedance in existing semi-solid lithium-ion battery polymer electrolytes by proposing the use of pyrrole-based ionic liquids to modify the polymer matrix to improve performance. However, pyrrole-based ionic liquids without structural regulation are prone to microphase separation with polar polymers, leading to the disruption of ion transport channels and deterioration of electrode / electrolyte interface stability, which in turn restricts the improvement of electrochemical performance. To overcome this technical contradiction, this invention provides a pyrrole polymer electrolyte membrane for energy storage lithium batteries, its preparation method, and its application, achieving synergistic stabilization of the "ionic liquid-polymer-electrode" triple interface through molecular design.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing a pyrrole polymer electrolyte membrane in an energy storage lithium battery, comprising:

[0007] 1-Methylpyrrolidine and n-bromobutane were reacted in an inert atmosphere to give 1-methyl-1-butylpyrrolidine bromide ionic liquid;

[0008] The 1-methyl-1-butylpyrrolidine bromide ionic liquid was reacted with lithium difluoromethanesulfonylimide in a first organic solvent to obtain the 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid.

[0009] A precursor solution was prepared by uniformly mixing 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, polyethylene glycol methyl ether methacrylate, acrylonitrile, lithium bis(trifluoromethanesulfonylimide), divinylbenzene and benzoin ether.

[0010] The precursor solution was coated and then cured with ultraviolet light to obtain a pyrrole-based ionic liquid polymer electrolyte membrane.

[0011] The molar ratio of 1-methylpyrrolidine to n-bromobutane is 1:(1~3).

[0012] The process of reacting 1-methylpyrrolidine and n-butane in an inert atmosphere to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid specifically involves: stirring 1-methylpyrrolidine and n-butane in an inert atmosphere at 24-26 °C for 2-3 h to obtain crude 1-methyl-1-butylpyrrolidine bromide ionic liquid; washing the crude 1-methyl-1-butylpyrrolidine bromide ionic liquid with a second organic solvent at 0-5 °C to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid; the second organic solvent includes ethyl acetate and anhydrous diethyl ether.

[0013] The molar ratio of the 1-methyl-1-butylpyrrolidine bromide ionic liquid to lithium difluoromethanesulfonylimide is 1:(1~3).

[0014] The first organic solvent includes one or more of anhydrous methanol, anhydrous ethanol, or isopropanol.

[0015] The step of reacting 1-methyl-1-butylpyrrolidine bromide ionic liquid with lithium difluoromethanesulfonylimide in a first organic solvent to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid is as follows: 1-methyl-1-butylpyrrolidine bromide ionic liquid and lithium difluoromethanesulfonylimide are added to the first organic solvent and reacted for 2-3 h. After the reaction, extraction is performed to obtain crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. The crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid is washed with a third organic solvent. After washing, it is placed in a vacuum environment at a temperature of 60-70 °C and dried for 20-24 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. The third organic solvent is liquid diethyl ether.

[0016] The mass ratio of the 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, polyethylene glycol methyl ether methacrylate, acrylonitrile, lithium bis(trifluoromethanesulfonylimide), divinylbenzene, and benzoin ether is (30~60):(35~50):(35~50):(25~40):(5-10):(3~5).

[0017] The ultraviolet curing process specifically involves using ultraviolet light with a wavelength of 200-260 μm; first, irradiating with pulsed ultraviolet light for 10-15 minutes, followed by continuous irradiation with ultraviolet light for 25-30 minutes.

[0018] This invention also provides a pyrrole polymer electrolyte membrane for energy storage lithium batteries, prepared according to the above-described method for preparing pyrrole polymer electrolyte membranes for energy storage lithium batteries. The structural formula of the pyrrole ionic liquid in the pyrrole ionic liquid polymer electrolyte membrane is shown below:

[0019]

[0020] Among them, FSI - It is a bis(fluoromethanesulfonyl)imide anion.

[0021] The present invention also provides the application of the pyrrole polymer electrolyte membrane in the above-mentioned energy storage lithium battery, wherein the pyrrole ionic liquid polymer electrolyte membrane is used to prepare a semi-solid lithium battery.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] This invention is based on a synergistic mechanism of "molecular steric hindrance regulation-microregion interpenetration," achieving triple optimization of ion transport, mechanical strength, and interfacial stability through precise design of the molecular configuration of pyrrolidinyl ionic liquids and the topology of polymer networks. Compared to traditional imidazole systems, the saturated cyclic structure of pyrrolidinyl effectively blocks cation migration through steric hindrance. The hydrophobic butyl chain of the ionic liquid and the polar ethylene oxide (EO) segments of PEGMEMA form ordered ion-enriched regions through microphase separation, significantly reducing ion transport tortuosity. Simultaneously, the strong binding force between the rigid pyrrolidinyl ring and the PAN cyano group inhibits ion liquid leakage at high temperatures, ensuring long-term cycling stability. Combined with UV gradient polymerization, dynamically formed FSI... - -TFSI - The coordination network not only promotes lithium salt dissociation but also adapts to changes in electrode volume, maintaining interfacial contact integrity. This invention addresses the "performance imbalance" problem of traditional composite electrolytes, providing a solution for high-voltage, wide-temperature-range semi-solid-state batteries that combines intrinsic safety with high-efficiency conductivity.

[0024] The pyrrole-based ionic liquid polymer electrolyte membrane of this invention exhibits breakthroughs in multiple dimensions: in terms of electrochemical performance, the room temperature ionic conductivity reaches 1.38 × 10⁻⁶. -4 The tensile strength remained at 6.7 MPa, controlled by molecular chain entanglement and cross-linking networks, with a high voltage chemical stability window of 4.7 V at room temperature. Regarding interfacial stability, the assembled lithium battery achieved an initial discharge specific capacity of 156 mAh·g at a 0.2 C rate. -1 This provides a new path for high-safety, long-life semi-solid-state batteries. Attached Figure Description

[0025] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 The image shows the 1H NMR (Nuclear Magnetic Resonance Spectroscopy of Hydrogen) spectrum of the pyrrole polymer electrolyte membrane in the energy storage lithium battery prepared in Example 1.

[0027] Figure 2 A comparison of the tensile strength of the polymer electrolyte membranes prepared in Example 1, Example 2 and Comparative Example 1;

[0028] Figure 3 The image shows a comparison of the voltammetric curves of the polymer electrolyte membranes prepared in Examples 1, 2, and 1. Detailed Implementation

[0029] To make the technical problem to be solved, the technical solution, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.

[0030] In this invention, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0031] In this invention, "at least one" refers to one or more items, and "more than one" refers to two or more items. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c," or "at least one of a, b, and c," can both represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or multiple.

[0032] It should be understood that in various embodiments of the present invention, the order of the above-mentioned processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0033] The terminology used in the embodiments of this invention is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms “a,” “the,” and “the” as used in the embodiments of this invention and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0034] The weights of the relevant components mentioned in the embodiments of this invention can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this invention is within the scope disclosed in the embodiments of this invention. Specifically, the mass described in the embodiments of this invention can be a mass unit known in the chemical industry, such as μg, mg, g, or kg.

[0035] This invention provides a method for preparing a pyrrole polymer electrolyte membrane in an energy storage lithium battery, comprising:

[0036] 1-Methylpyrrolidine and n-butane bromide were mixed uniformly and reacted in an inert atmosphere to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid; 1-methyl-1-butylpyrrolidine bromide ionic liquid and lithium difluoromethanesulfonylimide were added to a first organic solvent to react and obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid; 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, polyethylene glycol methyl ether methacrylate, acrylonitrile (AN), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), divinylbenzene (DVB) and benzoin ether were mixed uniformly to obtain a precursor solution; the precursor solution was coated and then cured with ultraviolet light to obtain a pyrrole-based ionic liquid polymer electrolyte membrane.

[0037] In some embodiments, the molar ratio of 1-methylpyrrolidine to n-butane bromide is 1:(1~3). Using an appropriate molar ratio of 1-methylpyrrolidine to n-butane bromide in the preparation of 1-methyl-1-butylpyrrolidine bromide ionic liquid can reduce the occurrence of side reactions.

[0038] In some embodiments, 1-methylpyrrolidine and n-butane bromide are stirred in an inert atmosphere at a temperature of 24-26°C for 2-3 hours to obtain a crude product, 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude product, 1-methyl-1-butylpyrrolidine bromide ionic liquid, is washed with a second organic solvent at a temperature of 0-5°C to obtain another 1-methyl-1-butylpyrrolidine bromide ionic liquid. The second organic solvent includes ethyl acetate and anhydrous diethyl ether.

[0039] In some embodiments, the molar ratio of 1-methyl-1-butylpyrrolidine bromide ionic liquid to lithium difluoromethanesulfonylimide is 1:(1~3).

[0040] In some embodiments, the first organic solvent includes anhydrous methanol, anhydrous ethanol, and isopropanol.

[0041] In some embodiments, 1-methyl-1-butylpyrrolidine bromide ionic liquid and lithium difluoromethanesulfonylimide are added to a first organic solvent and reacted for 2-3 h. After the reaction, extraction is performed to obtain crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. The crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid is washed with a third organic solvent. After washing, it is dried in a vacuum environment at a temperature of 60-70 °C for 20-24 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. The third organic solvent is liquid diethyl ether.

[0042] In some embodiments, the mass ratio of the 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, polyethylene glycol methyl ether methacrylate, acrylonitrile, lithium bis(trifluoromethanesulfonylimide), divinylbenzene, and benzoin ether is (30~60): (35~50): (35~50): (25~40): (5-10): (3~5).

[0043] In some embodiments, during UV curing, the wavelength of the UV light used is 200~260μm; first, pulsed UV light irradiation is applied for 10~15 minutes, followed by continuous UV light irradiation for 25~30 minutes. This method employs gradient irradiation, first using pulsed irradiation to suppress local overheating, with an on / off cycle of 1s / 2s; then, continuous irradiation is used to promote the polymerization reaction.

[0044] In some embodiments, the precursor solution is cast onto the surface of a first film-forming mold, platinum wires are placed at each of the four corners of the first film-forming mold, and then a second film-forming mold is placed on top of the platinum wires to spread the precursor solution evenly. The platinum wires are 2 cm long and 35 μm in diameter, the misalignment angle between the first and second film-forming molds is 45°, and the temperature during the coating process is 22–28 °C. Placing the platinum wires in the center of the film-forming mold ensures the thickness of the polymer electrolyte membrane and also helps maintain the uniformity of the film thickness.

[0045] The pyrrole-based ionic liquid polymer electrolyte membrane is stored in an argon-filled glove box, where water content is <0.1 ppm and oxygen content is <0.1 ppm. This prevents the membrane from being affected by moisture and oxygen, thus ensuring stable performance and extending its service life.

[0046] This invention prepares a pyrrole polymer electrolyte membrane for energy storage lithium batteries using the above-described preparation method. The structural formula of the pyrrole ionic liquid in the pyrrole ionic liquid polymer electrolyte membrane is shown below:

[0047]

[0048] Among them, FSI- It is a bis(fluoromethanesulfonyl)imide anion.

[0049] This invention is based on a pyrrolidinyl ionic liquid composite polymer electrolyte, and through a synergistic design of "steric hindrance regulation-micro-region interpenetration," it achieves synergistic optimization of ion transport, mechanical strength, and interface stability. For example... Figure 1 As shown, the ionic liquid's 1 ¹H NMR showed characteristic peaks that perfectly matched the theoretical structure, confirming successful synthesis. The rigid saturated cyclic structure of the pyrrolidinyl group interacts strongly with the cyano group of PAN through steric hindrance, effectively suppressing ionic liquid aggregation. The hydrophobic butyl chain of the ionic liquid and the ethylene oxide segment of PEGMEMA form ordered ion transport channels through microphase separation, significantly reducing lithium-ion migration resistance. Tensile strength test curves show that this electrolyte membrane maintains high ionic conductivity while exhibiting significantly superior mechanical strength compared to traditional polymer electrolyte systems. Its balance between elongation at break and tensile strength effectively suppresses interfacial delamination during battery cycling. Linear sweep voltammetry curves show an electrochemical window exceeding 4.7V, thanks to the high oxidation stability of the pyrrolidinyl group and FSI. - The anion-mediated interface passivation makes it suitable for high-voltage cathode materials. Furthermore, the formation of the dynamic coordination network not only promotes lithium salt dissociation but also adapts to changes in electrode volume. Combined with the in-situ generated LiF-rich interface layer, this allows the battery to maintain excellent cycle stability over a wide temperature range and under fast-charging conditions.

[0050] Applying the pyrrole polymer electrolyte membrane provided by this invention to a semi-solid lithium battery can significantly improve the discharge specific capacity of the semi-solid lithium battery.

[0051] In the following embodiments, unless otherwise specified, all materials used can be obtained through ordinary channels; the testing methods used are conventional methods in the art.

[0052] Example 1

[0053] 1.0 g of 1-methylpyrrolidine and 1.93 g of n-butane bromide were added to a three-necked flask and stirred for 2 hours under a nitrogen atmosphere at 25 °C to obtain the crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed three times with ethyl acetate and anhydrous diethyl ether, respectively, to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid, denoted as [PYR14]Br. [PYR14]Br was stored in a vacuum at 0 °C for 8 hours before use.

[0054] 1.0 g of [PYR14]Br and 2.2 g of LiFSI were added to anhydrous methanol and mixed evenly. The mixture was stirred for 2 hours to carry out the reaction. The solution after the reaction was placed in a separatory funnel for extraction to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. After washing three times with liquid diethyl ether, the solution was dried in a vacuum environment at 60 °C for 24 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, denoted as [PYR14][FSI].

[0055] 1.2 g [PYR14][FSI], 0.8 g PEGMEMA, 0.8 g AN, 0.6 g LiTFSI, 0.14 g DVB, and 0.06 g benzoin ether were added to a beaker and stirred to obtain a precursor solution.

[0056] The precursor solution is cast onto the surface of the first glass mold. A piece of platinum wire, 3 cm long and 35 μm in diameter, is placed at each of the four corners of the first glass mold. The second glass mold is then placed on top of the platinum wire. The first and second glass molds are offset by 45° so that the precursor solution is evenly spread between the glass molds to the required thickness. The temperature of the entire coating process is 22~28 ℃.

[0057] The glass mold coated with the precursor solution from the previous step was placed horizontally in the ultraviolet reaction chamber and irradiated with ultraviolet light (UV) with a wavelength of 200 μm in pulse mode (on / off cycle of 1 s / 2 s). After continuous irradiation for 25 minutes, gradient polymerization was initiated. After curing, a pyrrole-based ionic liquid polymer electrolyte membrane was obtained, denoted as PPA2-[PYR14][FSI]1.

[0058] like Figure 1 As shown, the [PYR14][FSI] prepared in this embodiment... 1 The 1H NMR spectrum shows that... 1 ¹H NMR (500 MHz, D₂O): 3.35-3.45 (4H, C-CH₂-N), 3.21-3.24 (2H, N=CH₂-C), 2.95-2.98 (3H, N-CH₃), 2.09-2.14 (4H, CH₂-CH₂), 1.65-1.72 (2H, C-CH₂-C), 1.26-1.33 (2H, C-CH₂-C), 0.83-0.87 (3H, -CH₃). These characteristic peaks indicate that [PYR₁₄][FSI] was successfully prepared in this embodiment. H at each position can be found in the NMR spectrum, and no obvious impurity peaks appear, indicating high product purity.

[0059] The PPA2-[PYR14][FSI]1 prepared in this embodiment was assembled with a positive electrode (lithium iron phosphate) and a negative electrode (lithium metal sheet) into a 2025 model button cell. Performance testing was conducted, and the conductivity at room temperature was measured to be 2.73 × 10⁻⁶. -4 S / cm. To test the application of polymer electrolyte in semi-solid lithium batteries, it was assembled into a LiFePO4 / PPA2-[PYR14][FSI]1 / Li battery and charged-discharge cycled at 60℃; the initial discharge specific capacity of the battery at 0.2 C rate was measured to be 133 mAh·g. -1 .

[0060] Example 2

[0061] 1.0 g of 1-methylpyrrolidine and 1.93 g of n-butane bromide were added to a three-necked flask and stirred for 2 hours under a nitrogen atmosphere at 25 °C to obtain the crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed three times with ethyl acetate and anhydrous diethyl ether, respectively, to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid, denoted as [PYR14]Br. [PYR14]Br was stored in a vacuum at 0 °C for 8 hours before use.

[0062] 1.0 g of [PYR14]Br and 2.2 g of LiFSI were added to anhydrous methanol and mixed evenly. The mixture was stirred for 2 hours to carry out the reaction. The solution after the reaction was placed in a separatory funnel for extraction to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. After washing three times with liquid diethyl ether, the solution was dried in a vacuum environment at 60 °C for 24 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, denoted as [PYR14][FSI].

[0063] Add 0.9 g [PYR14][FSI], 0.8 g PEGMEMA, 0.8 g AN, 0.6 g LiTFSI, 0.14 g DVB, and 0.06 g benzoin ether to a beaker and stir to obtain a precursor solution.

[0064] The precursor solution is cast onto the surface of the first glass mold. A piece of platinum wire, 3 cm long and 35 μm in diameter, is placed at each of the four corners of the first glass mold. The second glass mold is then placed on top of the platinum wire. The first and second glass molds are offset by 45° so that the precursor solution is evenly spread between the glass molds to the required thickness. The temperature of the entire coating process is 22~28 ℃.

[0065] The glass mold coated with the precursor solution from the previous step was placed horizontally in a UV reaction chamber and irradiated with UV light at a wavelength of 200 μm in pulse mode (on / off cycle of 1 s / 2 s), followed by continuous irradiation for 25 minutes to initiate gradient polymerization. After curing, a pyrrole-based ionic liquid polymer electrolyte membrane was obtained, denoted as PPA4-[PYR14][FSI]. 1.5 .

[0066] The PPA4-[PYR14][FSI] prepared in this embodiment 1.5 The battery was assembled with a positive electrode (lithium iron phosphate) and a negative electrode (lithium metal sheet) into a 2025 model button cell. Performance testing was conducted, and the conductivity at room temperature was measured to be 2.67 × 10⁻⁶. -4 S / cm. To investigate the application of polymer electrolytes in semi-solid-state lithium batteries, they were assembled into LiFePO4 / PPA4-[PYR14][FSI]. 1.5 The Li battery was tested for charge-discharge cycles at 60 °C; the initial discharge specific capacity at 0.5 C rate was measured to be 136 mAh·g. -1 .

[0067] Example 3

[0068] 1.0 g of 1-methylpyrrolidine and 1.93 g of n-butane bromide were added to a three-necked flask and stirred for 2 hours under a nitrogen atmosphere at 25 °C to obtain the crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed three times with ethyl acetate and anhydrous diethyl ether, respectively, to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid, denoted as [PYR14]Br. [PYR14]Br was stored in a vacuum at 0 °C for 8 hours before use.

[0069] 1.0 g of [PYR14]Br and 2.20 g of LiFSI were added to anhydrous methanol and mixed evenly for 2 hours to carry out the reaction. The solution after the reaction was placed in a separatory funnel for extraction to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. After washing three times with liquid diethyl ether, it was dried in a vacuum environment at 60 °C for 24 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, denoted as [PYR14][FSI].

[0070] Add 0.6 g [PYR14][FSI], 0.8 g PEGMEMA, 0.8 g AN, 0.6 g LiTFSI, 0.14 g DVB, and 0.06 g benzoin ether to a beaker and stir to obtain a precursor solution.

[0071] The precursor solution is cast onto the surface of the first glass mold. A piece of platinum wire, 3 cm long and 35 μm in diameter, is placed at each of the four corners of the first glass mold. The second glass mold is then placed on top of the platinum wire. The first and second glass molds are offset by 45° so that the precursor solution is evenly spread between the glass molds to the required thickness. The temperature of the entire coating process is 22~28 ℃.

[0072] The glass mold containing the precursor solution from the previous step was placed horizontally in the UV reaction chamber and irradiated with UV light at a wavelength of 200 μm in pulse mode (on / off cycle of 1 s / 2 s). After irradiation for 25 minutes, gradient polymerization was initiated. After curing, a pyrrole-based ionic liquid composite polymer electrolyte was obtained, denoted as PPA4-[PYR14][FSI]1.

[0073] The PPA4-[PYR14][FSI]1 prepared in this embodiment was assembled with a positive electrode (lithium iron phosphate) and a negative electrode (lithium metal sheet) into a 2025 model button cell. Performance testing was conducted, and the conductivity at room temperature was measured to be 1.38 × 10⁻⁶. -4 S / cm. To test the application of polymer electrolyte in semi-solid lithium batteries, it was assembled into a LiFePO4 / PPA4-[PYR14][FSI]1 / Li battery and charged-discharge cycled at 60℃; the initial discharge specific capacity of the battery at 0.5C rate was measured to be 142 mAh·g. -1 .

[0074] Example 4

[0075] 1.0 g of 1-methylpyrrolidine and 3.22 g of n-butane bromide were added to a three-necked flask and stirred for 3 hours under a nitrogen atmosphere at 26 °C to obtain the crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed three times each with ethyl acetate and anhydrous diethyl ether at 5 °C to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid, denoted as [PYR14]Br. [PYR14]Br was stored in a vacuum at 0 °C for 8 hours before use.

[0076] 1.0 g of [PYR14]Br and 1.27 g of LiFSI were added to anhydrous ethanol and mixed evenly. The mixture was stirred for 3 hours to carry out the reaction. The solution after the reaction was placed in a separatory funnel for extraction to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. After washing three times with liquid diethyl ether, the solution was dried in a vacuum environment at 65 °C for 22 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, denoted as [PYR14][FSI].

[0077] Add 0.7 g [PYR14][FSI], 0.7 g PEGMEMA, 0.7 g AN, 0.5 g LiTFSI, 0.1 g DVB, and 0.1 g benzoin ether to a beaker and stir to obtain a precursor solution.

[0078] The precursor solution is cast onto the surface of the first glass mold. A piece of platinum wire, 3 cm long and 35 μm in diameter, is placed at each of the four corners of the first glass mold. The second glass mold is then placed on top of the platinum wire. The first and second glass molds are offset by 45° so that the precursor solution is evenly spread between the glass molds to the required thickness. The temperature of the entire coating process is 22~28 ℃.

[0079] The glass mold coated with the precursor solution from the previous step was placed horizontally in the UV reaction chamber and irradiated with UV light at a wavelength of 260 μm in pulse mode (on / off cycle of 1 s / 2 s) for 10 minutes, followed by continuous irradiation for 25 minutes to initiate gradient polymerization. After curing, a pyrrole-based ionic liquid polymer electrolyte membrane was obtained, denoted as PPA3-[PYR14][FSI]1.

[0080] The PPA3-[PYR14][FSI]1 prepared in this embodiment was assembled with a positive electrode (lithium iron phosphate) and a negative electrode (lithium metal sheet) into a 2025 model button cell. Performance testing was conducted, and the conductivity at room temperature was measured to be 2.87 × 10⁻⁶. -4 S / cm. To test the application of polymer electrolyte in semi-solid lithium batteries, it was assembled into a LiFePO4 / PPA3-[PYR14][FSI]1 / Li battery and charged-discharge cycled at 60℃; the initial discharge specific capacity of the battery at 0.5C rate was measured to be 131 mAh·g. -1 .

[0081] Example 5

[0082] 1.0 g of 1-methylpyrrolidine and 4.83 g of n-butane bromide were added to a three-necked flask and stirred for 3 hours under a nitrogen atmosphere at 24 °C to obtain the crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude product 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed three times each with ethyl acetate and anhydrous diethyl ether at 3 °C to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid, denoted as [PYR14]Br. [PYR14]Br was stored in a vacuum at 0 °C for 8 hours before use.

[0083] 1.0 g of [PYR14]Br and 0.85 g of LiFSI were added to anhydrous ethanol and mixed evenly. The mixture was stirred for 2.5 hours to carry out the reaction. The solution after the reaction was placed in a separatory funnel for extraction to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. After washing three times with liquid diethyl ether, the solution was dried in a vacuum environment at 70 °C for 20 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, denoted as [PYR14][FSI].

[0084] Add 1.0 g [PYR14][FSI], 0.7 g PEGMEMA, 0.7 g AN, 0.8 g LiTFSI, 0.2 g DVB, and 0.1 g benzoin ether to a beaker and stir to obtain a precursor solution;

[0085] The precursor solution is cast onto the surface of the first glass mold. A piece of platinum wire, 3 cm long and 35 μm in diameter, is placed at each of the four corners of the first glass mold. The second glass mold is then placed on top of the platinum wire. The first and second glass molds are offset by 45° so that the precursor solution is evenly spread between the glass molds to the required thickness. The temperature of the entire coating process is 22~28 ℃.

[0086] The glass mold coated with the precursor solution from the previous step was placed horizontally in the UV reaction chamber and irradiated with UV light at a wavelength of 220 μm in pulse mode (on / off cycle of 1 s / 2 s) for 15 minutes, followed by continuous irradiation for 30 minutes to initiate gradient polymerization. After curing, a pyrrole-based ionic liquid polymer electrolyte membrane, denoted as PPA, was obtained. 2.5 -[PYR14][FSI]1.

[0087] The PPA prepared in this embodiment 2.5 -[PYR14][FSI]1 was assembled with a positive electrode (lithium iron phosphate) and a negative electrode (lithium metal sheet) into a 2025 model button cell. Performance testing was conducted, and the conductivity at room temperature was measured to be 2.52 × 10⁻⁶. -4 S / cm. To test the application of polymer electrolytes in semi-solid lithium batteries, they were assembled into LiFePO4 / PPA. 2.5 The [PYR14][FSI]1 / Li battery was tested for charge-discharge cycles at 60 °C; the initial discharge specific capacity at 0.5 C rate was measured to be 142 mAh·g. -1 .

[0088] Example 6

[0089] 1.0 g of 1-methylpyrrolidine and 1.65 g of n-butane bromide were added to a three-necked flask and stirred for 2.5 hours under a nitrogen atmosphere at 25 °C to obtain crude 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed three times each with ethyl acetate and anhydrous diethyl ether at 0 °C to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid, denoted as [PYR14]Br. [PYR14]Br was stored in a vacuum at 0 °C for 8 hours before use.

[0090] 1.0 g of [PYR14]Br and 1.65 g of LiFSI were added to isopropanol and mixed evenly. The mixture was stirred for 3 hours to carry out the reaction. The solution after the reaction was placed in a separatory funnel for extraction to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. After washing three times with liquid diethyl ether, the solution was dried in a vacuum environment at 70 °C for 24 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, denoted as [PYR14][FSI].

[0091] Add 1.0 g [PYR14][FSI], 0.9 g PEGMEMA, 0.9 g AN, 0.5 g LiTFSI, 0.12 g DVB, and 0.08 g benzoin ether to a beaker and stir to obtain a precursor solution.

[0092] The precursor solution is cast onto the surface of the first glass mold. A piece of platinum wire, 3 cm long and 35 μm in diameter, is placed at each of the four corners of the first glass mold. The second glass mold is then placed on top of the platinum wire. The first and second glass molds are offset by 45° so that the precursor solution is evenly spread between the glass molds to the required thickness. The temperature of the entire coating process is 22~28 ℃.

[0093] The glass mold coated with the precursor solution from the previous step was placed horizontally in the UV reaction chamber and irradiated with UV light at a wavelength of 250 μm in pulse mode (on / off cycle of 1 s / 2 s) for 12 minutes, followed by continuous irradiation for 28 minutes to initiate gradient polymerization. After curing, a pyrrole-based ionic liquid polymer electrolyte membrane, denoted as PPA, was obtained. 2.5 -[PYR14][FSI]1.

[0094] The PPA prepared in this embodiment 2.5 -[PYR14][FSI]1 was assembled with a positive electrode (lithium iron phosphate) and a negative electrode (lithium metal sheet) into a 2025 model button cell. Performance testing was conducted, and the conductivity at room temperature was measured to be 2.70 × 10⁻⁶. -4S / cm. To test the application of polymer electrolytes in semi-solid lithium batteries, they were assembled into LiFePO4 / PPA. 2.5 The [PYR14][FSI]1 / Li battery was tested for charge-discharge cycles at 60 °C; the initial discharge specific capacity at 0.5 C rate was measured to be 135 mAh·g. -1 .

[0095] Example 7

[0096] 1.0 g of 1-methylpyrrolidine and 4.15 g of n-butane bromide were added to a three-necked flask and stirred for 2 hours under a nitrogen atmosphere at 26 °C to obtain crude 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed three times each with ethyl acetate and anhydrous diethyl ether at 0 °C to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid, denoted as [PYR14]Br. [PYR14]Br was stored in a vacuum at 0 °C for 8 hours before use.

[0097] 1.0 g of [PYR14]Br and 2.55 g of LiFSI were added to a mixture of anhydrous methanol and isopropanol and stirred for 3 hours to react. The resulting solution was extracted in a separatory funnel to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. After washing three times with liquid diethyl ether, the solution was dried in a vacuum environment at 60 °C for 20 h to obtain 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, denoted as [PYR14][FSI].

[0098] Add 1.0 g [PYR14][FSI], 1.0 g PEGMEMA, 1.0 g AN, 0.8 g LiTFSI, 0.12 g DVB, and 0.08 g benzoin ether to a beaker and stir to obtain a precursor solution.

[0099] The precursor solution is cast onto the surface of the first glass mold. A piece of platinum wire, 3 cm long and 35 μm in diameter, is placed at each of the four corners of the first glass mold. The second glass mold is then placed on top of the platinum wire. The first and second glass molds are offset by 45° so that the precursor solution is evenly spread between the glass molds to the required thickness. The temperature of the entire coating process is 22~28 ℃.

[0100] The glass mold coated with the precursor solution from the previous step was placed horizontally in the UV reaction chamber and irradiated with UV light at a wavelength of 250 μm in pulse mode (on / off cycle of 1 s / 2 s) for 10 minutes, followed by continuous irradiation for 30 minutes to initiate gradient polymerization. After curing, a pyrrole-based ionic liquid polymer electrolyte membrane was obtained, denoted as PPA3-[PYR14][FSI]1.

[0101] The PPA3-[PYR14][FSI]1 prepared in this embodiment was assembled with a positive electrode (lithium iron phosphate) and a negative electrode (lithium metal sheet) into a 2025 type button cell. Performance testing was conducted, and the conductivity at room temperature was measured to be 2.24 × 10⁻⁶. -4 S / cm. To test the application of polymer electrolyte in semi-solid lithium batteries, it was assembled into a LiFePO4 / PPA3-[PYR14][FSI]1 / Li battery and charged-discharge cycled at 60℃; the initial discharge specific capacity of the battery at a 0.5 C rate was measured to be 141 mAh·g. -1 .

[0102] Comparative Example 1

[0103] The specific steps for preparing the polymer electrolyte membrane in Comparative Example 1 are as follows: 2.0 g of polyvinylidene difluoride (PVDF) and 0.40 g of LiTFSI were dissolved in 20 ml of N-methylpyrrolidone (NMP) solution. The resulting solution was poured onto the surface of a glass mold and dried in a vacuum environment at 60 ℃ for 24 hours to obtain the polymer electrolyte membrane, denoted as PVDF. It was assembled into a LiFePO4 / PVDF / Li battery, and its charge-discharge cycle performance was tested at 60 ℃. The conductivity of the polymer electrolyte membrane at room temperature was measured to be 1.26 × 10⁻⁶. -5 The S / cm ratio indicates that the initial discharge specific capacity of the battery, measured at a 0.2C rate, is 83 mAh·g. -1 .

[0104] The mechanical properties (tensile strength and fracture strain) of the electrolyte membranes prepared in the examples and comparative examples were further measured using a universal tensile testing machine. Figure 2 As shown, PVDF exhibits the highest stress value at approximately 8.4 ± 0.1 MPa, while its strain value is relatively poor at 22.5%. After the addition of ionic liquids to PPA, PPA2-[PYR14][FSI]1 and PPA4-[PYR14][FSI]... 1.5 The tensile properties were significantly improved; among them, the tensile strength and elongation at break of PPA2-[PYR14][FSI]1 were 1.6±0.1 MPa and 38.2%, respectively, and those of PPA4-[PYR14][FSI] were also significantly improved. 1.5The tensile strength and elongation at break were 2.1 ± 0.1 MPa and 72.3%, respectively. (PPA4-[PYR14][FSI)) 1.5 The high strain value is due to the addition of ionic liquid, which enhances the mobility of PEGMEMA chain segments.

[0105] The electrochemical stability of the electrolyte membranes prepared in the examples and comparative examples at 25°C was evaluated using linear sweep voltammetry. Figure 3 As shown, compared to PVDF with an electrochemical window of 4.0 V, PPA2-[PYR14][FSI]1 and PPA4-[PYR14][FSI]1... 1.5 The electrochemical windows of the electrolyte membrane were 4.5 V and 4.7 V, respectively. This result indicates that PPA4-[PYR14][FSI]... 1.5 It exhibits electrochemical stability for both lithium metal and high-voltage cathodes.

[0106] This invention, based on a "steric hindrance-micro-region synergy" design strategy, overcomes the performance bottleneck of traditional composite electrolytes by precisely matching the molecular configuration of pyrrolidinyl ionic liquids with the topology of polymer networks. Compared to conventional systems, the saturated cyclic structure of pyrrolidinyl significantly suppresses the competitive migration of cations and lithium ions (increasing the lithium ion transference number to 0.61) through a unique steric hindrance effect. Small-angle X-ray scattering (SAXS) confirmed the layered ordered structure. The hydrophobic butyl side chain and the ethylene oxide segments of PEGMEMA form ordered hydrophilic-hydrophobic micro-regions through microphase separation, constructing low-torsion ion transport channels and achieving a synergistic improvement in ionic conductivity and mechanical strength. Simultaneously, the strong interaction between the rigid pyrrolidinyl ring and the PAN cyano group, characterized by binding energy shift using X-ray photoelectron spectroscopy, effectively anchors the ionic liquid, preventing component leakage during high-temperature cycling. In-depth analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS) indicates that FSI... - The synergistic coordination network between anions and lithium salts not only promotes efficient lithium salt dissociation but also generates a dense and stable LiF-rich layer in situ at the electrode interface, suppressing dendrite growth and reducing interfacial impedance. Combined with the dynamic control of UV gradient polymerization, the electrolyte membrane exhibits stable interfacial contact and cycling performance over a wide temperature range (-40~120 ℃). In-situ electrochemical impedance spectroscopy (EIS) shows impedance fluctuations of <5%, providing an innovative solution for high-voltage, fast-charging semi-solid-state lithium batteries that combines high safety and long lifespan.

[0107] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0108] The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can still make modifications or equivalent substitutions to the specific implementation of the present invention. Any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention are within the protection scope of the claims of the present invention pending approval.

Claims

1. A method for preparing a pyrrole polymer electrolyte membrane in an energy storage lithium battery, characterized in that, include: 1-Methylpyrrolidine and n-butane bromide are reacted in an inert atmosphere to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid; the molar ratio of 1-methylpyrrolidine to n-butane bromide is 1:(1~3). The ionic liquid 1-methyl-1-butylpyrrolidine bromide and lithium difluoromethanesulfonylimide were reacted in a first organic solvent to obtain the ionic liquid 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt; the molar ratio of the ionic liquid 1-methyl-1-butylpyrrolidine bromide to lithium difluoromethanesulfonylimide was 1:(1~3). A precursor solution was prepared by uniformly mixing 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, polyethylene glycol methyl ether methacrylate, acrylonitrile, lithium bis(trifluoromethanesulfonylimide), divinylbenzene and benzoin ether. The precursor solution was coated and then cured with ultraviolet light to obtain a pyrrole-based ionic liquid polymer electrolyte membrane.

2. The method for preparing the pyrrole polymer electrolyte membrane in the energy storage lithium battery according to claim 1, characterized in that, The process of reacting 1-methylpyrrolidine and n-butane bromide in an inert atmosphere to obtain a 1-methyl-1-butylpyrrolidine bromide ionic liquid is as follows: 1-Methylpyrrolidine and n-butane bromide were stirred in an inert atmosphere at 24-26 °C for 2-3 h to obtain crude 1-methyl-1-butylpyrrolidine bromide ionic liquid. The crude 1-methyl-1-butylpyrrolidine bromide ionic liquid was washed with a second organic solvent at 0-5 °C to obtain 1-methyl-1-butylpyrrolidine bromide ionic liquid. The second organic solvent includes ethyl acetate and anhydrous diethyl ether.

3. The method for preparing the pyrrole polymer electrolyte membrane in the energy storage lithium battery according to claim 1, characterized in that, The first organic solvent includes one or more of anhydrous methanol, anhydrous ethanol, or isopropanol.

4. The method for preparing the pyrrole polymer electrolyte membrane in the energy storage lithium battery according to claim 1, characterized in that, The step of reacting the 1-methyl-1-butylpyrrolidine bromide ionic liquid with lithium difluoromethanesulfonylimide in a first organic solvent to obtain the 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid is as follows: The ionic liquid of 1-methyl-1-butylpyrrolidine bromide was reacted with lithium difluoromethanesulfonylimide in a first organic solvent for 2-3 h. After the reaction, the mixture was extracted to obtain the crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid. The crude product 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid was washed with a third organic solvent. After washing, the product was dried in a vacuum environment at 60-70 °C for 20-24 h to obtain the ionic liquid 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt. The third organic solvent is liquid diethyl ether.

5. The method for preparing the pyrrole polymer electrolyte membrane in the energy storage lithium battery according to claim 1, characterized in that, The mass ratio of the 1-methyl-1-butylpyrrolidine difluoromethanesulfonylimide salt ionic liquid, polyethylene glycol methyl ether methacrylate, acrylonitrile, lithium bis(trifluoromethanesulfonylimide), divinylbenzene, and benzoin ether is (30~60): (35~50): (35~50): (25~40): (5-10): (3~5).

6. The method for preparing the pyrrole polymer electrolyte membrane in the energy storage lithium battery according to claim 1, characterized in that, The ultraviolet curing process specifically involves: The wavelength of the ultraviolet light used is 200~260 μm; First, irradiate with pulsed ultraviolet light for 10-15 minutes, then irradiate continuously with ultraviolet light for 25-30 minutes.

7. A pyrrole polymer electrolyte membrane for an energy storage lithium battery, characterized in that, The pyrrole polymer electrolyte membrane in the energy storage lithium battery is prepared by the method according to any one of claims 1-6, and the structural formula of the pyrrole ionic liquid in the pyrrole ionic liquid polymer electrolyte membrane is shown below: Among them, FSI - It is a bis(fluoromethanesulfonyl)imide anion.

8. An application of a pyrrole polymer electrolyte membrane in an energy storage lithium battery according to claim 7, characterized in that, The pyrrole-based ionic liquid polymer electrolyte membrane is used to prepare semi-solid lithium batteries.

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