Self-repairing MOF ionic liquid quasi-solid electrolyte membrane suitable for black start of energy storage coupled combustion engine and preparation method and application thereof

Abstract

This disclosure provides a self-healing MOF ionic liquid quasi-solid-state electrolyte membrane adapted for black start of energy storage coupled gas turbines, its preparation method, and its application. The preparation method includes obtaining polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds; obtaining ESBI zwitterionic liquid; obtaining amino-modified NH2-Zr-MOF-808; dispersing the amino-modified NH2-Zr-MOF-808 in a first solvent; adding ESBI zwitterionic liquid; and obtaining ESBI@NH2-Zr-MOF-808 through water bath reaction, centrifugation, washing, and drying. A second solvent was added to propylene oxide-b-polytrimethylene carbonate, and the mixture was stirred and dispersed to obtain a block copolymer base solution. A mixture of ESBI zwitterionic liquid and LiTFSI was added to the block copolymer base solution and stirred to form [LiTFSI][ESBI] ionic liquid. ESBI@NH2-Zr-MOF-808 and DTT were added and dispersed and stirred to obtain a composite precursor solution. The composite precursor solution was subjected to evaporation, hot pressing, and cooling treatment. The membrane was immersed in LiTFSI / dimethyl carbonate solution and dried to obtain a self-healing quasi-solid electrolyte membrane.

Description

Technical Field

[0001] This disclosure belongs to the field of black start technology for energy storage coupled gas turbines, specifically relating to a self-healing MOF ionic liquid quasi-solid electrolyte membrane adapted for black start of energy storage coupled gas turbines, its preparation method, and its application. Background Technology

[0002] Thermal power energy storage frequency regulation is one of the core technologies for smoothing load fluctuations and improving the efficiency of thermal power generation in the current power system. Its core requirements for energy storage devices are "high power response speed, long cycle life, wide temperature adaptability, and high safety performance." Currently, thermal power energy storage frequency regulation mostly uses liquid electrolyte lithium batteries. However, liquid electrolytes have problems such as leakage, flammability, and poor electrode interface stability during cycling. During frequency regulation, the energy storage device needs frequent charging and discharging. Liquid electrolytes are prone to a surge in interface impedance due to uneven ion transport, thus reducing the frequency regulation response speed. Simultaneously, frequent power fluctuations exacerbate electrode volume changes, and liquid electrolytes cannot alleviate interface stress, resulting in a capacity retention rate often below 80% after 1000 cycles, making it difficult to meet the "≥5000 cycles" lifespan requirement for thermal power energy storage frequency regulation.

[0003] Quasi-solid polymer electrolytes have become a key direction for replacing liquid electrolytes due to their lack of leakage risk and excellent thermal stability. However, existing quasi-solid electrolytes still face three major bottlenecks: First, it is difficult to balance ionic conductivity and mechanical strength. Traditional polymers (such as PEO and PVDF) either have low ionic conductivity (<1×10⁻⁶) or... -3 S cm -1 First, they have several drawbacks. First, they lack sufficient mechanical strength (tensile strength < 10 MPa), making them unsuitable for the high-power charging and discharging of thermal power plants with frequency regulation. Second, they have poor interface stability. Conventional ionic liquid-based electrolytes are prone to exacerbating side reactions at the electrode-electrolyte interface due to ionic liquid leakage, leading to a continuous increase in interface impedance and a gradual decrease in response speed during frequency regulation. Third, they lack self-healing capabilities. Frequent power fluctuations during thermal power plant frequency regulation can cause microcracks in the electrolyte film, which traditional quasi-solid-state electrolytes cannot repair, ultimately leading to battery failure.

[0004] Furthermore, existing quasi-solid-state electrolyte preparation processes mostly rely on high-temperature, high-pressure equipment or toxic solvents, resulting in high production costs. Moreover, their thermal decomposition temperatures are mostly below 300℃, posing safety hazards in outdoor operating conditions of thermal power energy storage (where summer ambient temperatures can reach above 40℃). Therefore, developing a quasi-solid-state polymer electrolyte that simultaneously possesses "high ion conductivity, high mechanical strength, self-healing function, and high interfacial stability" is a key technological requirement for adapting to frequency regulation scenarios in thermal power energy storage. Summary of the Invention

[0005] This disclosure aims to at least address the shortcomings of existing quasi-solid polymer electrolytes, such as difficulty in balancing "ion conduction-mechanical strength-self-healing performance," poor interface stability, and insufficient thermal safety, and provides a self-healing MOF ionic liquid quasi-solid electrolyte membrane adapted for black start of energy storage coupled gas turbines, its preparation method, and its application.

[0006] One aspect of this disclosure provides a method for preparing a self-healing MOF ionic liquid quasi-solid-state electrolyte membrane adapted for black start of energy storage coupled gas turbines, the preparation method comprising: S110, Obtain polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds; S120, Obtain ESBI zwitterionic liquid; S130. Obtain amino-modified NH2-Zr-MOF-808, disperse the amino-modified NH2-Zr-MOF-808 in a first solvent, add the ESBI zwitterionic liquid, and after water bath reaction, centrifugation, washing and drying, obtain dual-functionalized ESBI@NH2-Zr-MOF-808. S140. Add a second solvent to the polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds, and stir to disperse to obtain a block copolymer base solution. S150. Add the mixture of ESBI zwitterionic liquid and LiTFSI to the block copolymer base solution, stir to form [LiTFSI][ESBI] ionic liquid, and add ESBI@NH2-Zr-MOF-808 and DTT, disperse and stir to obtain a composite precursor solution. S160. The composite precursor solution is subjected to evaporation, hot pressing, and cooling treatment. The preliminarily formed membrane is then immersed in a LiTFSI / dimethyl carbonate solution and dried to obtain a self-healing quasi-solid electrolyte membrane.

[0007] Optionally, the disulfide-containing polypropylene carbonate-b-polytrimethylene carbonate is formed using the following method: An initiator was added to PPC prepolymer and PTMC prepolymer, and the mixture was stirred at 80~100℃ for 4~6 hours to obtain PPC-b-PTMC block copolymer. A disulfide monomer was added to the PPC-b-PTMC block copolymer, the temperature was raised to 100-120℃, and the reaction was continued for 3-5 hours. The disulfide monomer was grafted onto the block copolymer segments through transesterification. After the reaction was completed, the product was cooled to room temperature. The product was dissolved in ultra-dry THF, and then anhydrous ethanol was added for precipitation. The collected precipitate was dried to obtain polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds.

[0008] Optionally, the ESBI zwitterionic liquid is formed using the following method: A solvent was added to 1-vinyl-3-methylimidazolium bromide and 1,4-butane sulfonyl lactone, and the mixture was stirred at 50-70°C for 8-12 h to obtain a 3-(1-vinyl-3-imidazolium) sulfonate intermediate. Epichlorohydrin and an alkaline catalyst were added to the 3-(1-vinyl-3-imidazolium)sulfonate intermediate, and the temperature was raised to 60-80°C. The reaction was continued for 6-10 hours to induce epoxidation of the vinyl group. After the reaction was completed, the mixture was filtered, and the filtrate was concentrated by rotary evaporation, precipitated, collected by centrifugation, and dried to obtain ESBI zwitterionic liquid.

[0009] Optionally, the amino-modified NH2-Zr-MOF-808 is formed using the following method: ZrOCl2 8H2O and 2-aminoterephthalic acid were dissolved in a DMF-formic acid mixed solvent and stirred to form a homogeneous suspension. The mixture was then subjected to a constant temperature solvothermal reaction at 110~130℃ for 20~28h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The reaction solution was centrifuged and the bottom precipitate was collected. The precipitate was washed and dried to obtain amino-modified NH2-Zr-MOF-808.

[0010] Optionally, in step S130, the content of the amino-modified NH2-Zr-MOF-808 is 8-12 parts by mass; The first solvent is ultra-dry DMSO, with a content of 250-350 parts by weight; The content of the ESBI zwitterionic liquid is 4-8 parts by mass; The water bath reaction temperature is 70~90℃, the stirring speed is 200~300r / min, and the reaction time is 6~10h; The drying process is carried out at a temperature of 50-70°C for 10-14 hours.

[0011] Optionally, in step S140, the content of the disulfide-containing polypropylene carbonate-b-polytrimethylene carbonate is 50-70 parts by weight. The second solvent is ultra-dry THF, with a content of 350-450 parts by weight; The stirring and dispersion treatment is carried out at a speed of 250~350 r / min for 1.5-2.5 h, and ultrasonic-assisted dispersion is performed for 3-7 min every 30 min.

[0012] Optionally, in step S150, the content of the ESBI zwitterionic liquid is 30-50 parts by mass; The mixture content of LiTFSI is 20-32 parts by weight; The content of ESBI@NH2-Zr-MOF-808 is 8-18 parts by weight; The DTT content is 0.3-0.9 parts by weight.

[0013] Optionally, in step S160, the hot pressing temperature is 50~70℃, the pressure is 4~8MPa, and the hot pressing time is 10~20min; The drying process is carried out at a temperature of 50~70℃ for 1.5-2.5 hours. The thickness of the self-healing quasi-solid electrolyte membrane is 80~100μm.

[0014] In another aspect of this disclosure, a self-healing MOF ionic liquid quasi-solid electrolyte membrane adapted for black start of energy storage coupled gas turbines is proposed, wherein the self-healing MOF ionic liquid quasi-solid electrolyte membrane adapted for black start of energy storage coupled gas turbines is prepared by the method described above.

[0015] Another aspect of this disclosure proposes an application of a self-healing MOF ionic liquid quasi-solid electrolyte membrane adapted for black start of energy storage coupled gas turbines. The self-healing MOF ionic liquid quasi-solid electrolyte membrane described above is applied to a flexible lithium battery system in a thermal power energy storage frequency regulation scenario.

[0016] This disclosure presents a self-healing MOF ionic liquid quasi-solid-state electrolyte membrane adapted for black start of energy storage coupled gas turbines, its preparation method, and its application. Compared with the prior art, it has the following advantages: Firstly, traditional quasi-solid electrolytes often use single-segment polymers (such as PEO and PVDF), which easily lead to the contradiction of "high conductivity but low strength" due to the single function of the segments. In this invention, the PPC-b-PTMC-gSS block copolymer provides flexibility through the PPC segment, enhances oxidation resistance through the PTMC segment, and achieves dynamic cross-linking through disulfide bonds. At the same time, the disulfide bonds can undergo "breakage-reorganization" under DTT catalysis, which not only ensures the mechanical strength of the membrane (tensile strength up to 14.8 MPa) but also endows it with self-healing function. When cracks appear in the membrane, the disulfide bonds can quickly reorganize and repair the interface, avoiding the interruption of ion transport. Mechanistically, it achieves a balance of "flexibility-strength-self-healing" and the structure-performance synergy of the dynamically cross-linked block copolymer, breaking through the performance bottleneck of traditional single polymers.

[0017] Secondly, addressing the issue of increased interfacial impedance due to ionic liquid leakage in traditional ionic liquid-based electrolytes, this invention utilizes a customized [LiTFSI][ESBI] ionic liquid that covalently bonds epoxy groups to amino groups on the MOF surface. This not only prevents ionic liquid migration and leakage but also regulates the Li content through the MOF pore confinement effect. +Transport path; at the same time, the sulfonic acid group of ESBI can provide additional ion sites, forming a "dual ion conduction network" with the carboxyl group of MOF, which increases the lithium ion transference number to 0.76, much higher than the 0.5~0.6 of conventional systems. Mechanistically, it achieves the synergy of "high ion conduction-low interfacial impedance-long cycle stability", breaking through the bottleneck of ion transport and interfacial stability of traditional electrolytes.

[0018] Thirdly, addressing the issue that some existing electrolyte processes rely on high-temperature, high-pressure equipment or toxic solvents and have insufficient thermal stability, the raw materials used in this invention are all conventional industrial reagents. The solvents THF and DMSO can be recovered by rotary evaporation, and the decomposition products of the composite sulfurizing agent have no toxic residues. At the same time, the process parameters are mild, requiring no special equipment, and the "thermal barrier" effect of the functionalized MOF raises the electrolyte thermal decomposition temperature to 385°C, far exceeding the traditional electrolyte's temperature below 300°C. This reduces energy consumption and safety risks from a mechanistic perspective, making it more suitable for the large-scale production of flexible lithium batteries, and significantly improving both economy and safety. Attached Figure Description

[0019] Figure 1 The flowchart is a specific embodiment of the preparation method of a self-healing MOF / ionic liquid quasi-solid electrolyte membrane containing disulfide block copolymers according to the present disclosure. Figure 2 The impedance spectra of Embodiments 1, 12 and Comparative Example 2 of this disclosure are shown below; Figure 3 This is a polarization curve diagram of Embodiment 12 of this disclosure; Figure 4 The impedance spectra before and after polarization in Embodiment 12 of this disclosure are shown. Figure 5 This is a capacity decay diagram for 200 cycles of Embodiment 12 and Comparative Example 3 of this disclosure. Detailed Implementation

[0020] To enable those skilled in the art to better understand the technical solutions of this disclosure, the disclosure will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain this disclosure and represent a part of the embodiments of this disclosure, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this disclosure without creative effort are within the protection scope of this disclosure.

[0021] As shown in Figure 1, one aspect of this disclosure provides a method for preparing a self-healing MOF ionic liquid quasi-solid-state electrolyte membrane adapted for black start of energy storage coupled gas turbines, specifically including the following steps S110~S160: S110, Obtain polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds.

[0022] In step S110, the disulfide-containing polypropylene carbonate-b-polytrimethylene carbonate (PPC-b-PTMC-gSS) is prepared by the following method: Weigh 40-60 parts by mass of polypropylene carbonate prepolymer (PPC prepolymer) and 40-60 parts by mass of polytrimethylene carbonate prepolymer (PTMC) and place them in an argon-protected three-necked flask. Add 0.1-0.3 parts of initiator, heat to 80-100℃, and stir for 4-6 hours to obtain PPC-b-PTMC block copolymer. Then add 5-10 parts of disulfide monomer, heat to 100-120℃, and continue the reaction for 3-5 hours to graft the disulfide monomer onto the block copolymer segments via transesterification. After the reaction is complete, cool to room temperature and dissolve the product in 100-150 parts of ultra-dry tetrahydrofuran (ultra-dry THF). Then slowly add the product dropwise to 300-400 parts of anhydrous ethanol to precipitate. Filter and collect the precipitate, and vacuum dry at 50-70℃ for 12-16 hours to obtain PPC-b-PTMC-gSS, which is then sealed and stored in an argon-protected glove box.

[0023] In some preferred embodiments, the PPC prepolymer is used as a component of the polymer backbone to synthesize the PPC-b-PTMC block copolymer. The PPC segments have good flexibility and certain ion conductivity, making them a scaffold material for constructing the quasi-solid electrolyte matrix.

[0024] In some preferred embodiments, PTMC prepolymer reacts with PPC prepolymer to form PPC-b-PTMC block copolymer, and the PTMC segments typically have good mechanical properties and biocompatibility. Their introduction can regulate the mechanical properties and crystallinity of the copolymer, which helps to form a more stable electrolyte membrane structure.

[0025] In some preferred embodiments, the initiator may be stannous octoate.

[0026] In some preferred embodiments, the content of PPC prepolymer is preferably 50 parts by mass, the content of PTMC prepolymer is preferably 50 parts by mass, the content of initiator is preferably 0.2 parts by mass, and the content of disulfide monomer is preferably 8 parts by mass. Of course, in other embodiments, the above components may be selected in other parts by mass, and there is no specific limitation on this.

[0027] In some preferred embodiments, the ratio of PPC to PTMC in the prepared disulfide block copolymer (PPC-b-PTMC-gSS) is 5:5-7:3, and the number-average molecular weight is 8000-15000. That is, by adjusting the ratio of PPC and PTMC blocks, the crystallinity, flexibility, and ion transport capacity of the polymer can be precisely controlled. Simultaneously, the PPC segments provide flexibility and the polarity of the CO2 groups, which helps dissolve lithium salts, while the PTMC segments provide good mechanical strength and hydrophobicity, improving dimensional stability. Furthermore, the above molecular weight range ensures that the polymer segments have sufficient length to form an effective crosslinking network and mechanical strength, while avoiding difficulties in melt or solution processing due to excessively high molecular weight.

[0028] It should be noted that this embodiment introduces disulfide bonds, which endow the material with intrinsic self-healing ability. When the material develops microcracks due to stress or damage, the disulfide bonds can undergo dynamic exchange under mild conditions, thereby achieving autonomous healing of the cracks.

[0029] In step S110, PPC-b-PTMC block copolymers are first synthesized, and then disulfide monomers are grafted onto them via ester exchange, thereby achieving molecular-level structural design and functionalization.

[0030] S120, Obtain ESBI zwitterionic liquid.

[0031] In step S120, 1-(2-epoxyethyl)-3-(4-sulfonate butyl)imidazolium (ESBI) is prepared by the following method: Weigh 30-40 parts by mass of 1-vinyl-3-methylimidazolium bromide and 25-35 parts by mass of 1,4-butane sulfonyl lactone into a 250 mL three-necked flask, add 80-120 parts by mass of anhydrous ethanol as solvent, and stir at 50-70 °C for 8-12 h to obtain 3-(1-vinyl-3-imidazolium) sulfonate intermediate; after cooling to room temperature, add 15-25 parts by mass of epichlorohydrin and 3-5 parts by mass of alkaline catalyst, heat to 60-80 °C, and continue the reaction for 6-10 h to induce epoxidation of vinyl groups; after the reaction is complete, filter to remove solid impurities, concentrate the filtrate by rotary evaporation to 1 / 3-1 / 2 of the original volume, then add 200-300 parts by mass of anhydrous diethyl ether to precipitate, collect the precipitate by centrifugation, and dry under vacuum at 60-80 °C for 10-14 h to obtain ESBI zwitterionic liquid, which is then sealed and stored for later use.

[0032] In some preferred embodiments, the alkaline catalyst is preferably sodium hydroxide.

[0033] In some preferred embodiments, the content of 1-vinyl-3-methylimidazolium bromide is preferably 35 parts by weight, the content of 1,4-butanesulfonyl lactone is preferably 30 parts by weight, the content of anhydrous ethanol is preferably 100 parts by weight, the content of epichlorohydrin is preferably 20 parts by weight, and the content of alkaline catalyst is preferably 4 parts by weight.

[0034] In this embodiment, a zwitterionic liquid was prepared, which has a zwitterionic structure with positive and negative charge centers and can react with Li. + The formation of strong ion pairs / complexes helps to promote Li + The dissociation and migration of ions improve ionic conductivity and lithium-ion transference number.

[0035] In step S120, ESBI with epoxy group and sulfonic acid inner salt structure was synthesized, laying the foundation for its grafting with MOF and its complexation with lithium salt.

[0036] S130. Obtain amino-modified NH2-Zr-MOF-808, disperse the amino-modified NH2-Zr-MOF-808 in a first solvent, add the ESBI zwitterionic liquid, and after water bath reaction, centrifugation, washing and drying, obtain dual-functionalized ESBI@NH2-Zr-MOF-808.

[0037] It should be noted that in step S130, the MOF is first modified with amino groups to provide reaction sites for subsequent grafting. Then, zwitterionic liquid grafting modification is performed. Through the reaction of epoxy groups and amino groups, zwitterionic liquid is covalently grafted onto the MOF surface. This makes the MOF not only have traditional Lewis acidic Zr nodes (which can fix anions and increase the lithium ion transference number), but its surface is also covered with an ionic liquid layer, forming a fast ion channel inside the MOF and an interface with excellent compatibility with the polymer matrix / ionic liquid electrolyte.

[0038] In step S130, amino-modified NH2-Zr-MOF-808 is prepared by the following method: Weigh out 15-25 parts of ZrOCl2 by weight. 8H2O and 14-22 parts of 2-aminoterephthalic acid were dissolved in 400-600 parts of a DMF-formic acid mixed solvent (volume ratio of 3:1-5:1). After stirring to form a homogeneous suspension, the mixture was transferred to a polytetrafluoroethylene-lined reactor, sealed, and placed in a forced-air drying oven for a constant-temperature solvothermal reaction at 110-130℃ for 20-28 hours. After the reaction was completed, the mixture was naturally cooled to room temperature, and the reaction solution was transferred to a centrifuge tube. The precipitate was collected by centrifugation at 3500-4500 r / min for 12-18 min. The precipitate was washed three times with DMF and twice with anhydrous ethanol (centrifuged after each wash). The precipitate was then placed in a vacuum drying oven and dried at 50-70℃ for 10-14 hours to obtain amino-modified NH2-Zr-MOF-808.

[0039] In some preferred embodiments, ZrOCl2 The content of 8H2O is preferably 20 parts by mass, the content of 2-aminoterephthalic acid is preferably 18 parts by mass, and the content of the mixed solvent is preferably 500 parts by mass.

[0040] Further, 8-12 parts of the above NH2-Zr-MOF-808 were dispersed in 250-350 parts of ultra-dry DMSO, and 4-8 parts of ESBI were added. The mixture was reacted for 6-10 hours under the conditions of a water bath at 70-90℃ and magnetic stirring at 200-300 r / min, so that the epoxy group of ESBI could undergo an addition reaction with the amino group on the surface of MOF, thereby achieving covalent anchoring of the zwitterionic liquid. After the reaction, the precipitate was separated by centrifugation again, washed twice with DMSO and once with ultra-dry THF, and vacuum dried at 50-70℃ for 10-14 hours to obtain the dual-functionalized ESBI@NH2-Zr-MOF-808, which was then sealed and stored in an argon glove box.

[0041] In some preferred embodiments, the content of NH2-Zr-MOF-808 is preferably 10 parts by mass, and the content of ESBI is preferably 6 parts by mass.

[0042] In step S130, NH2-Zr-MOF-808 is directly synthesized, with the amino group as part of the MOF skeleton. In addition, the zwitterionic liquid is chemically bonded and anchored on the MOF surface through a ring-opening addition reaction to form a stable multifunctional composite filler.

[0043] S140. Add a second solvent to the polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds, and stir to disperse, to obtain a block copolymer base solution.

[0044] In step S140, 50-70 parts by mass of the PPC-b-PTMC-gSS prepared in step S110 are weighed and placed in a three-necked flask under argon protection. 350-450 parts of ultra-dry THF are added, and the mixture is magnetically stirred at 250-350 r / min at room temperature for 1.5-2.5 h. During this period, ultrasonic dispersion is performed for 3-7 min every 30 min (power 180-220 W) to ensure that the copolymer is completely dissolved and the solution is homogeneous and transparent, thus obtaining the block copolymer base solution, which is then transferred to an argon glove box for later use.

[0045] In some preferred embodiments, the content of PPC-b-PTMC-gSS is preferably 60 parts by weight, and the content of THF is preferably 400 parts by weight.

[0046] S150. Add the mixture of ESBI zwitterionic liquid and LiTFSI to the block copolymer base solution, stir to form [LiTFSI][ESBI] ionic liquid, and add ESBI@NH2-Zr-MOF-808 and dithiothreitol (DTT), disperse and stir to obtain a composite precursor solution.

[0047] In step S150, in an argon glove box, a mixture of 30-50 parts ESBI and 20-32 parts LiTFSI is slowly added to the block copolymer base solution and magnetically stirred at 200-300 r / min for 6-10 h to allow ESBI and LiTFSI to fully compound and form [LiTFSI][ESBI] ionic liquid. Then, 8-18 parts ESBI@NH2-Zr-MOF-808 and 0.3-0.9 parts DTT are added. The mixture is first ultrasonically dispersed for 15-25 min (power 220-280 W) to break up MOF agglomeration, and then stirred for another 6-10 h to allow MOF to form multiple interactions with the polymer matrix and ionic liquid, ultimately obtaining a homogeneous composite precursor solution without obvious particles.

[0048] In some preferred embodiments, the mass ratio of ESBI to LiTFSI is preferably 1.2:1 to 1.8:1. At this ratio, the molar concentration of LiTFSI is at a relatively high level, providing sufficient Li + Charge carriers, and simultaneously, excess ESBI (sulfonate groups) can react with Li + This forms appropriate coordination, promotes the dissociation of LiTFSI, and reduces the number of tight ion pairs (Li). + TFSI - The formation of Li+ increases lithium-ion conductivity and lithium-ion transference number; that is, under appropriate ratios, Li+... + It can be used with one ESBI molecule and one or more TFSIs - Anions form dynamic complexes with diverse coordination structures.

[0049] In some preferred embodiments, the content of ESBI is preferably 40 parts by mass, the content of LiTFSI is preferably 26 parts by mass, the content of ESBI@NH2-Zr-MOF-808 is preferably 12 parts by mass, and the content of DTT is preferably 0.5 parts by mass.

[0050] In step S150, the dynamic polymer solution, the self-synthesized ionic liquid electrolyte, and the dual-functionalized MOF are combined, and the DTT reducing agent is added to achieve homogeneous mixing of the ionic conductor (ESBI / LiTFSI), the structural framework (polymer / MOF), and the dynamic bond activator (DTT).

[0051] S160. The composite precursor solution is subjected to evaporation, hot pressing, and cooling treatment. The preliminarily formed membrane is then immersed in a LiTFSI / dimethyl carbonate solution and dried to obtain a self-healing quasi-solid electrolyte membrane.

[0052] In step S160, the composite precursor solution is uniformly cast into a polytetrafluoroethylene mold in an argon-filled glove box and allowed to stand at room temperature for 6-10 hours to evaporate THF until the solution reaches a semi-dry gel state. The mold is then transferred to a hot press molding machine, set to a temperature of 50-70°C and a pressure of 4-8 MPa, and hot-pressed for 10-20 minutes to promote dynamic cross-linking of the disulfide bonds in the copolymer segments and simultaneously strengthen the interfacial bonding between the MOF and the polymer matrix. After hot pressing, the membrane is naturally cooled to room temperature, and the preliminarily formed membrane is immersed in a 0.08-0.12 mol / L LiTFSI / dimethyl carbonate solution for 3-8 minutes to activate the self-healing active sites of the disulfide bonds. Finally, the membrane is removed, placed in a vacuum drying oven, and dried at 50-70°C for 1.5-2.5 hours to remove residual solvent, yielding a self-healing quasi-solid electrolyte membrane, which is then sealed and stored in an argon-filled glove box.

[0053] In some preferred embodiments, the composite precursor solution is uniformly cast into a polytetrafluoroethylene mold, and the room temperature evaporation time is preferably 8 hours, the hot pressing temperature is preferably 60°C, the pressure is preferably 6 MPa, the hot pressing time is preferably 15 minutes, the activation time is preferably 5 minutes, the drying temperature is preferably 60°C, and the drying time is preferably 2 hours.

[0054] In some preferred embodiments, the thickness of the self-healing quasi-solid electrolyte film is 80~100μm.

[0055] In step S160, a gel-state network is initially formed to prevent component segregation. Then, at a lower temperature, heat and pressure are used to promote the dynamic exchange and recombination of disulfide bonds, thereby achieving dynamic cross-linking of polymer chains. At the same time, the interfacial bonding between MOF and polymer is enhanced. Furthermore, the dynamic exchange reaction of disulfide bonds / thiol groups is chemically activated, enabling the cross-linked network to have responsiveness to external stimuli (such as mechanical damage) and self-healing ability.

[0056] In the preparation process disclosed herein, a dynamic crosslinked block copolymer of polypropylene carbonate-b-polytrimethylene carbonate (PPC-b-PTMC-gSS) containing disulfide bonds is first prepared. Then, a dual-functionalized ESBI@NH2-Zr-MOF-808 is prepared by "amino modification + zwitterionic liquid grafting". Finally, the block copolymer, customized [LiTFSI][ESBI] ionic liquid and functionalized MOF are combined by "composite dispersion-dynamic crosslinking-hot pressing film formation" process to obtain a quasi-solid electrolyte membrane.

[0057] Another aspect of this disclosure proposes a self-healing MOF / ionic liquid quasi-solid electrolyte membrane adapted for black start of energy storage coupled gas turbines. This self-healing MOF / ionic liquid quasi-solid electrolyte membrane is prepared by the method described above. For details, please refer to the above description and it will not be repeated here.

[0058] Another aspect of this disclosure proposes an application of a self-healing MOF / ionic liquid quasi-solid electrolyte membrane adapted for black start of energy storage coupled gas turbines. The self-healing MOF / ionic liquid quasi-solid electrolyte membrane described above is applied to a flexible lithium battery system in a thermal power energy storage frequency regulation scenario.

[0059] The preparation method of the self-healing MOF / ionic liquid quasi-solid electrolyte membrane containing disulfide block copolymers will be further explained below with reference to specific embodiments: Example 1 Step 1: Preparation of polypropylene carbonate-b-polytrimethylene carbonate (PPC-b-PTMC-gSS) containing disulfide bonds: Weigh 50 parts by mass of PPC prepolymer and 50 parts by mass of PTMC prepolymer into a three-necked flask under argon protection. Add 0.2 parts by mass of stannous octoate as an initiator, heat to 90°C, and stir for 56 h to obtain PPC-b-PTMC block copolymer. Then add 8 parts by mass of disulfide monomer, heat to 110°C, and continue to react for 4 h to graft the disulfide monomer onto the block copolymer segments via transesterification. After the reaction is completed, cool to room temperature, dissolve the product in 120 parts by mass of ultra-dry THF, and then slowly add it dropwise to 350 parts by mass of anhydrous ethanol to precipitate. Filter and collect the precipitate, and dry it under vacuum at 60°C for 14 h to obtain PPC-b-PTMC-gSS (PPC:PTMC=6:4, number average molecular weight of 12000), which is then sealed and stored in an argon glove box.

[0060] Step 2: Preparation of 1-(2-epoxyethyl)-3-(4-sulfonate butyl)imidazolium (ESBI): Weigh 35 parts by mass of 1-vinyl-3-methylimidazolium bromide and 30 parts by mass of 1,4-butane sulfonyl lactone into a 250 mL three-necked flask, add 100 parts by mass of anhydrous ethanol as solvent, and stir at 60 °C for 12 h to obtain 3-(1-vinyl-3-imidazolium) sulfonate intermediate; after cooling to room temperature, add 20 parts by mass of epichlorohydrin and 4 parts by mass of sodium hydroxide as alkaline catalyst, heat to 70 °C, and continue the reaction for 8 h to induce epoxidation of vinyl groups; after the reaction is complete, filter to remove solid impurities, concentrate the filtrate to 1 / 3 of its original volume by rotary evaporation, then add 250 parts by mass of anhydrous diethyl ether to precipitate, collect the precipitate by centrifugation, and dry under vacuum at 70 °C for 12 h to obtain ESBI zwitterionic liquid, which is sealed and stored for later use.

[0061] Step 3: Dual-functionalization modification of MOFs First, amino modification of the MOF is performed according to parts by weight. Weigh 20 parts of ZrOCl2. 8H₂O and 18 parts of 2-aminoterephthalic acid were dissolved in 500 parts of a DMF-formic acid mixed solvent (volume ratio 4:1). After stirring to form a homogeneous suspension, the solution was transferred to a polytetrafluoroethylene-lined reactor, sealed, and placed in a forced-air drying oven for a solvothermal reaction at 120℃ for 24 h. After the reaction, the solution was allowed to cool naturally to room temperature, transferred to centrifuge tubes, and centrifuged at 4000 r / min for 15 min to collect the bottom precipitate. The precipitate was washed three times with DMF and twice with anhydrous ethanol (centrifuged after each wash). The precipitate was then placed in a vacuum drying oven and dried at 60℃ for 12 h to obtain amino-modified NH₂-Zr- MOF-808 was then modified by zwitterionic liquid grafting: 10 parts of the above NH2-Zr-MOF-808 were dispersed in 300 parts of ultra-dry DMSO, and 6 parts of ESBI were added. The mixture was reacted for 8 hours under the conditions of 80℃ water bath and 250r / min magnetic stirring, so that the epoxy group of ESBI could undergo an addition reaction with the amino group on the surface of MOF, thereby achieving covalent anchoring of zwitterionic liquid. After the reaction, the precipitate was separated by centrifugation again, washed twice with DMSO and once with ultra-dry THF, and vacuum dried at 60℃ for 12 hours to obtain dual-functionalized ESBI@NH2-Zr-MOF-808, which was sealed and stored in an argon glove box.

[0062] Step 4: Preparation of block copolymer solution Weigh 60 parts by mass of the PPC-b-PTMC-gSS prepared in step 1 and place it in a three-necked flask under argon protection. Add 400 parts of ultra-dry THF and stir magnetically at 300 r / min for 2 h at room temperature. During this period, ultrasonically assist dispersion for 5 min every 30 min (power 200 W) to ensure that the copolymer is completely dissolved and the solution is uniform and transparent. The block copolymer base solution is then transferred to an argon glove box for later use.

[0063] Step 5: Preparation of the composite precursor solution Inside an argon glove box, 40 parts of a mixture of ESBI and 26 parts of LiTFSI prepared in step 2 were slowly added to the block copolymer base solution prepared in step 4. The mixture was magnetically stirred at 250 r / min for 8 h to allow ESBI and LiTFSI to fully combine and form a [LiTFSI][ESBI] ionic liquid. Subsequently, 12 parts of ESBI@NH2-Zr-MOF-808 prepared in step 3 and 0.5 parts of DTT were added. The mixture was first ultrasonically dispersed for 20 min (power 250 W) to break up MOF agglomeration, and then stirred for another 8 h to allow MOF to form multiple interactions with the polymer matrix and ionic liquid, ultimately resulting in a homogeneous composite precursor solution without obvious particles.

[0064] Step 6: Dynamic cross-linking film formation and self-repair activation Inside an argon-filled glove box, the composite precursor solution was uniformly cast into a polytetrafluoroethylene mold and allowed to stand at room temperature for 8 hours to evaporate THF until the solution reached a semi-dry gel state. The mold was then transferred to a hot press molding machine, set to 60°C and 6 MPa, and hot-pressed for 15 minutes to promote dynamic cross-linking of the disulfide bonds in the copolymer segments, while simultaneously strengthening the interfacial bonding between the MOF and the polymer matrix. After hot pressing, the membrane was naturally cooled to room temperature, and the preliminarily formed membrane was immersed in a 0.1 mol / L LiTFSI / dimethyl carbonate solution for 5 minutes to activate the self-healing active sites of the disulfide bonds. Finally, the membrane was removed, placed in a vacuum drying oven, and dried at 60°C for 2 hours to remove residual solvent, yielding a 90 μm thick self-healing quasi-solid electrolyte membrane, which was then sealed and stored in an argon-filled glove box.

[0065] Example 2 The preparation method of this example is the same as that of Example 1, except that the amount of MOF used in this example has been optimized and the content of ESBI@NH2-Zr-MOF-808 in step 5 has been modified to 8 parts by mass. The other conditions are the same as those in Example 1.

[0066] Example 3 The preparation method of this example is the same as that of Example 1, except that the amount of MOF used in this example has been optimized and the content of ESBI@NH2-Zr-MOF-808 in step 5 has been modified to 18 parts by mass. The other conditions are the same as those in Example 1.

[0067] Example 4 The preparation method of this example is the same as that of Example 1. The difference is that the ratio of ionic liquids has been optimized in this example. The amount of ESBI in step 5 is modified to 30 parts and the amount of LiTFSI to 20 parts, with a mass ratio of 1.5:1. The other conditions are the same as those in Example 1.

[0068] Example 5 The preparation method of this example is the same as that of Example 1. The difference is that the ratio of ionic liquids has been optimized in this example. The amount of ESBI in step 5 is modified to 50 parts and the amount of LiTFSI to 32 parts, with a mass ratio of 1.56:1. The other conditions are the same as those in Example 1.

[0069] Example 6 The preparation method of this example is the same as that of Example 1, except that the amount of dynamic crosslinking agent is optimized and the amount of DTT in step 5 is modified to 0.3 parts by mass. The other conditions are the same as those of Example 1.

[0070] Example 7 The preparation method of this example is the same as that of Example 1, except that the amount of dynamic crosslinking agent is optimized and the amount of DTT in step 5 is modified to 0.9 parts by mass. The other conditions are the same as those of Example 1.

[0071] Example 8 The preparation method of this example is the same as that of Example 1, except that the block copolymer ratio has been optimized in this example. In step 1, 50 parts of PPC prepolymer and 50 parts of PTMC prepolymer are modified, and the PPC:PTMC ratio of PPC to PTMC in the prepared PPC-b-PTMC-gSS is 5:5. The other conditions are the same as those in Example 1.

[0072] Example 9 The preparation method of this example is the same as that of Example 1, except that the block copolymer ratio has been optimized in this example. In step 1, 70 parts of PPC prepolymer and 30 parts of PTMC prepolymer are modified, and the PPC:PTMC ratio of the prepared PPC-b-PTMC-gSS is 7:3. The other conditions are the same as those in Example 1.

[0073] Example 10 The preparation method of this example is the same as that of Example 1. The difference is that the hot pressing process has been optimized in this example. The hot pressing temperature and pressure in step 6 have been modified to 50°C and 4MPa, respectively. The other conditions are the same as those in Example 1.

[0074] Example 11 The preparation method of this example is the same as that of Example 1. The difference is that the hot pressing process has been optimized in this example. The hot pressing temperature and pressure in step 6 have been modified to 70°C and 8MPa, respectively. The other conditions are the same as those in Example 1.

[0075] Example 12 The preparation method in this example is the same as that in Example 1, except that the double lithium salt system has been optimized in this example. In step 5, LiTFSI is replaced with 20 parts LiTFSI + 6 parts LiDFOB, and the other conditions are the same as in Example 1.

[0076] Comparative Example 1 The preparation method of this example is the same as that of Example 1, except that this example uses a conventional block copolymer-based electrolyte, that is, step 1 is omitted, and the PPC-b-PTMC-gSS prepared in step 1 is replaced with an equal number of PEO-b-PCL (PEO:PCL=6:4, number average molecular weight 12000), and the other conditions are the same as those of Example 1.

[0077] Comparative Example 2 The preparation method of this example is the same as that of Example 1, except that the electrolyte of this example is non-functionalized MOF, that is, step 3 is omitted, and ESBI@NH2-Zr-MOF-808 is not added in step 5. The other conditions are the same as those of Example 1.

[0078] Comparative Example 3 The preparation method in this example is the same as that in Example 1, except that the electrolyte of the zwitterionic liquid is not customized in this example. That is, step 2 is omitted and the ESBI prepared in step 2 is replaced with equal parts of [LiTFSI][VIPS] (conventional imidazole propanesulfonate zwitterionic liquid). The other conditions are the same as in Example 1.

[0079] Table 1 Results of each embodiment and comparative example

[0080] The test data in Table 1 indicate that the synergistic effect of functionalized MOF and customized zwitterionic liquid dominates the optimization of ion transport performance. The comparison between Examples 1-3 and Comparative Example 2 shows that the dual functionalization modification of ESBI@NH2-Zr-MOF-808 is the core of improving ionic conductivity and lithium-ion transference number: the pore confinement effect of MOF can regulate ion transport paths and reduce lithium-ion aggregation, while ESBI, through covalent bonding, is anchored on the MOF surface and within the pores, preventing ionic liquid leakage and providing additional ion sites through sulfonic acid groups, thus enhancing lithium transport performance. + This creates a "multi-point synergistic conduction" effect. The lithium-ion transference number in Example 3 reached 0.75, a 29.3% increase compared to Comparative Example 2, precisely because the high amount of MOF constructed a denser confined channel; however, more MOF is not always better. The ionic conductivity of Example 3 (2.1 × 10⁻⁶) was... -3 S cm -1 Slightly lower than Example 1 (2.3 × 10⁻⁶) -3 S cm -1 Excess MOF tends to aggregate, leading to localized ion transport obstruction. The conventional PEO-b-PCL-based electrolyte (Comparative Example 1) has a room temperature ionic conductivity of only 1.5 × 10⁻⁶. - 3 S cm -1 After 1000 cycles, the capacity retention rate was 82.4%. Example 12 used a LiTFSI+LiDFOB dual lithium salt system. The fluorooxide groups of LiDFOB can inhibit Li + The strong interaction with the sulfonic acid group accelerates Li + The desolvation process resulted in an ionic conductivity of 2.6 × 10⁻⁶. -3 S cm -1With a lithium-ion transference number of 0.76 and a capacity retention of 95.1% after 500 cycles, along with a 95% self-healing efficiency and a thermal decomposition temperature of 385℃, it became the optimal ion transport scheme. Comparative Example 3 used conventional [LiTFSI][VIPS]. Because VIPS lacks epoxy groups, it cannot covalently bind with MOF, and the ionic liquid easily migrates, leading to increased interfacial impedance. The ionic conductivity and transference number were both lower than in Example 1, confirming the necessity of the ESBI "bifunctional group (epoxy group + sulfonic acid group)" design.

[0081] Please refer to Table 1. The structural characteristics of the dynamically crosslinked block copolymer determine the mechanical strength, self-healing properties, and thermal stability of the membrane. The comparisons of Examples 1, 6-7, and Comparative Example 1 clearly demonstrate that the dynamic disulfide bonds and block structure of PPC-b-PTMC-gSS achieve a balance between flexibility, strength, and self-healing: the flexible segments of the PPC segment enhance the membrane's extensibility, the rigid structure of the PTMC segment strengthens oxidation resistance and mechanical support, and the disulfide bonds can undergo breakage and recombination under DTT catalysis, thus imparting self-healing functionality. Example 7 exhibits a self-healing efficiency of 95% and a tensile strength of 15.2 MPa, which is superior to Example 6 (strength 11.6 MPa) because sufficient crosslinking agent promotes dynamic exchange of disulfide bonds and strengthens the polymer network density. Example 9 exhibits a tensile strength of 15.6 MPa and a thermal decomposition temperature of 392°C, which is superior to Example 8 because the increased PTMC content enhances molecular chain rigidity and thermal stability. Comparative Example 1 uses conventional PEO-b-PCL, which has no dynamic crosslinking sites and poor chain segment regularity. It not only lacks self-healing function, but also has a tensile strength of only 8.7 MPa and a thermal decomposition temperature of 335℃, which is 50℃ lower than that of Example 1 (385℃). This highlights the breakthrough of PPC-b-PTMC-gSS in terms of structural stability.

[0082] Please refer to Table 1 for further details. The synergistic effect of the multi-component system ensures the long-cycle stability of the electrolyte, verifying the practical value of the solution. A comprehensive comparison between Example 1 and Comparative Examples 1-3 shows that the triple system of "dynamically cross-linked block copolymer + functionalized MOF + customized ionic liquid" in this solution forms a closed-loop synergy: the dynamic cross-linking of the polymer network can alleviate the interfacial stress caused by the change in electrode volume during charging and discharging; the functionalized MOF acts as a "physical reinforcing phase" to inhibit excessive swelling of the film; and the customized ESBI forms a stable interfacial phase with the electrode surface, reducing the irreversible growth of the SEI film. Example 12 (dual lithium salt) achieved a capacity retention rate of 95.1% after 500 cycles, an improvement of 15.4% compared to Comparative Example 1 (82.4%). This is precisely because the synergistic effect of dual lithium salt + functionalized MOF + dynamic cross-linking ensures both high ion conduction efficiency and a stable electrode-electrolyte interface. Comparative Example 2, lacking physical reinforcement and confinement, had a high swelling rate, leading to ion channel distortion during cycling and a capacity retention rate of only 85.6%. Comparative Example 1, lacking self-healing function, experienced continuous accumulation of interface cracks, ultimately resulting in cycle failure. This fully demonstrates the irreplaceable nature of each innovative component in this solution and the core value of multi-component synergistic design in resolving the contradiction of "high conductivity-high stability-self-healing" in quasi-solid electrolytes.

[0083] like Figure 2 As shown, the curve in Example 12 intersects the X-axis at a point close to 8Ω. cm 2 The overall impedance is the lowest. This is because the dual lithium salt (LiTFSI+LiDFOB) synergistic functionalization of the MOF both inhibits anion migration through LiDFOB and regulates Li through the confinement of the MOF channels. + The transmission path, along with the covalent anchoring of ESBI, reduces interfacial side reactions, ultimately lowering both bulk impedance and interfacial impedance; the curve corresponding to Example 1 intersects the X-axis at approximately 12Ω. cm 2 The impedance is slightly higher than that of Example 12; the curve corresponding to Comparative Example 2 (without MOF) intersects the X-axis at approximately 16 Ω. cm 2 Due to the lack of physical enhancement from MOF, membrane swelling leads to ion channel distortion, while poor interfacial compatibility triggers side reactions, resulting in a significant increase in total impedance.

[0084] like Figure 3 As shown in the figure, this is the polarization current-time curve result of the lithium-ion transference number test. The initial current decays rapidly and then tends to stabilize: This curve corresponds to Example 12 (double lithium salt system), with an initial current of approximately 4.5 mA, a steady-state current of approximately 0.8 mA, and a lithium-ion transference number of 0.76. This is because LiDFOB in the double lithium salt can react with the anion (TFSI). -The formation of weak interactions inhibits the migration of anions; simultaneously, the pore confinement effect of the functionalized MOF further restricts the movement of anions, allowing Li to... + They become the dominant carriers in the migration, ultimately achieving a high lithium-ion transference number.

[0085] like Figure 4 As shown in the figure, this is the Nyquist impedance spectrum result before and after polarization in Example 12. According to the results, the high-frequency semicircle radius of the curve before polarization is smaller, indicating a low initial interfacial impedance; the semicircle radius of the curve after polarization only increases slightly, indicating excellent interfacial stability. Mechanistically, the dynamically crosslinked block copolymer of Example 12 can alleviate the interfacial stress during polarization through disulfide bond self-healing. At the same time, the covalent bonding between the functionalized MOF and ESBI inhibits ionic liquid leakage, avoids irreversible growth of the SEI film, and ultimately maintains the stability of the interfacial impedance before and after polarization.

[0086] like Figure 5 As shown in the figure, this figure represents the specific capacity change results of Example 12 and Comparative Example 3 after 200 cycles. According to the results, the specific capacity of Example 12 (dual lithium salt system) remains stable at 150mAh. g -1 The degradation after 200 cycles is less than 3%. This is because the combination of dual lithium salt, functionalized MOF, and dynamic cross-linked network creates a synergistic effect of "high ion conductivity + stable interface + self-healing structure," ensuring that Li... + The efficient transport of the sample also suppressed interfacial side reactions; while the specific capacity of Comparative Example 3 ([LiTFSI][VIPS] ionic liquid) continued to decrease, eventually dropping to 135mAh. g -1 Because [LiTFSI][VIPS] lacks epoxy groups, it cannot stably bind with MOFs. As the ionic liquid migrates during cycling, the interfacial impedance increases and the capacity decays rapidly, confirming the necessity of ESBI's "epoxy group + sulfonic acid group" bifunctional design.

[0087] It is understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of this disclosure, and this disclosure is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and substance of this disclosure, and these modifications and improvements are also considered to be within the scope of protection of this disclosure.

Claims

1. A method for preparing a self-healing MOF ionic liquid quasi-solid-state electrolyte membrane adapted for black start of energy storage coupled gas turbines, characterized in that, The preparation method includes: S110, Obtain polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds; S120, Obtain ESBI zwitterionic liquid; S130. Obtain amino-modified NH2-Zr-MOF-808, disperse the amino-modified NH2-Zr-MOF-808 in a first solvent, add the ESBI zwitterionic liquid, and after water bath reaction, centrifugation, washing and drying, obtain dual-functionalized ESBI@NH2-Zr-MOF-808. S140. Add a second solvent to the polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds, and stir to disperse to obtain a block copolymer base solution. S150. Add the mixture of ESBI zwitterionic liquid and LiTFSI to the block copolymer base solution, stir to form [LiTFSI][ESBI] ionic liquid, and add ESBI@NH2-Zr-MOF-808 and DTT, disperse and stir to obtain a composite precursor solution. S160. The composite precursor solution is subjected to evaporation, hot pressing, and cooling treatment. The preliminarily formed membrane is then immersed in a LiTFSI / dimethyl carbonate solution and dried to obtain a self-healing quasi-solid electrolyte membrane.

2. The preparation method according to claim 1, characterized in that, The disulfide-containing polypropylene carbonate-b-polytrimethylene carbonate is formed by the following method: An initiator was added to PPC prepolymer and PTMC prepolymer, and the mixture was stirred at 80~100℃ for 4~6 hours to obtain PPC-b-PTMC block copolymer. A disulfide monomer was added to the PPC-b-PTMC block copolymer, the temperature was raised to 100-120℃, and the reaction was continued for 3-5 hours. The disulfide monomer was grafted onto the block copolymer segments through transesterification. After the reaction was completed, the product was cooled to room temperature. The product was dissolved in ultra-dry THF, and then anhydrous ethanol was added for precipitation. The collected precipitate was dried to obtain polypropylene carbonate-b-polytrimethylene carbonate containing disulfide bonds.

3. The preparation method according to claim 1, characterized in that, The ESBI zwitterionic liquid is formed using the following method: A solvent was added to 1-vinyl-3-methylimidazolium bromide and 1,4-butane sulfonyl lactone, and the mixture was stirred at 50-70°C for 8-12 h to obtain a 3-(1-vinyl-3-imidazolium) sulfonate intermediate. Epichlorohydrin and an alkaline catalyst were added to the 3-(1-vinyl-3-imidazolium)sulfonate intermediate, and the temperature was raised to 60-80°C. The reaction was continued for 6-10 hours to induce epoxidation of the vinyl group. After the reaction was completed, the mixture was filtered, and the filtrate was concentrated by rotary evaporation, precipitated, collected by centrifugation, and dried to obtain ESBI zwitterionic liquid.

4. The preparation method according to claim 1, characterized in that, The amino-modified NH2-Zr-MOF-808 is formed by the following method: ZrOCl2 8H2O and 2-aminoterephthalic acid were dissolved in a DMF-formic acid mixed solvent and stirred to form a homogeneous suspension. The mixture was then subjected to a constant temperature solvothermal reaction at 110~130℃ for 20~28h. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The reaction solution was centrifuged and the bottom precipitate was collected. The precipitate was washed and dried to obtain amino-modified NH2-Zr-MOF-808.

5. The preparation method according to claim 1, characterized in that, In step S130, the content of the amino-modified NH2-Zr-MOF-808 is 8-12 parts by mass; The first solvent is ultra-dry DMSO, with a content of 250-350 parts by weight; The content of the ESBI zwitterionic liquid is 4-8 parts by mass; The water bath reaction temperature is 70~90℃, the stirring speed is 200~300r / min, and the reaction time is 6~10h; The drying process is carried out at a temperature of 50-70°C for 10-14 hours.

6. The preparation method according to claim 1, characterized in that, In step S140, the content of the disulfide-containing polypropylene carbonate-b-polytrimethylene carbonate is 50-70 parts by weight. The second solvent is ultra-dry THF, with a content of 350-450 parts by weight; The stirring and dispersion treatment is carried out at a speed of 250~350 r / min for 1.5-2.5 h, and ultrasonic-assisted dispersion is performed for 3-7 min every 30 min.

7. The preparation method according to claim 1, characterized in that, In step S150, the content of the ESBI zwitterionic liquid is 30-50 parts by mass; The content of LiTFSI is 20-32 parts by weight; The content of ESBI@NH2-Zr-MOF-808 is 8-18 parts by weight; The DTT content is 0.3-0.9 parts by weight.

8. The preparation method according to claim 1, characterized in that, In step S160, the hot pressing temperature is 50~70℃, the pressure is 4~8MPa, and the hot pressing time is 10~20min; The drying process is carried out at a temperature of 50~70℃ for 1.5-2.5 hours. The thickness of the self-healing quasi-solid electrolyte membrane is 80~100μm.

9. A self-healing MOF ionic liquid quasi-solid-state electrolyte membrane adapted for black start of energy storage coupled gas turbines, characterized in that, The self-healing MOF ionic liquid quasi-solid electrolyte membrane is prepared by the method described in any one of claims 1 to 8.

10. An application of a self-healing MOF ionic liquid quasi-solid-state electrolyte membrane adapted for black start of energy storage coupled gas turbines, characterized in that, The self-healing MOF / ionic liquid quasi-solid electrolyte membrane described in claim 9 is applied to a flexible lithium battery system in a thermal power energy storage frequency regulation scenario.

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