Flexible solid-state lithium battery with high interfacial stability and preparation method and application thereof

Abstract

The present application relates to a flexible solid-state lithium battery with high interface stability and its preparation method and application, the preparation steps are: preparation of reactive electrode sheet, preparation of reactive flexible solid-state electrolyte precursor solution, assembly of flexible solid-state lithium battery, and excitation by spontaneous, ultraviolet light or heating means, after the interface reaction between the reactive positive electrode sheet, the reactive negative electrode sheet and the reactive functional groups on the reactive flexible solid-state electrolyte precursor solution, a flexible solid-state lithium battery with high stability interface is obtained. The reactive functional groups of the reaction electrode can react in situ with the flexible solid-state electrolyte with reactive functional groups to form strong covalent bonds at the interface. The flexible solid-state lithium battery can realize the stable interface of the flexible solid-state lithium battery under different conditions such as bending, folding, winding and other conditions, and the stable ion rapid transmission at the interface, which provides a valuable solution for realizing the interface stable contact and interface stable transmission of the flexible solid-state lithium battery in different application scenarios.

Description

Technical Field

[0001] This invention relates to the field of new energy lithium battery technology, and in particular to a flexible solid-state lithium battery with high interface stability, its preparation method and application. Background Technology

[0002] Over the past decade, the rapid growth in demand for wearable devices and flexible displays has generated widespread interest in flexible electronic devices. Lithium-ion batteries, as the most promising energy source in flexible electronics, need to adapt to the flexibility requirements of various application scenarios. Flexible solid-state lithium batteries (FSSLBs) are considered ideal for next-generation flexible electrochemical energy storage systems due to their inherent safety and high energy density. The widespread realization of FSSLBs largely depends on developing electrode / electrolyte interfaces with high interfacial stability. Since the electrode and electrolyte are two incompatible solid materials, their inherently rigid solid-solid contact often leads to poor interfacial contact in FSSLBs, resulting in unstable interfacial contact and hindered interfacial transport, especially under various mechanical deformation conditions such as bending and winding. This is significantly different from the close liquid-solid contact of traditional lithium-ion batteries using liquid electrolytes. Even with solid polymer electrolytes that have good adhesion and ductility, it remains difficult to meet the requirements of FSSLBs in practical applications.

[0003] However, most research on FSSLBs focuses only on the flexibility of the electrolyte or electrode itself, with limited attention paid to the bendability and fracture resistance of the interface between the electrode and the solid electrolyte. Currently, even using flexible electrodes and solid electrolytes, constructing high-performance flexible solid-state lithium batteries remains challenging. The main reason is likely that the physical interactions between the interfaces in current FSSLBs are still too weak, making it easy for the electrode to separate from the solid electrolyte when bent or folded, leading to a continuous increase in interfacial resistance and severe degradation of electrochemical performance. This cannot guarantee the electrochemical / mechanical stability of flexible electronic devices under different application scenarios, especially when FSSLBs are subjected to complex mechanical forces and deformations, where this adverse condition worsens. This severely limits the performance of FSSLBs during cycling. Therefore, designing and establishing a tightly contacted and stable solid electrolyte / electrode interface to improve the mechanical and electrochemical performance of FSSLBs is essential, but also challenging.

[0004] A significant positive benefit of strong chemical bonds is the high mechanical stability imparted to solid-state lithium batteries under certain extreme operating conditions. Strong chemical bonds help the electrodes maintain interfacial stability by tightly connecting with the solid electrolyte under significant mechanical deformation and repeated bending and folding. Therefore, flexible solid-state lithium batteries with strongly bonded interfaces hold promise for achieving better mechanical flexibility and electrochemical performance. Summary of the Invention

[0005] Technical problem solved: Addressing the shortcomings of existing technologies, this invention provides a flexible solid-state lithium battery with high interfacial stability, its preparation method, and its applications. In this flexible solid-state lithium battery, the reactive functional groups of the reactive electrode can undergo in-situ reactions with the reactive flexible solid electrolyte to form strong covalent bonds, thereby constructing a flexible solid-state lithium battery with high interfacial stability.

[0006] Technical solution: A method for preparing a flexible solid-state lithium battery with high interfacial stability, comprising the following steps: Step 1, Preparation of reactive electrode sheet: 1) The electrode active material and conductive agent are mixed and ground to obtain a mixed powder. The mixed powder is dispersed in a 75% ethanol solution and magnetically stirred to obtain a suspension. Separately, a polymer with reactive functional groups at both ends is added to a 90% ethanol solution. The pH is adjusted to 4-6 with 0.1 mol / L hydrochloric acid solution, and hydrolyzed under magnetic stirring to obtain a mixed solution. The suspension and mixed solution are combined in a single-necked round-bottom flask, placed in an oil bath, and reacted under magnetic stirring. After the reaction is complete, the mixture is filtered and washed until no precipitate is found in the filtrate after silver nitrate testing. Finally, the mixture is heated to 80°C. The mixture was dried overnight in a constant temperature oven at ℃ to obtain the modified mixture. The weight ratio of the electrode active material to the conductive agent was (6-9):1, the material-to-liquid ratio of the mixed powder to the 75% ethanol solution was (0.93:20) g / mL, the material-to-liquid ratio of the polymer with reactive functional groups at both ends to the 90% ethanol solution was (0.2:26.34) g / mL, and the weight ratio of the mixed powder to the polymer with reactive functional groups at both ends was 1:(0.05-0.25). 2) In an argon-filled glove box, the binder, polymer with reactive functional groups at both ends, additives, and lithium salt were placed in a 30 mL finger bottle. An initiator and solvent were then added, and the mixture was magnetically stirred to dissolve, yielding a composite binder. The weight ratio of the binder, polymer with reactive functional groups at both ends, additives, and lithium salt was 1.5:1.5:4:3. The weight ratio of the initiator to the polymer with reactive functional groups at both ends was (0.0001-0.05):1. The solvent weight was 10% of the total weight of the binder, polymer with reactive functional groups at both ends, additives, and lithium salt. 3) Place the modified mixture and composite binder into a 30 mL finger bottle, seal the finger bottle and take it out from the glove box. Stir it magnetically at room temperature to obtain a reactive electrode slurry. Then, use a coater to coat the slurry onto carbon-coated aluminum foil or copper foil. After the solvent evaporates, place it in a vacuum drying oven and let it stand at room temperature overnight. Then cut it into the required size to obtain a reactive electrode sheet. This electrode sheet can be used as a reactive positive electrode sheet and a reactive negative electrode sheet. The weight ratio of the modified mixture and the composite binder is (6-9):1. Step 2, Preparation of reactive flexible solid electrolyte precursor solution: In an argon-filled glove box, polymer monomers or modified reactive inorganic substances were added to a 30 mL finger bottle with a mouth diameter greater than 16 mm, followed by lithium salt and additives. The mixture was magnetically stirred at room temperature for 1 hour to prepare a transparent reactive flexible solid electrolyte precursor solution. The weight ratio of polymer monomers, lithium salt, and additives was 3:3:4, and the weight ratio of modified reactive inorganic substances, lithium salt, and additives was 7:0.84:3. The method for preparing the modified reactive inorganic compound involves dispersing the inorganic powder in a 75% ethanol solution and magnetically stirring to obtain a suspension; then adding the polymer with reactive functional groups at both ends to a 90% ethanol solution, and using 0.1... The pH of the suspension was adjusted to 4-6 with mol / L hydrochloric acid solution, and hydrolyzed under magnetic stirring to obtain a mixed solution. The suspension and the mixed solution were then mixed in a single-necked round-bottom flask, placed in an oil bath, and reacted under magnetic stirring. After the reaction was completed, the mixture was filtered and washed until no precipitate was found in the filtrate after testing with silver nitrate. Finally, the mixture was dried overnight in a constant temperature oven at 80℃ to obtain the modified reactive inorganic compound. The ratio of inorganic powder to 75% ethanol solution was (0.93:20) g / mL, the ratio of polymer with reactive functional groups at both ends to 90% ethanol solution was (0.2:26.34) g / mL, and the weight ratio of inorganic powder to polymer with reactive functional groups at both ends was 1:(0.05-0.25). Step 3, Assembly of flexible solid-state lithium batteries: In an argon-filled glove box where the moisture and oxygen content is kept below 0.1 ppm, aluminum tabs, reactive positive electrode sheets, reactive flexible solid electrolyte precursor solution, reactive negative electrode sheets, and nickel tabs are sequentially assembled in an aluminum-plastic film to obtain a flexible solid-state lithium battery. Step 4: Fabrication of flexible solid-state lithium batteries with highly stable interfaces: By stimulating the reactive positive electrode, reactive negative electrode and reactive flexible solid electrolyte precursor liquid through spontaneous, ultraviolet light or heating means, an interfacial reaction is carried out between the reactive functional groups, resulting in a flexible solid lithium battery with a highly stable interface.

[0007] The electrode active material in step 1) above is lithium iron phosphate, lithium cobalt oxide, nickel cobalt manganese, lithium titanate, graphite, silicon, silicon suboxide, sulfur or lithium metal, and the conductive agent is Super P, acetylene black, Ketjen black, C65, carbon nanotubes, conductive graphite, graphene or carbon fiber; the binder in step 2) is one or more of polyvinylidene fluoride, polyethylene oxide, polyvinylidene fluoride hexafluoropropylene, polystyrene butadiene, polyvinylpyrrolidone, lithium-ionized polyacrylic acid, sodium carboxymethyl cellulose, and the solvent is N-methylpyrrolidone, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide or deionized water.

[0008] The polymer monomer in step two above is one or more of polyethylene oxide, polyethylene glycol diacrylate, polyvinylidene fluoride, polycarbonate, butyl acrylate, and ethoxylated trimethylolpropane triacrylate; the inorganic powder in step two is lithium lanthanum titanium oxide inorganic particles, lithium lanthanum zirconium oxide inorganic particles, lithium titanium aluminum phosphate inorganic particles, lithium phosphorus sulfur chlorine inorganic particles, or lithium germanium phosphorus sulfur inorganic particles.

[0009] The additives in steps 1(2) and 2 described above are all one or more of fluoroethylene carbonate, succinic anion, polyethylene glycol dimethyl ether, N,N-dimethylformamide, and ethylene-vinyl acetate; the lithium salts in steps 1(2) and 2 are all one or more of lithium bis(trifluoromethanesulfonyl)imide, lithium hexafluorophosphate, lithium perchlorate, and lithium difluorooxalate borate; the initiators in steps 1(2) and 2 are all azobisisobutyronitrile, benzoyl peroxide, 2-hydroxy-2-methylphenylacetone, or 2,2-difluoroisobutyronitrile. -Dimethoxy-2-acetophenone; the polymers with reactive functional groups at both ends in steps 1), 2) and 2 are all γ-aminopropyltriethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanopropyltriethoxysilane, diamino polyethylene glycol, dimercapto polyethylene glycol, diisocyanate polyethylene glycol, ethylene oxide polyethylene glycol, or polyethylene glycol diacrylate.

[0010] In the reaction process of step two described above, an initiator also needs to be added. The weight ratio of the initiator to the modified reactive inorganic material is (0.0001-0.05):1, and the weight ratio of the initiator to the polymer monomer is (0.0001-0.05):1.

[0011] The specific assembly process in step three above is as follows: the size of the reactive positive electrode is 20×50 mm, the size of the reactive negative electrode is 20×50 mm, a support film with a size of 30×60 mm is placed between the positive and negative electrodes, 150 μL of reactive flexible solid electrolyte precursor liquid is dropped onto the support film, and after being fully wetted, the battery is taken out of the glove box for packaging and vacuuming.

[0012] The aforementioned support membrane is a polypropylene membrane, a cellulose membrane, a polyvinylidene fluoride hexafluoropropylene support membrane, or an electrospun oxide membrane.

[0013] The flexible solid-state lithium battery with a highly stable interface is prepared by the preparation method described above.

[0014] In the aforementioned flexible solid-state lithium battery with a highly stable interface, the reactive flexible solid electrolyte precursor can undergo in-situ reactions with both the reactive positive electrode and the reactive negative electrode to form strong covalent bonds.

[0015] Application of flexible solid-state lithium batteries with highly stable interfaces prepared by the above-described method in flexible devices.

[0016] Beneficial Effects: The flexible solid-state lithium battery with high interface stability, its preparation method, and its application provided by this invention have the following beneficial effects: 1. This flexible solid-state lithium battery customizes and fabricates reactive electrodes by transforming hydroxyl groups into specific target functional groups through surface functionalization of electrode materials. The reactive functional groups of the reactive electrodes can react in situ with the reactive flexible solid electrolyte to directly form covalent bonds without the need for an additional intermediate layer. This ensures close contact between the electrode and the solid electrolyte interface, enabling stable bonding of the interface under different conditions such as bending, folding, and winding, as well as stable and rapid ion transport at the interface. This provides a valuable solution for achieving stable interface contact and stable ion transport in different application scenarios of flexible solid-state lithium batteries. 2. No harmful byproducts are generated during the interface reaction of this flexible solid-state lithium battery, and the transport performance at the interface is not affected. 3. The constructed covalent bonds exhibit good ionic conductivity, strong affinity, and reduced resistance; 4. Currently, traditional electrode / solid electrolyte interfaces are all physical contacts, and chemical covalent bonds enhance the interfacial bonding strength on this basis. Attached Figure Description

[0017] Figure 1 The infrared spectra of the mixture of lithium iron phosphate modified with γ-(methacryloyloxy)propyltrimethoxysilane and Super P in Example 1, and the mixture of lithium iron phosphate and Super P in Comparative Example 1.

[0018] Figure 2 These are EIS impedance diagrams of the flexible solid-state lithium batteries of Example 1 and Comparative Example 1 at a bending angle of 0°.

[0019] Figure 3These are EIS impedance diagrams of the flexible solid-state lithium batteries of Example 1 and Comparative Example 1 at a bending angle of 60°.

[0020] Figure 4 These are the EIS impedance diagrams of the flexible solid-state lithium batteries of Example 1 and Comparative Example 1 at a 90° bending angle.

[0021] Figure 5 These are EIS impedance diagrams of the flexible solid-state lithium batteries of Example 1 and Comparative Example 1 at a bending angle of 180°.

[0022] Figure 6 The graphs show the constant current charge-discharge cycle test results of the flexible solid-state lithium batteries of Example 1 and Comparative Example 1 at different bending angles.

[0023] Figure 7 The flexible solid-state lithium battery prepared in Example 1 was tested under different bending conditions.

[0024] Figure 8 This is a schematic diagram of the flexible solid-state lithium battery of the present invention. Implementation

[0025] The sources of the substances and instruments used in the following examples are as follows: Lithium iron phosphate, graphite, Super P, and polypropylene separators were all purchased from Guangdong Zhuguang New Energy Technology Co., Ltd.; carbonized copper foil, carbonized aluminum foil, aluminum tabs, nickel tabs, aluminum-plastic film, and lithium foil were all purchased from Shenzhen Kejing Zhida Technology Co., Ltd.; γ-(methacryloyloxy)propyltrimethoxysilane, polyethylene oxide, polyethylene glycol diacrylate, fluoroethylene carbonate, lithium bis(trifluoromethanesulfonyl)imide, and acetonitrile were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; azobisisobutyronitrile was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; ethanol was purchased from Shanghai Titan Technology Co., Ltd.; deionized water was prepared in-house; silver nitrate and hydrochloric acid were both purchased from Guangzhou Chemical Reagent Factory.

[0026] The Fourier transform infrared spectrometer used was the Nicolet IS10 from Thermo Fisher Scientific; the glove box used was the Super series from Shanghai Microna Electromechanical Technology Co., Ltd.; the electrochemical workstation used was the CHI660E from Shanghai Chenhua Instrument Co., Ltd.; the battery testing system used was the BTS 8.0 from Shenzhen Xinwei Electronics Co., Ltd.; the electronic balance used was the PWN125DZH from Ohaus Instruments (Changzhou) Co., Ltd.; the electric thermostatic drying oven used was the DHG-9070A from Shanghai Jinghong Experimental Equipment Co., Ltd.; the vacuum thermostatic drying oven used was the D2F-6050 from Shanghai Yiheng Scientific Instruments Co., Ltd.; the thermostatic magnetic stirrer used was the DF-101S from Gongyi Yuhua Instrument Co., Ltd.; the high-speed centrifuge used was the H1650 from Hunan Xiangyi Laboratory Instrument Development Co., Ltd.; and the vacuum sealing machine used was the MSK-115A-Ⅲ from Shenzhen Kejing Zhida Technology Co., Ltd. Example

[0027] This embodiment provides a method for preparing a flexible solid-state lithium battery with high interface stability, including the following steps: Step 1, Preparation of reactive electrode sheet: 7.5 g and 1 g of lithium iron phosphate powder and Super P conductive agent were weighed separately and ground thoroughly in an agate mortar to obtain a mixed powder. 0.93 g of the mixed powder was weighed and dispersed in 20 mL of 75% ethanol solution. The mixture was magnetically stirred at room temperature for 2 h to obtain a suspension. 0.2 g of γ-(methacryloyloxy)propyltrimethoxysilane was added to 26.34 mL of 90% ethanol solution, and the pH was adjusted to 5 with 0.1 mol / L hydrochloric acid solution. The γ-(methacryloyloxy)propyltrimethoxysilane was hydrolyzed for 1.5 h under magnetic stirring to obtain a mixed solution. The above suspension and mixed solution were mixed in a 150 mL single-necked round-bottom flask and placed in an oil bath. The mixture was reacted at 75 °C under magnetic stirring for 2 h. After the reaction, the resulting suspension was filtered and washed until no precipitate was found in the filtrate after silver nitrate testing. Finally, the filtrate was heated to 80 °C. Drying in a constant temperature oven at ℃ overnight yields a mixture of γ-(methacryloyloxy)propyltrimethoxysilane modified lithium iron phosphate and SuperP.

[0028] Subsequently, in an argon-filled glove box, polyethylene oxide (PEO, Mw=60w), polyethylene glycol diacrylate (PEGDA, Mw=1000), fluoroethylene carbonate (FEC), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were weighed out at 1.5g, 1.5g, 4g, and 3g respectively and placed in 30 mL finger bottles. Then, 0.0075g of azobisisobutyronitrile (AIBN) thermal initiator was added, and finally 5mL of acetonitrile was added as a solvent. The mixture was then magnetically stirred until completely dissolved to obtain a translucent composite adhesive.

[0029] Weigh 0.85g of the modified lithium iron phosphate and Super P mixture and 0.15g of composite binder into a 30mL finger bottle. Seal the finger bottle and remove it from the glove box. Stir magnetically at room temperature for 4 hours to ensure homogeneity, obtaining a reactive positive electrode slurry. Apply the slurry to carbon-coated aluminum foil using a coater. After most of the solvent has evaporated, place it in a vacuum drying oven and let it stand at room temperature overnight. Then cut it into 20×50 mm pieces to obtain the reactive positive electrode sheet.

[0030] Step 2, Preparation of reactive flexible solid electrolyte precursor solution: In an argon-filled glove box, 3g, 4g, and 3g of polyethylene glycol diacrylate (PEGDA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and fluoroethylene carbonate (FEC) were added to a 30 mL finger bottle with a mouth diameter greater than 16 mm. Then, 0.0075g of azobisisobutyronitrile (AIBN) initiator was added. The mixture was magnetically stirred at room temperature for 1 hour to prepare a transparent reactive flexible solid electrolyte precursor solution.

[0031] Step 3, Assembly of flexible solid-state lithium batteries: In an argon-filled glove box where the moisture and oxygen content is maintained below 0.1 ppm, aluminum tabs, reactive positive electrode sheets, reactive flexible solid electrolyte precursor solutions, lithium foil (reactive negative electrode sheets), and nickel tabs are sequentially assembled in an aluminum-plastic film. The reactive positive electrode sheet and the lithium foil are both 20×50 mm in size. A non-woven fabric separator with a size of 30×60 mm is placed between the positive and negative electrodes as a support membrane. 150 μL of reactive flexible solid electrolyte precursor solution is dropped onto the polypropylene separator. After fully wetting, the battery is removed from the glove box for packaging and vacuuming to obtain a flexible solid-state lithium battery. Step 4: Fabrication of flexible solid-state lithium batteries with highly stable interfaces: The assembled flexible solid-state lithium battery is heated at 80°C for 30 minutes. After the reactive functional groups on the reactive positive electrode, lithium foil and reactive flexible solid electrolyte precursor liquid undergo an interfacial reaction, a flexible solid-state lithium battery with a highly stable interface is obtained.

[0032] Comparative Example 1 provides a method for preparing a flexible solid-state lithium battery without chemical bonding interfaces. The only difference between this method and Example 1 is the preparation of the mixture of lithium iron phosphate and Super P in step one. The preparation method of this comparative example is as follows: weigh lithium iron phosphate powder and Super P conductive agent in a weight ratio of 7.5:1 in an agate mortar and grind them thoroughly to obtain the mixture of lithium iron phosphate and Super P.

[0033] The FTIR spectra of the mixture of γ-(methacryloyloxy)propyltrimethoxysilane modified lithium iron phosphate and Super P (intermediate product of Example 1) and the mixture of lithium iron phosphate and Super P (intermediate product of Comparative Example 1) were analyzed using an infrared spectrometer. The infrared spectra are shown below. Figure 1 As shown. By Figure 1 It can be seen that the presence of C=C and Si-O-Si bonds in the Fourier transform infrared (FTIR) spectrum proves that γ-(methacryloyloxy)propyltrimethoxysilane in Example 1 has been successfully grafted onto LFP.

[0034] EIS analysis was performed on the flexible solid-state lithium battery with high interfacial stability prepared in Example 1 and the flexible solid-state lithium battery without chemical bonding interface prepared in Comparative Example 1 using a CHI 660E electrochemical workstation in the frequency range of 100 kHz to 10 mHz. The results are as follows: Figure 2-5 As shown, the Rct of the flexible solid-state lithium battery with chemically bonded interface in Example 1 remains stable under different degrees of bending.

[0035] Constant current charge-discharge tests were conducted using a Newway battery tester within the range of 2.5–4.0 V. The constant current charge-discharge cycle test results at different bending angles are shown in the figures for the flexible solid-state lithium battery with high interfacial stability prepared in Example 1 and the flexible solid-state lithium battery without chemical bonding interfaces prepared in Comparative Example 1. Figure 6 As shown. By Figure 6 It can be seen that, in the initial state, the reversible capacity of the flexible solid-state lithium battery with high interfacial stability prepared in Example 1 is 152.9 mAh g⁻¹. -1 Furthermore, it maintains stable discharge capacity even when bent to 60°, 90°, and 180°; the reversible capacity of the flexible solid-state lithium battery without chemical bonding interface prepared in Comparative Example 1 is 129.4 mAh g. -1 Furthermore, as the device was bent to 60°, 90°, and 180°, the discharge capacity rapidly decreased to 20.9, 0.5, and 1.1 mAh g, respectively. -1 .

[0036] The flexible solid-state lithium battery prepared in Example 1, exhibiting high interfacial stability, can illuminate LEDs even under various states such as bending, winding, and folding. Figure 7 As shown.

[0037] The LED light can be lit in different states such as bending, winding, and folding, such as... Figure 7 As shown. Example

[0038] This embodiment provides a method for preparing a flexible solid-state lithium battery with high interface stability, including the following steps: Step 1, Preparation of reactive electrode sheet: 7.5 g and 1 g of graphite powder and Super P conductive agent were weighed separately and ground thoroughly in an agate mortar to obtain a mixed powder. 0.93 g of the mixed powder was weighed and dispersed in 20 mL of 75% ethanol solution. The mixture was magnetically stirred at room temperature for 2 h to obtain a suspension. 0.2 g of γ-(methacryloyloxy)propyltrimethoxysilane was added to 26.34 mL of 90% ethanol solution, and the pH was adjusted to approximately 5 with 0.1 mol / L hydrochloric acid solution. Hydrolysis was carried out under magnetic stirring for 1.5 h to obtain a mixed solution. The above suspension and mixed solution were mixed in a 150 mL single-necked round-bottom flask and placed in an oil bath. The mixture was reacted under magnetic stirring at 75 °C for 2 h. After the reaction, the resulting suspension was filtered and washed until no precipitate was found in the filtrate after silver nitrate testing. Finally, the filtrate was heated to 80 °C. Drying in a constant temperature oven at ℃ overnight yields a mixture of γ-(methacryloyloxy)propyltrimethoxysilane modified graphite and Super P.

[0039] Subsequently, in an argon-filled glove box, polyethylene oxide (PEO, Mw=60w), polyethylene glycol diacrylate (PEGDA, Mw=1000), fluoroethylene carbonate (FEC), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were weighed out at mass values ​​of 1.5g, 1.5g, 4g, and 3g, respectively, and placed in 30 mL finger bottles. Then, 0.0075g of azobisisobutyronitrile (AIBN) thermal initiator was added, and finally, a certain amount of 5ml of acetonitrile was added as a solvent. The mixture was then magnetically stirred until it was completely dissolved, resulting in a translucent composite adhesive.

[0040] Weigh 0.85g of the modified graphite and Super P mixture and 0.15g of the composite binder into a 30mL finger bottle. Seal the finger bottle and remove it from the glove box. Stir magnetically at room temperature for 4 hours to ensure homogeneity, obtaining a reactive negative electrode slurry. Apply the slurry to carbon-coated copper foil using a coater. After most of the solvent has evaporated, place it in a vacuum drying oven and let it stand at room temperature overnight. Then cut it into 20×50 mm pieces to obtain the reactive negative electrode sheet. The reactive positive electrode sheet is prepared by replacing the graphite powder with lithium iron phosphate powder, with the other steps being the same as above.

[0041] Step 2, Preparation of reactive flexible solid electrolyte precursor solution: In an argon-filled glove box, 3g, 4g, and 3g of polyethylene glycol diacrylate (PEGDA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and fluoroethylene carbonate (FEC) were dissolved in a 30 mL finger bottle with a mouth diameter greater than 16 mm. Then, 0.0075g of azobisisobutyronitrile (AIBN) initiator was added, and the mixture was magnetically stirred at room temperature for 1 hour to prepare a transparent reactive flexible solid electrolyte precursor solution.

[0042] Step 3, Assembly of flexible solid-state lithium batteries: In an argon-filled glove box where the moisture and oxygen content is maintained below 0.1 ppm, aluminum tabs, reactive positive electrode sheets, reactive flexible solid electrolyte precursor solutions, reactive negative electrode sheets, and nickel tabs are sequentially assembled within an aluminum-plastic film. The reactive positive electrode sheet and the reactive negative electrode sheet are both 20×50 mm in size. A 30×60 mm polypropylene separator is placed between the positive and negative electrodes as a support membrane. 150 μL of reactive flexible solid electrolyte precursor solution is dropped onto the polypropylene separator and fully wetted. The battery is then removed from the glove box for encapsulation and vacuuming to obtain a flexible solid-state lithium battery. Step 4: Fabrication of flexible solid-state lithium batteries with highly stable interfaces: The assembled flexible solid-state lithium battery is heated at 80°C for 30 minutes. After the reactive positive electrode, reactive negative electrode and reactive flexible solid electrolyte precursor liquid undergo an interfacial reaction, a flexible solid-state lithium battery with a highly stable interface is obtained. Example

[0043] This embodiment provides a method for preparing a flexible solid-state lithium battery with high interface stability, including the following steps: Step 1, Preparation of reactive electrode sheet: 7.5 g and 1 g of lithium cobalt oxide powder and carbon nanotube conductive agent were weighed separately and ground thoroughly in an agate mortar to obtain a mixed powder. 0.93 g of the mixed powder was weighed and dispersed in 20 mL of 75% ethanol solution. The mixture was magnetically stirred at room temperature for 2 h to obtain a suspension. 0.2 g of γ-glycidoxypropyltrimethoxysilane was added to 26.34 mL of 90% ethanol solution, and the pH was adjusted to 5 with 0.1 mol / L hydrochloric acid solution. The mixture was hydrolyzed under magnetic stirring for 1.5 h to obtain a mixed solution. The above suspension and mixed solution were mixed in a 150 mL single-necked round-bottom flask and placed in an oil bath. The mixture was reacted under magnetic stirring at 75 °C for 2 h. After the reaction, the resulting suspension was filtered and washed until no precipitate was found in the filtrate after silver nitrate testing. Finally, the filtrate was heated to 80 °C. Drying in a constant temperature oven at ℃ overnight yields a mixture of γ-glycidyl etheroxypropyltrimethoxysilane modified lithium cobalt oxide and carbon nanotubes.

[0044] Subsequently, in an argon-filled glove box, polyvinylidene fluoride, diamino polyethylene glycol, succinate, and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were weighed out at mass levels of 1.5g, 1.5g, 4g, and 3g, respectively, and placed in 30 mL finger bottles. Finally, 5 mL of tetrahydrofuran was added as a solvent, and the mixture was magnetically stirred until it was completely dissolved, resulting in a translucent composite adhesive.

[0045] Weigh 0.85g of the modified lithium cobalt oxide and carbon nanotube mixture and 0.15g of composite binder into a 30mL finger bottle. Seal the finger bottle and remove it from the glove box. Stir magnetically at room temperature for 4 hours to ensure homogeneity, obtaining a reactive positive electrode slurry. Coat the slurry onto carbon-coated aluminum foil using a coater. After most of the solvent has evaporated, place it in a vacuum drying oven and let it stand at room temperature overnight. Then cut it into 20×50 mm pieces to obtain the reactive positive electrode sheet. For the preparation of the reactive negative electrode sheet, replace the lithium cobalt oxide powder with lithium titanate powder, and follow the same steps.

[0046] Step 2, Preparation of reactive flexible solid electrolyte precursor solution: In an argon-filled glove box, 2.25 g, 0.75 g, 3 g, and 4 g of polyvinylidene fluoride, diamino polyethylene glycol, lithium bis(trifluoromethanesulfonylimide (LiTFSI), and succinate were added to a finger bottle with a volume of 30 mL and a mouth diameter greater than 16 mm. The mixture was magnetically stirred at room temperature for 1 h to prepare a transparent reactive flexible solid electrolyte precursor solution.

[0047] Step 3, Assembly of flexible solid-state lithium batteries: In an argon-filled glove box where the moisture and oxygen content is maintained below 0.1 ppm, aluminum tabs, reactive positive electrode sheets, reactive flexible solid electrolyte precursor solutions, reactive negative electrode sheets, and nickel tabs are sequentially assembled within an aluminum-plastic film. The reactive positive electrode sheet and the reactive negative electrode sheet are both 20×50 mm in size. A cellulose membrane with a size of 30×60 mm is placed between the positive and negative electrodes as a support membrane. 150 μL of reactive flexible solid electrolyte precursor solution is dropped onto the cellulose support membrane and fully wetted. The battery is then removed from the glove box for encapsulation and vacuuming to obtain a flexible solid-state lithium battery. Step 4: Fabrication of flexible solid-state lithium batteries with highly stable interfaces: The assembled flexible solid-state lithium battery is heated at 60°C for 1 hour. After the reactive positive electrode, reactive negative electrode and reactive flexible solid electrolyte precursor liquid undergo an interfacial reaction, a flexible solid-state lithium battery with a highly stable interface is obtained. Example

[0048] This embodiment provides a method for preparing a flexible solid-state lithium battery with high interface stability, including the following steps: Step 1, Preparation of reactive electrode sheet: 7.5 g and 1 g of nickel-cobalt-manganese 811 powder and C65 conductive agent were weighed separately and ground thoroughly in an agate mortar to obtain a mixed powder. 0.93 g of the mixed powder was weighed and dispersed in 20 mL of 75% ethanol solution. The mixture was magnetically stirred for 2 h at room temperature to obtain a suspension. 0.2 g of 3-mercaptopropyltriethoxysilane was added to 26.34 mL of 90% ethanol solution, and the pH was adjusted to 5 with 0.1 mol / L hydrochloric acid solution. The mixture was hydrolyzed for 1.5 h under magnetic stirring to obtain a mixed solution. The above suspension and mixed solution were mixed in a 150 mL single-necked round-bottom flask and placed in an oil bath. The mixture was reacted at 75°C under magnetic stirring for 2 h. After the reaction, the resulting suspension was filtered and washed until no precipitate was found in the filtrate after silver nitrate testing. Finally, the mixture was heated to 80°C. Drying in a constant temperature oven at ℃ overnight yields a mixture of 3-mercaptopropyltriethoxysilane modified nickel cobalt manganese 811 powder and C65.

[0049] Subsequently, in an argon-filled glove box, polyvinylidene fluoride, polyethylene glycol diacrylate, polyethylene glycol dimethyl ether, and lithium difluorooxalate borate were weighed out at mass values ​​of 2.25 g, 0.75 g, 4 g, and 3 g, respectively, and placed in 30 mL finger bottles. Then, 0.0075 g of azobisisobutyronitrile was added, and finally, a certain amount of 5 mL of nitrogen-methylpyrrolidone was added as a solvent. The mixture was then completely dissolved under magnetic stirring to obtain a translucent composite adhesive.

[0050] Weigh 0.85g of the mixture of modified nickel-cobalt-manganese 811 powder and C65, and 0.15g of composite binder into a 30mL finger bottle. Seal the finger bottle and remove it from the glove box. Stir magnetically at room temperature for 4 hours to ensure homogeneity, obtaining a reactive positive electrode slurry. Coat the slurry onto carbon-coated aluminum foil using a coater. After most of the solvent has evaporated, place it in a vacuum drying oven and let it stand at room temperature overnight. Then cut it into 20×50 mm pieces to obtain the reactive positive electrode sheet. For the preparation of the reactive negative electrode sheet, replace the nickel-cobalt-manganese 811 powder with silicon powder, and follow the same steps.

[0051] Step 2, Preparation of reactive flexible solid electrolyte precursor solution: In an argon-filled glove box, 2.25 g, 0.75 g, 3 g, and 4 g of butyl acrylate, ethoxylated trimethylolpropane triacrylate, lithium difluorooxalate borate, and polyethylene glycol dimethyl ether were added to a finger bottle with a volume of 30 mL and a mouth diameter greater than 16 mm. 0.0075 g of initiator azobisisobutyronitrile was added to dissolve the mixture. The solution was magnetically stirred at room temperature for 1 hour to prepare a transparent reactive flexible solid electrolyte precursor solution.

[0052] Step 3, Assembly of flexible solid-state lithium batteries: In an argon-filled glove box where the moisture and oxygen content is maintained below 0.1 ppm, aluminum tabs, reactive positive electrode sheets, reactive flexible solid electrolyte precursor solutions, reactive negative electrode sheets, and nickel tabs are sequentially assembled within an aluminum-plastic film. The reactive positive electrode sheet and the reactive negative electrode sheet are both 20×50 mm in size. An electrospun lithium aluminum titanium phosphorus film with a size of 30×60 mm is placed between the positive and negative electrodes as a support film. 150 μL of reactive flexible solid electrolyte precursor solution is dropped onto the electrospun lithium aluminum titanium phosphorus support film. After being fully wetted, the battery is removed from the glove box for packaging and vacuuming to obtain a flexible solid-state lithium battery. Step 4: Fabrication of flexible solid-state lithium batteries with highly stable interfaces: The assembled flexible solid-state lithium battery is heated at 80°C for 1 hour. After the reactive positive electrode, reactive negative electrode and reactive flexible solid electrolyte precursor liquid undergo an interfacial reaction, a flexible solid-state lithium battery with a highly stable interface is obtained. Example

[0053] This embodiment provides a method for preparing a flexible solid-state lithium battery with high interface stability, including the following steps: Step 1, Preparation of reactive electrode sheet: 7.5 g and 1 g of graphite powder and Super P conductive agent were weighed separately and ground thoroughly in an agate mortar to obtain a mixed powder. 0.93 g of the mixed powder was weighed and dispersed in 20 mL of 75% ethanol solution. The mixture was magnetically stirred at room temperature for 2 h to obtain a suspension. 0.2 g of γ-(methacryloyloxy)propyltrimethoxysilane was added to 26.34 mL of 90% ethanol solution, and the pH was adjusted to 5 with 0.1 mol / L hydrochloric acid solution. The mixture was hydrolyzed under magnetic stirring for 1.5 h to obtain a mixed solution. The above suspension and mixed solution were mixed in a 150 mL single-necked round-bottom flask and placed in an oil bath. The mixture was reacted under magnetic stirring at 75 °C for 2 h. After the reaction, the resulting suspension was filtered and washed until no precipitate was found in the filtrate after silver nitrate testing. Finally, the filtrate was heated to 80 °C. Drying in a constant temperature oven at ℃ overnight yields a mixture of γ-(methacryloyloxy)propyltrimethoxysilane modified graphite and Super P.

[0054] Subsequently, in an argon-filled glove box, polyethylene oxide (PEO, Mw=60w), polyethylene glycol diacrylate (PEGDA, Mw=1000), fluoroethylene carbonate (FEC), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were weighed out at mass values ​​of 1.5g, 1.5g, 4g, and 3g, respectively, and placed in 30 mL finger bottles. Then, 0.0075g of azobisisobutyronitrile (AIBN) thermal initiator was added, and finally, a certain amount of 5mL of acetonitrile was added as a solvent. The mixture was then magnetically stirred until it was completely dissolved, resulting in a translucent composite adhesive.

[0055] Weigh 0.85g of the modified graphite and Super P mixture and 0.15g of the composite binder into a 30mL finger bottle. Seal the finger bottle and remove it from the glove box. Stir magnetically at room temperature for 4 hours to ensure homogeneity, obtaining a reactive negative electrode slurry. Apply the slurry to carbon-coated copper foil using a coater. After most of the solvent has evaporated, place it in a vacuum drying oven and let it stand at room temperature overnight. Then cut it into 20×50 mm pieces to obtain the reactive negative electrode sheet. The reactive positive electrode sheet is prepared by replacing the graphite powder with lithium iron phosphate powder, with the other steps being the same as above.

[0056] Step 2, Preparation of reactive flexible solid electrolyte precursor solution: Weigh 0.93 g of lithium aluminum titanium phosphate inorganic particles and disperse them in 20 mL of 75% ethanol solution. Stir magnetically for 2 h at room temperature to obtain a suspension. Add 0.2 g of γ-(methacryloyloxy)propyltrimethoxysilane to 26.34 mL of 90% ethanol solution and adjust the pH to 5 with 0.1 mol / L hydrochloric acid solution. Hydrolyze under magnetic stirring for 1.5 h to obtain a mixture. Mix the above suspension and mixture in a 150 mL single-necked round-bottom flask and place it in an oil bath. React under magnetic stirring at 75 ℃ for 2 h. After the reaction is complete, filter the obtained suspension and wash until no precipitate is found in the filtrate after testing with silver nitrate. Finally, dry in a constant temperature oven at 80 ℃ overnight to obtain γ-(methacryloyloxy)propyltrimethoxysilane modified lithium aluminum titanium phosphate powder.

[0057] In an argon-filled glove box, 1.4 g, 0.168 g, and 0.6 g of modified lithium aluminum titanium phosphorus powder, lithium bis(trifluoromethanesulfonylimide (LiTFSI), and polyethylene glycol dimethyl ether were dissolved in a 30 mL finger bottle with a mouth diameter greater than 16 mm. Then, 0.007 g of azobisisobutyronitrile (AIBN) initiator was added, and the mixture was magnetically stirred at room temperature for 1 h to prepare a homogeneous reactive flexible solid electrolyte precursor solution.

[0058] Step 3, Assembly of flexible solid-state lithium batteries: In an argon-filled glove box where the moisture and oxygen content is maintained below 0.1 ppm, aluminum tabs, reactive positive electrode sheets, reactive flexible solid electrolyte precursor solutions, reactive negative electrode sheets, and nickel tabs are sequentially assembled within an aluminum-plastic film. The reactive positive electrode sheet and the reactive negative electrode sheet are both 20×50 mm in size. A 30×60 mm polypropylene separator is placed between the positive and negative electrodes as a support membrane. 150 μL of reactive flexible solid electrolyte precursor solution is dropped onto the polypropylene separator and fully wetted. The battery is then removed from the glove box for encapsulation and vacuuming to obtain a flexible solid-state lithium battery. Step 4: Fabrication of flexible solid-state lithium batteries with highly stable interfaces: The assembled flexible solid-state lithium battery was heated at 80°C for 30 minutes. After an interfacial reaction occurred between the reactive positive electrode, the reactive negative electrode, and the reactive flexible solid electrolyte precursor liquid, a flexible solid-state lithium battery with a highly stable interface was obtained. Its structure is as follows: Figure 8 As shown.

[0059] The embodiments of the present invention have been described in detail above. For those skilled in the art, there may be changes in the specific implementation methods and application scope based on the ideas of the embodiments of the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A method for preparing a flexible solid-state lithium battery with high interfacial stability, characterized in that... The steps are as follows: Step 1, Preparation of reactive electrode sheet: 1) The electrode active material and conductive agent are mixed and ground to obtain a mixed powder. The mixed powder is dispersed in a 75% ethanol solution and magnetically stirred to obtain a suspension. Separately, a polymer with reactive functional groups at both ends is added to a 90% ethanol solution. The pH is adjusted to 4-6 with 0.1 mol / L hydrochloric acid solution, and hydrolyzed under magnetic stirring to obtain a mixed solution. The suspension and mixed solution are combined in a single-necked round-bottom flask, placed in an oil bath, and reacted under magnetic stirring. After the reaction is complete, the mixture is filtered and washed until no precipitate is found in the filtrate after silver nitrate testing. Finally, the mixture is heated to 80°C. The mixture was dried overnight in a constant temperature oven at ℃ to obtain the modified mixture. The weight ratio of the electrode active material to the conductive agent was (6-9):1, the material-to-liquid ratio of the mixed powder to the 75% ethanol solution was (0.93:20) g / mL, the material-to-liquid ratio of the polymer with reactive functional groups at both ends to the 90% ethanol solution was (0.2:26.34) g / mL, and the weight ratio of the mixed powder to the polymer with reactive functional groups at both ends was 1:(0.05-0.25). 2) In an argon-filled glove box, the binder, polymer with reactive functional groups at both ends, additives, and lithium salt were placed in a 30 mL finger bottle. An initiator and solvent were then added, and the mixture was magnetically stirred to dissolve, yielding a composite binder. The weight ratio of the binder, polymer with reactive functional groups at both ends, additives, and lithium salt was 1.5:1.5:4:

3. The weight ratio of the initiator to the polymer with reactive functional groups at both ends was (0.0001-0.05):

1. The solvent weight was 10% of the total weight of the binder, polymer with reactive functional groups at both ends, additives, and lithium salt. 3) Place the modified mixture and composite binder into a 30 mL finger bottle, seal the bottle, remove it from the glove box, and magnetically stir it at room temperature to obtain a reactive electrode slurry. Then, use a coater to coat the slurry onto carbon-coated aluminum foil or copper foil. After the solvent evaporates, place it in a vacuum drying oven and let it stand at room temperature overnight. Then, cut it into the required size to obtain a reactive electrode sheet. This electrode sheet can be used as a reactive positive electrode sheet and a reactive negative electrode sheet. The weight ratio of the modified mixture to the composite binder is (6-9):

1. The electrode active material in step 1) is lithium iron phosphate, lithium cobalt oxide, nickel cobalt manganese, lithium titanate, graphite, silicon, silicon suboxide, sulfur, or lithium metal; the conductive agent is Super P, acetylene black, Ketjen black, C65, carbon nanotubes, conductive graphite, graphene, or carbon fiber; the binder in step 1) is one or more of polyvinylidene fluoride, polyethylene oxide, polyvinylidene fluoride hexafluoropropylene, polystyrene butadiene, polyvinylpyrrolidone, lithium-ionized polyacrylic acid, and sodium carboxymethyl cellulose; and the solvent is N-methylpyrrolidone, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, or deionized water. Step 2, Preparation of reactive flexible solid electrolyte precursor solution: In an argon-filled glove box, polymer monomers or modified reactive inorganic substances were added to a 30 mL finger bottle with a mouth diameter greater than 16 mm, followed by lithium salt and additives. The mixture was magnetically stirred at room temperature for 1 hour to prepare a transparent reactive flexible solid electrolyte precursor solution. The weight ratio of polymer monomers, lithium salt, and additives was 3:3:4, and the weight ratio of modified reactive inorganic substances, lithium salt, and additives was 7:0.84:

3. The method for preparing the modified reactive inorganic compound involves dispersing the inorganic powder in a 75% ethanol solution and magnetically stirring to obtain a suspension; then adding the polymer with reactive functional groups at both ends to a 90% ethanol solution, and using 0.1... The pH of the solution was adjusted to 4-6 with mol / L hydrochloric acid, and hydrolyzed under magnetic stirring to obtain a mixed solution. The suspension and the mixed solution were then mixed in a single-necked round-bottom flask, placed in an oil bath, and reacted under magnetic stirring. After the reaction was completed, the mixture was filtered and washed until no precipitate was found in the filtrate after testing with silver nitrate. Finally, the mixture was dried overnight in a constant temperature oven at 80°C to obtain the modified reactive inorganic compound. The ratio of inorganic powder to 75% ethanol solution was (0.93:20) g / mL, the ratio of polymer with reactive functional groups at both ends to 90% ethanol solution was (0.2:26.34) g / mL, and the weight ratio of inorganic powder to polymer with reactive functional groups at both ends was 1:(0.05-0.25). The additives in steps 1(2) and 2 are all one or more of fluoroethylene carbonate, succinic anion, polyethylene glycol dimethyl ether, N,N-dimethylformamide, and ethylene-vinyl acetate; the lithium salts in steps 1(2) and 2 are all one or more of lithium bis(trifluoromethanesulfonyl)imide, lithium hexafluorophosphate, lithium perchlorate, and lithium difluorooxalate borate; the initiators in steps 1(2) and 2 are all azobisisobutyronitrile, benzoyl peroxide, 2-hydroxy-2-methylphenylacetone, or 2,2-difluoroisobutyronitrile. -Dimethoxy-2-acetophenone; the polymers with reactive functional groups at both ends in steps 1), 2) and 2 are all γ-aminopropyltriethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, γ-(methacryloyloxy)propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanopropyltriethoxysilane, diamino polyethylene glycol, dimercapto polyethylene glycol, diisocyanate polyethylene glycol, ethylene oxide polyethylene glycol, or polyethylene glycol diacrylate; Step 3, Assembly of flexible solid-state lithium batteries: In an argon-filled glove box where the moisture and oxygen content is kept below 0.1 ppm, aluminum tabs, reactive positive electrode sheets, reactive flexible solid electrolyte precursor solution, reactive negative electrode sheets, and nickel tabs are sequentially assembled in an aluminum-plastic film to obtain a flexible solid-state lithium battery. Step 4: Fabrication of flexible solid-state lithium batteries with highly stable interfaces: By stimulating the reactive positive electrode, reactive negative electrode and reactive flexible solid electrolyte precursor liquid through spontaneous, ultraviolet light or heating means, an interfacial reaction is carried out between the reactive functional groups, resulting in a flexible solid lithium battery with a highly stable interface.

2. The method for preparing a flexible solid-state lithium battery with high interface stability according to claim 1, characterized in that: The polymer monomer in step two is one or more of polyethylene oxide, polyethylene glycol diacrylate, polyvinylidene fluoride, polycarbonate, butyl acrylate, and ethoxylated trimethylolpropane triacrylate; the inorganic powder in step two is lithium lanthanum titanium oxide inorganic particles, lithium lanthanum zirconium oxide inorganic particles, lithium titanium aluminum phosphate inorganic particles, lithium phosphorus sulfur chlorine inorganic particles, or lithium germanium phosphorus sulfur inorganic particles.

3. The method for preparing a flexible solid-state lithium battery with high interfacial stability according to claim 2, characterized in that: In the reaction process of step two, an initiator also needs to be added. The weight ratio of the initiator to the modified reactive inorganic material is (0.0001-0.05):1, and the weight ratio of the initiator to the polymer monomer is (0.0001-0.05):

1.

4. The method for preparing a flexible solid-state lithium battery with high interfacial stability according to claim 1, characterized in that... The specific assembly process in step three is as follows: the size of the reactive positive electrode is 20×50 mm, the size of the reactive negative electrode is 20×50 mm, a support film with a size of 30×60 mm is placed between the positive and negative electrodes, 150 μL of reactive flexible solid electrolyte precursor liquid is dropped onto the support film, and after being fully wetted, the battery is taken out of the glove box for packaging and vacuuming.

5. The method for preparing a flexible solid-state lithium battery with high interfacial stability according to claim 4, characterized in that: The support membrane is a polypropylene membrane, a cellulose membrane, a polyvinylidene fluoride hexafluoropropylene support membrane, or an electrospun oxide membrane.

6. A flexible solid-state lithium battery with a highly stable interface prepared by the preparation method according to any one of claims 1 to 5.

7. A flexible solid-state lithium battery with a highly stable interface according to claim 6, characterized in that: In the flexible solid-state lithium battery with a highly stable interface, the reactive flexible solid electrolyte precursor liquid can undergo in-situ reactions with both the reactive positive electrode and the reactive negative electrode to form strong covalent bonds.

8. The application of a flexible solid-state lithium battery with a highly stable interface prepared by any one of claims 1 to 5 in flexible devices.

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