Porous stretchable salt-coated polymer solid electrolyte membrane and preparation method of flexible wearable all-solid-state battery

Abstract

The invention relates to the technical field of batteries, and provides a porous stretchable salt-coated polymer solid electrolyte membrane and a preparation method of a flexible wearable all-solid-state battery, the electrolyte membrane comprises a styrene-isoprene-styrene block copolymer (SIS), naphthenic oil and an electrolyte salt, the mass of the electrolyte membrane is 100%, the mass of the naphthenic oil is 100%, and the mass of the electrolyte salt is 100%. The mass percentage of the electrolyte salt is 70-90%, and the mass ratio of the styrene-isoprene-styrene block copolymer (SIS) to the naphthenic oil is 2: 1. The electrolyte membrane has excellent tensile property, the porosity increases the specific surface area of the electrolyte membrane, more transmission channels are provided for ions, and the ionic conductivity and stability are improved (the electrolyte membrane has stable ionic conductivity at room temperature to 70 DEG C). The preparation method is simple, low in cost and high in controllability, the provided method is not limited to production of an ionic electrolyte membrane, various solid electrolyte membranes such as lithium, zinc and potassium can be produced, and the method can be used for preparing a wearable all-solid-state flexible battery and serves as a flexible power supply at room temperature to supply power to electronic equipment such as a watch.

Description

Technical Field

[0001] The present invention relates to the field of battery technology, and in particular to a porous stretchable salt-encapsulated polymer solid electrolyte membrane and a method for preparing a flexible wearable all-solid-state zinc ion battery thereof. Background Art

[0002] With the continuous development of science and technology, the demand for energy storage and conversion equipment is increasing, especially in the fields of wearable devices, flexible displays and electric vehicles. Although traditional liquid electrolytes have high ion conductivity, they are prone to leakage and poor safety. Solid electrolytes not only have high ion conductivity, but also high safety, and can adapt to equipment of various shapes and sizes, providing strong support for the development of the energy field. Environmental issues are currently the focus of global attention. Traditional energy conversion and storage equipment may cause environmental pollution during production and use. The polymer electrolyte membrane has a relatively environmentally friendly production process and is not easy to produce harmful substances during use, which meets the requirements of sustainable development. With the continuous advancement of electronic information technology, the demand for high-performance and high-reliability electronic components is also increasing. Solid electrolyte membranes can provide better electrochemical performance and mechanical stability to meet the needs of these fields for high-performance electronic components.

[0003] In the prior art, Chinese patent application CN115911591A discloses an intrinsically stretchable polymer electrolyte, wherein the intrinsically stretchable electrolyte is composed of zwitterionic polymer monomers in an electrolyte salt system; wherein: based on deionized water, the amount of deionized water is 2 mL, the mass concentration range of the zwitterionic polymer monomer is 0.1-1.0 g / mL, and the molar concentration range of the electrolyte salt is 1-5 mol / L. CN116487692A discloses a method for preparing a porous PEO-based solid electrolyte material, which is characterized in that it comprises the following steps: Step 1) comprises the following schemes: Scheme 1: Mix polyethylene oxide with lithium bis(trifluoromethanesulfonylimide) and a solvent and stir for 12 to 30 hours; Scheme 2: Mix polyethylene oxide, lithium bis(trifluoromethanesulfonylimide), polyethylene glycol dimethacrylate and a solvent and stir for 8 to 14 hours, then add an inorganic lithium ion conductor and azobisisobutyronitrile and stir for 10 to 14 hours; Scheme 3: Mix polyethylene oxide with lithium bis(trifluoromethanesulfonylimide) and a solvent and stir for 8 to 14 hours, add a plasticizer and stir for 10 to 14 hours, then add an inorganic lithium ion conductor and stir for 10 to 16 hours; Step 2): Let the mixed solution obtained in step 1) stand for 4 to 8 hours; Step 3): Heat the solution obtained in step 2) to 60 to 90° C. to obtain the porous PEO-based solid electrolyte material. CN111574734A discloses a self-healing solid electrolyte film, characterized in that: the self-healing solid electrolyte film comprises the following raw materials: monomer, cross-linking agent, initiator and electrolyte salt, the molar ratio of the cross-linking agent to the monomer is 0.1%, the molar ratio of the initiator to the monomer is 1%, and the concentration of the electrolyte salt in the mixed solution of all raw materials is 0.1mol / L-0.9mol / L. CN110137564A discloses a method for preparing a porous solid electrolyte for lithium ion batteries, characterized in that it comprises the following steps: step S1: preparation of solid electrolyte powder: mixing solid electrolyte material and inorganic pore-forming agent in proportion to obtain solid electrolyte powder; step S2: preparation of solid electrolyte blank: taking the solid electrolyte powder obtained in step S1, preparing solid electrolyte blank by mold cold pressing method or tape casting method; step S3: preparation of solid electrolyte ceramic block: sintering the solid electrolyte blank obtained in step S2 under protective atmosphere to obtain porous solid electrolyte ceramic block.

[0004] However, the semi-solid hydrogel electrolytes in current technology have high liquid content, poor stability, fragile structure and easy failure; traditional all-solid electrolytes, such as PEO solid electrolytes, have high degree of crystallization, poor film forming properties and poor conductivity; porous solid electrolyte membranes such as (PVDFHFP) and porous polyimide (PI) have certain limitations, such as relatively complex preparation process, high cost and poor mechanical properties, which limit their promotion and application in certain fields. In addition, most of the solid electrolyte membrane preparation methods developed by people are based on the synthesis of a solid electrolyte membrane, which limits its scope of application. Summary of the invention

[0005] The embodiments of the present invention provide a porous stretchable salt-coated polymer solid electrolyte membrane and a method for preparing a flexible wearable all-solid-state battery to solve the above-mentioned technical problems of electrolyte membranes in the prior art.

[0006] According to the first aspect, an embodiment of the present invention provides a porous stretchable salt-coated polymer solid electrolyte membrane and a preparation method thereof, wherein the electrolyte membrane comprises: styrene-isoprene-styrene block copolymer (SIS), cyclohexane oil and electrolyte salt, wherein, based on the mass of the electrolyte membrane as 100%, the mass percentage of the electrolyte salt is 70% to 90%, and the mass ratio of styrene-isoprene-styrene block copolymer (SIS) to cyclohexane oil is 2:1. The wearable all-solid-state flexible battery comprises: the current collector is a flexible conductive carbon nanotube film, the battery material is Zn and V2O5 material, and the intermediate electrolyte membrane adopts one of the above-mentioned electrolyte membranes.

[0007] Preferably, the conductivity of the electrolyte membrane at 26 degrees Celsius to 70 degrees Celsius is 0.85*10 -4 ~4.12*10 -4 S cm -1 .

[0008] Preferably, the elastic deformation of the electrolyte membrane having a zinc salt content of 80% by mass is up to 1800%.

[0009] Preferably, the electrolyte salt includes one or more of lithium salt, zinc salt and potassium salt.

[0010] Preferably, the electrolyte salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide, lithium perfluoroethanesulfonyl imide, perfluoromethanesulfonylmethyl lithium, zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), zinc trifluoromethanesulfonate, and potassium bis(fluorosulfonyl)imide (KFSI).

[0011] Preferably, the electrolyte membrane is composed of styrene-isoprene-styrene block copolymer (SIS), cyclohexane oil and electrolyte salt, wherein, based on the mass of the electrolyte membrane as 100%, the mass percentage of the electrolyte salt is 70% to 90%, and the mass ratio of styrene-isoprene-styrene block copolymer (SIS) to cyclohexane oil is 2:1.

[0012] The preparation method comprises the following steps:

[0013] The stretchable porous all-solid polymer electrolyte membrane is obtained by adding electrolyte salt, styrene-isoprene-styrene block copolymer (SIS) and cyclohexane oil into the solvent, mixing and stirring for 2 to 12 hours, and drying for 12 to 36 hours.

[0014] Wherein, based on the mass of the electrolyte membrane being 100%, the mass percentage of the electrolyte salt is 70% to 90%, and the mass ratio of styrene-isoprene-styrene block copolymer (SIS) to cyclohexane oil is 2:1.

[0015] Preferably, the drying comprises pouring into a mold and drying at room temperature.

[0016] Preferably, the solvent includes: chloroform.

[0017] Preferably, the conductivity of the electrolyte membrane at 26 degrees Celsius to 70 degrees Celsius is 0.85*10 -4 ~4.12*10 -4 S cm -1 .

[0018] Preferably, the elastic deformation of the electrolyte membrane having a zinc salt content of 80% by mass is up to 1800%.

[0019] Preferably, the electrolyte salt includes one or more of lithium salt, zinc salt and potassium salt.

[0020] Preferably, the electrolyte salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide, lithium perfluoroethanesulfonyl imide, perfluoromethanesulfonylmethyl lithium, zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), zinc trifluoromethanesulfonate, and potassium bis(fluorosulfonyl)imide (KFSI).

[0021] Preferably, the mass volume ratio of the total mass of the styrene-isoprene-styrene block copolymer (SIS) and the naphthenic oil to the solvent is 0.02-0.06 g / ml.

[0022] The present invention also provides a porous stretchable salt-coated polymer solid electrolyte membrane, which is prepared by any of the methods described above.

[0023] The present invention also provides an application of the electrolyte membrane in a battery.

[0024] The present invention also provides a wearable all-solid-state flexible battery, characterized in that the battery comprises: the current collector is a flexible conductive carbon nanotube film, Zn material is electrodeposited on the conductive carbon nanotube film on one side, V2O5 material is coated on the carbon nanotube film on the other side, and the middle electrolyte membrane adopts one of the electrolyte membranes prepared above, and then is packaged. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The features and advantages of the present invention will be more clearly understood by referring to the accompanying drawings, which are schematic and should not be construed as limiting the present invention in any way. In the accompanying drawings:

[0026] Figure 1 Shown are (a) ionic solid electrolyte membranes containing zinc salt (ZnTFSI) with a mass percentage of 70%, 80% and 90%; (b) ionic solid electrolyte membranes containing lithium salt (LiTFSI) with a mass percentage of 70%, 80% and 90%; (c) ionic solid electrolyte membranes containing potassium salt (KFSI) with a mass percentage of 70%, 80% and 90%.

[0027] Figure 2 Shown are (a) actual size diagram of a zinc ion electrolyte membrane containing 80% zinc salt (ZnTFSI) by mass, (b) bending, (c) twisting, (d) stretching, and (e) actual diagram of the electrolyte membrane after recovery from flexibility tests.

[0028] Figure 3 Shown is a strain and stress curve of a zinc ion electrolyte membrane containing 80% by weight of zinc salt (ZnTFSI).

[0029] Figure 4 Shown are the ionic conductivity diagrams of three solid electrolyte membranes with a salt content of 80% by mass at different temperatures.

[0030] Figure 5 Shown is an all-solid-state wearable battery assembled using an 80% by mass zinc ion electrolyte membrane. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0032] The present invention creatively proposes to use a mixture of styrene-isoprene-styrene block copolymer (SIS) and naphthenic oil as the skeleton material of the electrolyte membrane, which has high elasticity and higher stability, while ensuring the tensile strength and environmental stability of the solid electrolyte. Based on this, a high-flexibility (elastic deformation up to 1800%), high conductivity (0.85*10 -4 ~4.21*10 -4 S cm -1 ) and highly safe all-solid-state electrolytes, which have promoted the development of electronic products such as flexible batteries.

[0033] The present invention provides a porous stretchable salt-coated polymer solid electrolyte membrane and a preparation method thereof, wherein the electrolyte membrane comprises: styrene-isoprene-styrene block copolymer (SIS), cyclohexane oil and electrolyte salt, wherein, based on the mass of the electrolyte membrane being 100%, the mass percentage of the electrolyte salt is 70% to 90%, and the mass ratio of styrene-isoprene-styrene block copolymer (SIS) to cyclohexane oil is 2:1.

[0034] Preferably, the conductivity of the electrolyte membrane at 26 degrees Celsius to 70 degrees Celsius is 0.85*10 -4 ~4.12*10 -4 S cm -1 .

[0035] Preferably, the elastic deformation of the electrolyte membrane having a zinc salt content of 80% by mass is up to 1800%.

[0036] Preferably, the electrolyte salt includes one or more of lithium salt, zinc salt and potassium salt.

[0037] Preferably, the electrolyte salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide, lithium perfluoroethanesulfonyl imide, perfluoromethanesulfonylmethyl lithium, zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), zinc trifluoromethanesulfonate, and potassium bis(fluorosulfonyl)imide (KFSI).

[0038] Preferably, the electrolyte membrane is composed of styrene-isoprene-styrene block copolymer (SIS), cyclohexane oil and electrolyte salt, wherein the mass percentage of the electrolyte salt is 70% to 90% based on the mass of the electrolyte membrane being 100%.

[0039] The preparation method comprises the following steps:

[0040] The stretchable porous all-solid polymer electrolyte membrane is obtained by adding electrolyte salt, styrene-isoprene-styrene block copolymer (SIS) and cyclohexane oil into the solvent, mixing and stirring for 2 to 12 hours, and drying for 12 to 36 hours.

[0041] Wherein, based on the mass of the electrolyte membrane being 100%, the mass percentage of the electrolyte salt is 70% to 90%, and the mass ratio of styrene-isoprene-styrene block copolymer (SIS) to cyclohexane oil is 2:1.

[0042] Preferably, the drying comprises pouring into a mold and drying at room temperature.

[0043] Preferably, the solvent includes: chloroform.

[0044] Preferably, the conductivity of the electrolyte membrane at 26 degrees Celsius to 70 degrees Celsius is 0.85*10 -4 ~4.12*10 -4 S cm -1 .

[0045] Preferably, the elastic deformation of the electrolyte membrane having a zinc salt content of 80% by mass is up to 1800%.

[0046] Preferably, the electrolyte salt includes one or more of lithium salt, zinc salt and potassium salt.

[0047] Preferably, the electrolyte salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide, lithium perfluoroethanesulfonyl imide, perfluoromethanesulfonylmethyl lithium, zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), zinc trifluoromethanesulfonate, and potassium bis(fluorosulfonyl)imide (KFSI).

[0048] Preferably, the mass volume ratio of the total mass of the styrene-isoprene-styrene block copolymer (SIS) and the naphthenic oil to the solvent is 0.02-0.06 g / ml.

[0049] The present invention also provides a porous stretchable salt-coated polymer solid electrolyte membrane, which is prepared by any of the methods described above.

[0050] The present invention also provides an application of the electrolyte membrane in a battery.

[0051] The present invention also provides a battery, comprising: a positive electrode, a negative electrode, and an electrolyte membrane disposed between the positive electrode and the negative electrode, wherein the electrolyte membrane is any one of the above-mentioned electrolyte membranes.

[0052] The porous stretchable salt-coated polymer solid electrolyte membrane and the preparation method thereof provided by the present invention can achieve the following beneficial technical effects:

[0053] 1. Stretchable and porous salt-coated polymer solid electrolyte membranes are relatively scarce. The stretchable solid electrolyte membrane of the present invention has strong mechanical properties, and the porosity improves the ionic conductivity and stability of the electrolyte membrane.

[0054] 2. The existing production of solid electrolyte membranes uses relatively complex technology, while the preparation method provided by the present invention is simple, low-cost and highly controllable.

[0055] 3. The conventional method for preparing solid electrolyte membranes is limited to the production of a single ion electrolyte membrane, while the method provided by the present invention is not limited to the production of a single ion electrolyte membrane, and can produce a variety of solid electrolyte membranes such as lithium, zinc and potassium.

[0056] 4. The present invention provides an all-solid-state electrolyte with high flexibility, high conductivity and high safety, which promotes the development of electronic products such as flexible batteries.

[0057] 5. The hydrogel electrolyte in the prior art has a high liquid component content, poor stability, fragile structure and easy failure. The present invention selects polystyrene-block-polyisoprene-block-polystyrene with high elasticity and higher stability as the skeleton material, while ensuring the tensile property and environmental stability of the solid electrolyte.

[0058] 6. Traditional all-solid-state electrolytes, such as PEO solid-state electrolytes, have a high degree of crystallization, poor film-forming properties, and poor electrical conductivity. The various solid-state electrolyte membranes of the present invention have high flexibility and a porous morphology, and have excellent ionic conductivity, thereby improving battery performance.

[0059] 7. Traditional porous solid electrolyte membranes such as (PVDF HFP) and porous polyimide (PI) have certain limitations, such as relatively complex preparation process and high cost, which limits their promotion and application in certain fields. The method of the present invention is low-cost and simple to operate.

[0060] 8. Traditional liquid electrolyte batteries have safety hazards such as leakage, flammability and explosion, while solid electrolytes can effectively solve these problems. The stretchable porous solid electrolyte membrane provided by the present invention has high ionic conductivity and mechanical flexibility, which can improve the energy density, cycle stability and safety of the battery, thereby improving the overall performance of the battery. Since the stretchable porous solid electrolyte membrane has excellent flexibility and stretchability, it can be used to manufacture batteries of various shapes and sizes, including wearable devices, electric vehicles, aerospace and other fields. This will greatly expand the application field of batteries and provide power support for various new devices.

[0061] Example 1

[0062] The present invention provides a method for preparing a zinc ion electrolyte membrane: 1.2 g of zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), 0.33 g of styrene-isoprene-styrene block copolymer (SIS) and 0.17 g of cyclohexane oil are added to 8-20 ml of chloroform solution, mixed and stirred for 8 hours, poured into a mold and dried at room temperature for 12 hours, and a stretchable porous solid zinc ion electrolyte membrane containing 70% by mass of zinc salt is obtained. Figure 1 (a) The leftmost side shows a solid electrolyte membrane containing 70% by weight of zinc salt (ZnTFSI). Figure 1 As shown, each electrolyte membrane is porous.

[0063] Example 2

[0064] The present invention provides a method for preparing a zinc ion electrolyte membrane: 2.0 g of zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), 0.33 g of styrene-isoprene-styrene block copolymer (SIS) and 0.17 g of cyclohexane oil are added to 8-20 ml of chloroform solution, mixed and stirred for 8 hours, poured into a mold and dried at room temperature for 12 hours, and a stretchable porous solid zinc ion electrolyte membrane containing 80% zinc salt can be obtained. Figure 1 (a) The middle shows a solid electrolyte membrane containing 80% by mass of zinc salt (ZnTFSI). Figure 1 As shown, each electrolyte membrane is porous.

[0065] Figure 2 Shown are (a) the actual size of a zinc ion electrolyte membrane containing 80% zinc salt (ZnTFSI) by mass, (b) bending, (c) twisting, (d) stretching, and (e) the actual picture of the electrolyte membrane after recovery from flexibility test. Figure 2 It can be seen that the original size of the zinc ion electrolyte membrane containing 80% by mass of zinc salt (ZnTFSI) is about 1.8 mm in diameter, and it can still recover to its original size after being stretched to 10 mm, that is, its elastic deformation can reach at least about 555%.

[0066] Figure 3 The strain and stress curve of the zinc ion electrolyte membrane containing 80% zinc salt (ZnTFSI) by mass is shown. Figure 3 It can be seen that its maximum elastic deformation can reach 1800%, and the corresponding strain can reach about 2.5MPa.

[0067] Figure 4 The results show that the prepared membrane with a salt content of 80% has a high conductivity of 1.05*10 -4 ~4.12*10 -4S cm -1 .

[0068] Figure 5 It shows an all-solid-state wearable battery assembled using an 80% by mass zinc ion electrolyte membrane.

[0069] Example 3

[0070] The present invention provides a method for preparing a zinc ion electrolyte membrane: 4.5 g of zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), 0.33 g of styrene-butadiene-styrene three-stage copolymer and 0.17 g of cyclohexane oil are added to 8-20 ml of chloroform solution, mixed and stirred for 8 hours, poured into a mold and dried at room temperature for 12 hours, and a porous stretchable solid zinc ion electrolyte membrane containing 90% by mass of zinc salt is obtained. Figure 1 (a) The last side shows a solid electrolyte membrane containing 90% by weight of zinc salt (ZnTFSI). Figure 1 As shown, each electrolyte membrane is porous.

[0071] The zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI) in the above-mentioned Examples 1-3 may also be replaced by zinc trifluoromethanesulfonate, and a porous all-solid polymer electrolyte membrane may also be obtained.

[0072] Example 4

[0073] The present invention provides a method for preparing a lithium ion electrolyte membrane: 1.2 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 0.33 g of styrene-butadiene-styrene three-stage copolymer and 0.17 g of cyclohexane oil are added to 8-20 ml of chloroform solution, mixed and stirred for 12 hours, poured into a mold and dried at room temperature for 36 hours, and a stretchable porous solid lithium ion electrolyte membrane containing 70% by mass of lithium salt can be obtained. The above operations are all completed in a glove box.

[0074] like Figure 1 (b) The leftmost side shows a solid electrolyte membrane containing 70% lithium salt (LiTFSI) by mass. Figure 1 As shown, each electrolyte membrane is porous.

[0075] Example 5

[0076] The present invention provides a method for preparing a lithium ion electrolyte membrane: 2.0 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 0.33 g of styrene-butadiene-styrene three-stage copolymer and 0.17 g of cyclohexane oil are added to 8-20 ml of chloroform solution, mixed and stirred for 12 hours, poured into a mold and dried at room temperature for 36 hours, and a stretchable porous solid lithium ion electrolyte membrane containing 80% by mass of lithium salt can be obtained. The above operations are all completed in a glove box.

[0077] like Figure 1 (b) The middle shows a solid electrolyte membrane containing 80% lithium salt (LiTFSI) by mass. Figure 1 As shown, each electrolyte membrane is porous. Figure 4 The results show that the solid electrolyte membrane with a salt content of 70% has a high conductivity of 0.95*10 -4 ~3.1*10 -4 S cm -1 .

[0078] Example 6

[0079] The present invention provides a method for preparing a lithium ion electrolyte membrane: 4.5 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 0.33 g of styrene-isoprene-styrene block copolymer (SIS) and 0.17 g of cyclohexane oil are added to 8-20 ml of chloroform solution, mixed and stirred for 12 hours, poured into a mold and dried at room temperature for 36 hours, and a stretchable porous solid lithium ion electrolyte membrane containing 80% by mass of lithium salt can be obtained. The above operations are all completed in a glove box.

[0080] like Figure 1 (b) The last side shows a solid electrolyte membrane containing 90% lithium salt (LiTFSI) by mass. Figure 1 As shown, each electrolyte membrane is porous.

[0081] The lithium bistrifluoromethanesulfonyl imide (LiTFSI) in the above-mentioned embodiments 4-6 can also be replaced by lithium bis(trifluoromethanesulfonyl imide), lithium perfluoroethanesulfonyl imide, or lithium perfluoromethanesulfonylmethyl, and a porous all-solid-state polymer electrolyte membrane can also be obtained.

[0082] Example 7

[0083] The present invention provides a method for preparing a potassium ion electrolyte membrane: 1.2 g potassium bis(fluorosulfonyl)imide (KFSI), 0.33 g styrene-isoprene-styrene block copolymer (SIS) and 0.17 g cyclohexane oil are added to 8-20 ml chloroform solution, mixed and stirred for 12 hours, poured into an Ecoflex mold and dried at room temperature for 36 hours to obtain a stretchable porous solid potassium ion electrolyte membrane containing 70% potassium salt by mass, and the above operations are all completed in a glove box. Figure 1 (c) The leftmost side shows an ionic solid electrolyte membrane containing 70% potassium salt (KFSI) by mass. Figure 1 As shown, each electrolyte membrane is porous.

[0084] Example 8

[0085] The present invention provides a method for preparing a potassium ion electrolyte membrane: 2.0 g potassium bis(fluorosulfonyl)imide (KFSI), 0.33 g styrene-isoprene-styrene block copolymer (SIS) and 0.17 g cyclohexane oil are added to 8-20 ml chloroform solution, mixed and stirred for 12 hours, poured into an Ecoflex mold and dried at room temperature for 36 hours to obtain a stretchable porous solid potassium ion electrolyte membrane containing 80% potassium salt, and the above operations are all completed in a glove box. Figure 1 (c) The middle shows an ionic solid electrolyte membrane containing 80% potassium salt (KFSI) by mass. Figure 1 As shown, each electrolyte membrane is porous.

[0086] Figure 4 The results show that the solid electrolyte membrane with a salt content of 70% has a high conductivity of 0.85*10 -4 ~2.92*10 -4 S cm -1 .

[0087] Example 9

[0088] The present invention provides a method for preparing a potassium ion electrolyte membrane: 4.5 g potassium bis(fluorosulfonyl)imide (KFSI), 0.33 g styrene-isoprene-styrene block copolymer (SIS) and 0.17 g cyclohexane oil are added to 8-20 ml chloroform solution, mixed and stirred for 12 hours, poured into an Ecoflex mold and dried at room temperature for 36 hours to obtain a stretchable porous solid potassium ion electrolyte membrane containing 90% potassium salt by mass, and the above operations are all completed in a glove box. Figure 1 (c) The final measurement shows an ionic solid electrolyte membrane containing 90% potassium salt (KFSI) by mass. Figure 1 As shown, each electrolyte membrane is porous.

[0089] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Those skilled in the art may make various modifications and variations without departing from the spirit and scope of the present invention. Such modifications and variations shall all fall within the scope defined by the appended claims.

Claims

1. A porous stretchable salt-encapsulated polymer solid electrolyte membrane and a wearable all-solid-state flexible battery preparation method, characterized in that: The electrolyte membrane comprises: styrene-isoprene-styrene block copolymer (SIS), cyclohexane oil and electrolyte salt, wherein, based on the mass of the electrolyte membrane being 100%, the mass percentage of the electrolyte salt is 70% to 90%, and the mass ratio of styrene-isoprene-styrene block copolymer (SIS) to cyclohexane oil is 2:

1. The wearable all-solid-state flexible battery is characterized in that the electrode material of the battery is the above-mentioned porous stretchable salt-coated polymer solid electrolyte membrane, the current collector is a flexible conductive carbon nanotube membrane, and the electrode materials are zinc and commercial V2O5.

2. The electrolyte membrane according to claim 1, characterized in that The conductivity of the electrolyte membrane at 26 degrees Celsius to 70 degrees Celsius is 0.85*10 -4 ~4.12*10 -4 S cm -1 ; The elastic deformation of the electrolyte membrane containing 80% zinc salt by mass is up to 1800%.

3. The electrolyte membrane according to claim 1 or 2, characterized in that: The electrolyte salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide, lithium perfluoroethanesulfonylimide, perfluoromethanesulfonylmethyl lithium, zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), zinc trifluoromethanesulfonate and potassium bis(fluorosulfonyl)imide (KFSI); The electrolyte membrane is composed of styrene-isoprene-styrene block copolymer (SIS), cycloalkane oil and electrolyte salt, wherein the mass percentage of the electrolyte salt is 70% to 90% based on the mass of the electrolyte membrane being 100%.

4. A porous stretchable salt-coated polymer solid electrolyte membrane and a wearable all-solid-state flexible battery preparation method, characterized in that: The preparation method comprises the following steps: Add electrolyte salt, styrene-isoprene-styrene block copolymer (SIS), and cycloalkane oil into a solvent, mix and stir for 2 to 12 hours, and dry for 12 to 36 hours to obtain the stretchable porous all-solid-state polymer electrolyte membrane, wherein, based on the mass of the electrolyte membrane being 100%, the mass percentage of the electrolyte salt is 70% to 90%, and the mass ratio of styrene-isoprene-styrene block copolymer (SIS) to cycloalkane oil is 2:

1.

5. The method according to claim 4, characterized in that The drying comprises pouring into a mold and drying at room temperature; The solvent includes: chloroform; The conductivity of the electrolyte membrane at 26 degrees Celsius to 70 degrees Celsius is 0.85*10 -4 ~4.12*10 -4 Scm -1 ; The elastic deformation of the electrolyte membrane with a zinc salt content of 80% by mass is up to 1800%.

6. The method according to claim 4 or 5, characterized in that: The electrolyte salt includes one or more of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide, lithium perfluoroethanesulfonylimide, perfluoromethanesulfonylmethyl lithium, zinc bis(trifluoromethanesulfonyl)imide (ZnTFSI), zinc trifluoromethanesulfonate, and potassium bis(fluorosulfonyl)imide (KFSI).

7. The method according to claim 4 or 5, characterized in that: The mass volume ratio of the total mass of the styrene-isoprene-styrene block copolymer (SIS) and the naphthenic oil to the solvent is 0.02-0.06 g / ml.

8. A porous stretchable salt-coated polymer solid electrolyte membrane, characterized in that: The electrolyte membrane is prepared by the method according to any one of claims 4 to 7.

9. The wearable all-solid-state flexible battery is characterized in that: The battery comprises: a current collector which is a flexible conductive carbon nanotube film, a Zn material is electrodeposited on the conductive carbon nanotube film on one side, a V2O5 material is coated on the carbon nanotube film on the other side, and the middle electrolyte membrane is one of the electrolyte membranes described in any one of claims 1-2 and 8 prepared above, and then packaged.

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