Flexible energy storage device electrolyte material and method of making

Abstract

The application provides a flexible energy storage device electrolyte material and a preparation method thereof. The flexible energy storage device electrolyte material is a flexible gel composite film composed of a porous structure covalent organic framework material and a polymer framework material crosslinked based on PPO and TPPO; a stable artificial lithium ion covalent organic framework channel is constructed on the basis of the flexible polymer framework. The flexible energy storage device electrolyte material has good electrochemical performance on the basis of being bendable, foldable and having excellent tensile properties, can be applied to most flexible energy storage devices, is beneficial to promoting the development of flexible electronic devices, is expected to improve the battery energy storage product competitiveness of related industrial companies, and has important social and economic significance in the popularization and application of battery energy storage.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of flexible gel electrolyte material preparation, and particularly relates to a flexible energy storage device electrolyte material and a preparation method thereof. BACKGROUND

[0002] At present, as a relatively mature electrochemical energy storage technology, the rechargeable lithium ion battery has been widely used in portable electronic devices due to its high power, high energy density, no memory effect and other advantages. However, the traditional lithium ion battery is rigid and fragile, and cannot meet the requirements of wearable electronic products. With the rapid development of wearable electronic technology, people hope to design and develop flexible power supplies with high performance, excellent flexibility and durability for integration into electronic devices. Therefore, it is very important to manufacture wearable batteries with excellent flexibility and durability for wearable electronic devices.

[0003] So far, flexible LIB has been studied for decades, but it has not been well applied in commerce, and the reason may be low energy density, poor mechanical flexibility, poor safety, and unsuitable for scalable applications. Safety has always been a key issue for LIB, and for flexible LIB, safety becomes more challenging. At present, most of the reported flexible LIBs use organic carbonate solvents and polyolefin-based separators, and during the bending process of the flexible battery, the liquid electrolyte has strict requirements on the packaging material due to its fluidity. Once the packaging material is damaged, electrolyte leakage and battery short circuit will cause great safety hazards. Gel polymer electrolyte (GPE) is attracting a lot of interest and is considered a promising candidate to address the potential safety issues of LIBs. Compared with liquid electrolyte, GPE as a film has several advantages in terms of no internal short circuit, no leakage of liquid electrolyte and non-flammability.

[0004] The patent for application with publication number CN112993256A discloses an application of covalent organic framework material in lithium metal negative electrode protection. The COFs material is prepared by Schiff base reaction of monomer 1 and monomer 2, monomer 1 is one of 1,3,5-tris(4-aminophenyl)benzene, 1,3,5-tris(4'-formylphenyl)benzene, 1,3,5-triaminobenzene or benzene-1,3,5-tricarboxaldehyde, and monomer 2 is one of 2,5-dimethoxy-p-xylylene glycol, 2,5-dihydroxy-p-xylylene glycol, 2,5-dimethoxy-p-xylylene diamine, 2,5-dihydroxybenzene diamine, p-xylylene diamine or p-xylylene glycol. The large conjugated six-membered ring structure with C=N functional group as the node, and the three-dimensional spherical structure also contains a regular one-dimensional channel structure. However, the reaction time is long in the preparation process of the material, and a quenching reaction is also needed, which introduces a new solvent, so that multiple solvents need to be used for washing during washing, making the experimental process complex.

[0005] The patent with the publication number CN107437600A discloses a kind of skeleton and gel matrix integration's lithium ion battery active diaphragm and preparation method thereof.Porous membrane is prepared by using linear polymer PVDF or PVDF-HFP as the first component, and linear, comb or hyperbranched amphiphilic polymer with hydrophilic chain end as vinyl as the second component;The formula composition of gel matrix includes: monomer or oligomer containing unsaturated double bond, thermal initiator and solvent.However, azobisisobutyronitrile is used as initiator in the process of synthesizing the diaphragm material, but azobisisobutyronitrile will decompose to produce N2 in the process of thermal initiation, and the generation of bubbles in the polymerization process will cause defects on the surface and inside of the polymer.

[0006] Therefore, it is necessary to design a flexible energy storage device electrolyte material and a preparation method thereof to solve the above problems. SUMMARY

[0007] The present application provides a flexible energy storage device electrolyte material and a preparation method thereof.

[0008] To achieve the above-mentioned purpose of the application, the present application provides a flexible energy storage device electrolyte material, which is a flexible gel composite film composed of a porous covalent organic framework material and a polymer framework material based on PPO and TPPO crosslinking by physical blending and compounding;TPPO and PPO uniformly wrap the covalent organic framework material in the polymer framework material during crosslinking;

[0009] The mass ratio of the covalent organic framework material to the polymer framework material is 1:(23-25);

[0010] The flexible energy storage device electrolyte material builds stable artificial lithium ion covalent organic framework channels on the basis of flexible polymer framework, with an elastic modulus of 0.52 MPa, a tensile elongation at break of 364.07%, and an electrical conductivity of 1.511 x 10 -3 S cm -1 ;The bulk impedance is 4.446 Ω.

[0011] As a further improvement of the present application, the covalent organic framework material is prepared by Schiff base reaction of 1,3,4-tris(aminophenyl)benzene and p-phenylenedimethylaldehyde.

[0012] As a further improvement of the present application, the molar ratio of 1,3,4-tris(aminophenyl)benzene to p-phenylenedimethylaldehyde is 7:4.

[0013] As a further improvement of the present application, in the polymer framework material, PPO is PPO 2300 ;TPPO is TPPO 440 ;The molar ratio of PPO to TPPO is 3:2.

[0014] To achieve the above-mentioned purposes of the application, the application further provides a preparation method of the flexible energy storage device electrolyte material, comprising the following steps:

[0015] S1, preparation of a covalent organic framework material:

[0016] According to a predetermined proportion, 1,3,4-tris(aminophenyl)benzene and p-phenylenedimethylene are dissolved in tetraethylene glycol dimethyl ether, and then subjected to magnetic stirring at 50-70 DEG C oil bath for 0.5-2 h, followed by standing for 10-50 min, centrifugal washing and vacuum drying treatment at 120-180 DEG C, to obtain the covalent organic framework material;

[0017] S2, preparation of a polymer framework material solution:

[0018] According to a predetermined proportion, PPO and TPPO are respectively dissolved in dimethyl carbonate to form a PPO mixed solution and a TPPO mixed solution, and then the TPPO mixed solution is slowly added dropwise into the PPO mixed solution, and magnetic stirring is performed during the dropwise adding process, to obtain the polymer framework material solution;

[0019] S3, preparation of a flexible energy storage device electrolyte material:

[0020] The covalent organic framework material is added into dimethyl carbonate and subjected to ultrasonic treatment for 6-14 h, and then added into the polymer framework material solution, and the mixed solution is poured into a mold, inert gas is introduced for drying for 8-16 h, and then vacuum drying is performed at 40-80 DEG C for 8-16 h, to obtain the flexible energy storage device electrolyte material.

[0021] As a further improvement of the application, in step S1, the molar ratio of 1,3,4-tris(aminophenyl)benzene to p-phenylenedimethylene is 7:4.

[0022] As a further improvement of the application, in step S2, the PPO is PPO 2300 ; and the TPPO is TPPO 440 .

[0023] As a further improvement of the application, in step S2, the molar ratio of PPO to TPPO is 3:2.

[0024] As a further improvement of the application, in step S3, the addition ratio of the covalent organic framework material is 1 / 23-1 / 25 of the polymer framework material formed by crosslinking of TPPO and PPO.

[0025] To achieve the above-mentioned purposes of the application, the application further provides a lithium ion battery, which uses the above-mentioned flexible energy storage device electrolyte material as an electrolyte or a diaphragm.

[0026] The application has the following advantages:

[0027] 1. The preparation method of the flexible energy storage device electrolyte material provided by the application composites the covalent organic framework material with a porous structure and the polymer framework material crosslinked based on PPO and TPPO, and the obtained flexible gel composite film can construct stable artificial lithium ion covalent organic framework channels on the basis of the flexible polymer framework, so that the composite film has good electrochemical performance on the basis of being bendable, foldable and excellent in tensile performance, and can be applicable to most flexible energy storage devices. In the flexible gel composite film electrolyte material system, the porous structure of the covalent organic framework COF is beneficial to the rapid transmission of lithium ions, and the polymer framework makes the composite film flexible, and the working mechanism is as follows:

[0028] First, a flexible and stable polymer framework is established based on the crosslinking structure of PPO and TPPO, and the synthesis route of the polymer framework is as follows:

[0029]

[0030] Among them, the PPO molecule contains two isocyanate groups, and the TPPO molecule contains three amine groups, so the reaction is carried out according to TPPO: PPO = 2:3 (molar ratio) to make the crosslinking reaction system completely react, and as few reaction monomers as possible exist in the system; the crosslinking of PPO and TPPO obtains a polymer containing a polyurea group, which is similar to polyurethane and is a material with a two-phase structure, the chain segment contains hard segments and soft segments, the hard segments play a crosslinking role in the polymer system, and the soft segments can help ion conduction, which has certain mechanical strength and can improve the ion conductivity, avoiding the technical defect of low ion conductivity of a single polymer crosslinking system.

[0031] Then, the crosslinking reaction process of the stable flexible polymer framework is synchronously combined with the mixing process of the covalent organic framework COF, that is, in the process of generating the polymer framework, the polymer framework synchronously occurs physical blending between the covalent organic framework COF, and the polymer framework is generated on one side and the blending is synchronously performed on the other side. Because of the high reactivity, the polymer framework formed rapidly in the crosslinking reaction process can wrap the COF therein, resulting in a stable composite structure, and the stirring is continuously performed in the reaction process to make the COF uniformly distributed between the polymer frameworks.

[0032] Therefore, in the obtained flexible gel composite film, the stable artificial lithium ion channels are constructed based on the rich microporous structure of the COF, and the uniform electroplating / detaching process is caused. In the electrolyte material, the COF and the flexible polymer framework can synergistically act to promote the mechanical properties and electrochemical properties of the flexible gel composite film.

[0033] 2、The flexible energy storage device electrolyte material provided by the application constructs a stable artificial lithium ion covalent organic framework channel on the basis of a flexible polymer framework, the elastic modulus reaches 0.52 MPa, the tensile elongation at break reaches 364.07%, the conductivity reaches 1.511*10 -3 S cm -1 ; the bulk impedance is 4.446 omega, the safety of the electrolyte material is improved, meanwhile, excellent electrochemical performance is ensured, the electrolyte material can be applied to most flexible devices, is conducive to promoting the development of flexible electronic devices, and is expected to improve the battery energy storage product competitiveness of related industrial companies, and has important social and economic significance in the popularization and application of battery energy storage. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The tensile diagram of the flexible energy storage device electrolyte material provided for the embodiment 1 of the application.

[0035] Figure 2 The tensile stress-strain curve diagram of the flexible energy storage device electrolyte material provided for the embodiment 1 of the application.

[0036] Figure 3 The Arrhenius diagram of the flexible energy storage device electrolyte material provided for the embodiment 1 of the application between 30 DEG C and 80 DEG C.

[0037] Figure 4 The EIS characteristic diagram of the flexible energy storage device electrolyte material provided for the embodiment 1 of the application.

[0038] Figure 5 The rate characteristic (0.1C, 0.2C, 0.5C, 1C, 2C, 5C) diagram of the flexible energy storage device electrolyte material provided for the embodiment 1 of the application.

[0039] Figure 6 The EIS characteristic diagram of the flexible energy storage device electrolyte material provided for the embodiment 2 of the application.

[0040] Figure 7 The rate characteristic (0.1C, 0.2C, 0.5C, 1C, 2C, 5C) diagram of the flexible energy storage device electrolyte material provided for the embodiment 2 of the application.

[0041] Figure 8 The EIS characteristic diagram of the flexible energy storage device electrolyte material provided for the embodiment 3 of the application.

[0042] Figure 9 The rate characteristic (0.1C, 0.2C, 0.5C, 1C, 2C, 5C) diagram of the flexible energy storage device electrolyte material provided for the embodiment 3 of the application.

[0043] Figure 10 EIS characteristic diagram of the flexible energy storage device electrolyte material provided for Invention Comparative Example 1.

[0044] Figure 11 Rate characteristic (0.1C, 0.2C, 0.5C, 1C, 2C, 5C) diagram of the flexible energy storage device electrolyte material provided for Invention Comparative Example 1.

[0045] Figure 12 EIS characteristic diagram of the flexible energy storage device electrolyte material provided for Invention Comparative Example 2.

[0046] Figure 13 Rate characteristic (0.1C, 0.2C, 0.5C, 1C, 2C, 5C) diagram of the flexible energy storage device electrolyte material provided for Invention Comparative Example 2. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be described in detail below in combination with the drawings and specific embodiments.

[0048] Here, it also needs to be explained that, in order to avoid the present application being obscured by unnecessary details, only the structures and / or processing steps closely related to the scheme of the present application are shown in the drawings, and other details not closely related to the present application are omitted.

[0049] In addition, it also needs to be explained that the term “comprising”, “including” or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or includes elements inherent to such process, method, article or equipment.

[0050] The present application provides a preparation method of a flexible energy storage device electrolyte material, comprising the following steps:

[0051] S1, preparation of a covalent organic framework material:

[0052] Dissolve 1,3,4-tris(aminophenyl)benzene and p-phenylenedimethylene in tetraethylene glycol dimethyl ether at a predetermined ratio, magnetically stir in an oil bath at 50-70℃ for 0.5-2h, then stand for 10-50min, centrifugal wash and treat with vacuum drying at 120-180℃, to prepare the covalent organic framework material;

[0053] S2, preparation of a polymer framework material solution:

[0054] PPO, TPPO are dissolved in dimethyl carbonate respectively to form PPO mixed solution and TPPO mixed solution according to a predetermined ratio, then the TPPO mixed solution is slowly added into the PPO mixed solution, and magnetic stirring is carried out during the adding process, to obtain a polymer framework material solution;

[0055] S3, preparation of the flexible energy storage device electrolyte material:

[0056] The covalent organic framework material is added into dimethyl carbonate and ultrasonically treated for 6-14 h, then added into the polymer framework material solution, and the blended solution after mixing is poured into a mold, inert gas is introduced for drying for 8-16 h, and then vacuum drying is carried out at 40-80℃ for 8-16 h, to obtain the flexible energy storage device electrolyte material.

[0057] Preferably, in step S1, the molar ratio of 1,3,4-tris(aminophenyl)benzene to p-phenylenedimethylol is 7:4.

[0058] Preferably, in step S2, PPO is PPO 2300 ; and TPPO is TPPO 440 .

[0059] Preferably, in step S2, the molar ratio of PPO to TPPO is 3:2.

[0060] Preferably, in step S3, the adding ratio of the covalent organic framework material is 1 / 23-1 / 25 of the polymer framework material formed by crosslinking of TPPO and PPO.

[0061] Example 1

[0062] The example 1 of the present application provides a preparation method of the flexible energy storage device electrolyte material, which comprises the following steps:

[0063] S1, preparation of the covalent organic framework material: 141 mg of 1,3,4-tris(aminophenyl)benzene and 80 mg of p-phenylenedimethylol are weighed and dissolved in 10 ml of tetraethylene glycol dimethyl ether, and then magnetic stirring is carried out at 60℃ oil bath for 1 h, followed by standing for 30 min, centrifugal washing with DMF (N,N-dimethylformamide) for 5 times, and finally vacuum drying at 150℃ for 12 h, to obtain the covalent organic framework material COF.

[0064] S2, preparation of the polymer framework material solution: 2.3 g of PPO 2300 (isocyanate-terminated polypropylene oxide, Mw=2300) and 0.29 g of TPPO (amine-terminated polypropylene glycol amine, Mw=440) are respectively dissolved in dimethyl carbonate to form PPO mixed solution and TPPO mixed solution, and the TPPO mixed solution is slowly added into the PPO 2300The mixed solution is subjected to magnetic stirring during the dropping process to obtain a polymer framework material solution.

[0065] S3, preparation of a flexible energy storage device electrolyte material: 108 mg of COF was weighed and added to 10 mL of dimethyl carbonate and ultrasonically treated for 10 h, and then added to the polymer framework material solution. The blended solution was poured into a polytetrafluoroethylene mold, dried under inert gas for 12 h, and then vacuum dried at 60℃ for 12 h. The above operations were all carried out in a glove box to obtain a flexible energy storage device electrolyte material (flexible gel composite film), which was denoted as a PT / COF composite film.

[0066] The flexible energy storage device electrolyte material prepared in the application was applied to a lithium ion battery, including the following steps:

[0067] P1, preparation of a half battery:

[0068] The flexible gel composite film prepared above was used as a separator, 1M LiTFSI was used as the electrolyte of the battery, metal lithium was used as the negative electrode, and lithium iron phosphate was used as the positive electrode to prepare a lithium ion battery.

[0069] Performance test:

[0070] I. Thin film tensile property test:

[0071] The PT / COF composite film prepared in Example 1 was subjected to tensile property test, the sample width was 4 mm, the sample thickness was 0.15 mm, and the original gauge length of the sample was 43 mm.

[0072] II. Electrochemical performance test:

[0073] Electrochemical impedance spectroscopy (EIS): the test frequency was 0.01-100000 Hz, and the voltage amplitude was 5 mV.

[0074] Rate characteristic test: the theoretical capacity of the material was 160 mAh / g, and the test rate parameters were 0.1C, 0.2C, 0.5C, 1C, 2C and 5C.

[0075] Variable temperature conductivity test: the ionic conductivity was evaluated by Arrhenius plot, and the test temperature was 30℃, 40℃, 50℃, 60℃, 70℃ and 80℃.

[0076] Performance result analysis:

[0077] Please refer to Figure 1 The tensile schematic diagram shown in the figure indicates that the PT / COF composite electrolyte film can be bent, folded and stretched with a certain strength, and can be applied to most flexible devices.

[0078] Please refer to Figure 2The tensile stress-strain curve shows that the elastic modulus of the PT / COF composite electrolyte film is 0.52 MPa, and the breaking elongation is 364.07%, which has good flexibility.

[0079] Referring to Figure 3 The Arrhenius plot of the PT / COF composite electrolyte film between 30°C and 80°C shows that the plot is basically consistent with the Arrhenius equation, indicating that the conductivity of the PT / COF gel electrolyte is basically not affected by temperature.

[0080] The electrolyte material prepared in Example 1 constructs a stable artificial lithium ion covalent organic framework channel on the basis of a flexible polymer framework, with an elastic modulus of 0.52 MPa, a breaking elongation of 364.07%, and a conductivity of 1.511 x 10 -3 S cm -1 ; the bulk impedance is 4.446 Ω.

[0081] Referring to Figure 4 The EIS characteristic diagram of the PT / COF composite electrolyte film shows that Figure 5 The rate characteristic diagram of the PT / COF composite electrolyte film shows that the electrolyte material prepared in Example 1 has excellent electrochemical performance.

[0082] Comparative Example 1

[0083] Without adding COF, the polymer framework material is directly used for preparation of the electrolyte material.

[0084] Comparative Example 2

[0085] The PPO polymer is directly used for preparation of the polymer framework material.

[0086] Example 2-3

[0087] The difference from Example 1 is that the added mass of the covalent organic framework material COF in step S3 is different, and the others are the same as Example 1, which will not be repeated here.

[0088]

[0089] As can be seen from the above table, the electrolyte material prepared in Example 2 constructs a stable artificial lithium ion covalent organic framework channel on the basis of a flexible polymer framework, with an elastic modulus of 0.56 MPa, a breaking elongation of 369.27%, and a conductivity of 1.232 x 10 -3 S cm -1 ; the bulk impedance is 7.419 Ω.

[0090] The electrolyte material prepared in Example 3 constructs stable artificial lithium ion covalent organic framework channels on the basis of a flexible polymer framework, and has an elastic modulus of 0.46 MPa, a breaking elongation of 354.82%, and an ionic conductivity of 8.456 x 10 -4 S cm -1 ; and a bulk impedance of 5.651 Ω.

[0091] The data of Examples 2-3 show that the addition of COF in the process of cross-linking reaction to generate a polymer framework material can reduce the tensile properties of the polymer to a certain extent, the small amount of COF added in Example 2 cannot cover the entire polymer film, and the large amount of COF added in Example 3 can cause the COF to agglomerate to a certain extent on the surface of the polymer film, resulting in defects, so the ionic conductivity is lower than that of Example 1, and therefore, in the present application, the optimal ratio of COF to polymer framework material is 1:24.

[0092] It can be seen that the electrolyte materials of Examples 2-3 have excellent electrochemical properties. Figures 6-9

[0093] After testing, the bulk impedance of the electrolyte materials of Comparative Examples 1 and 2 is 13.73 Ω and 9.42 Ω, respectively, which is much higher than that of Example 1.

[0094] It can be seen from the above table and Figures 10-13 that the electrochemical properties of the electrolyte material of Example 1 are superior to those of Comparative Examples 1-2, indicating that in the electrolyte material provided by the present application, stable artificial lithium ion channels are constructed on the basis of the rich microporous structure of COF, and the COF and the flexible polymer framework can synergistically promote the mechanical properties and electrochemical properties of the flexible gel composite film.

[0095] In summary, the present application provides a flexible energy storage device electrolyte material and a preparation method thereof. The flexible energy storage device electrolyte material is a flexible gel composite film composed of a porous covalent organic framework material and a polymer framework material based on PPO and TPPO cross-linking; and stable artificial lithium ion covalent organic framework channels are constructed on the basis of a flexible polymer framework. The flexible energy storage device electrolyte material has excellent electrochemical properties on the basis of being bendable, foldable and having excellent tensile properties, and can be applied to most flexible energy storage devices, which is conducive to promoting the development of flexible electronic devices and is expected to improve the competitiveness of battery energy storage products of related industrial companies, and has important social and economic significance in the promotion and application of battery energy storage.

[0096] ​The above examples are only used to illustrate the technical solutions of the present application but not limit the present application. Although the present application is described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalent replaced without departing from the spirit and scope of the technical solutions of the present application.

Claims

1. A flexible energy storage device electrolyte material, characterized by: The flexible energy storage device electrolyte material is a flexible gel composite film prepared by physical blending and compounding of both a porous structure covalent organic framework material and a polymer framework material crosslinked based on PPO and TPPO; TPPO and PPO synchronously uniformly wrap the covalent organic framework material in the polymer framework material generated in the crosslinking reaction in the process of crosslinking; the mass ratio of the covalent organic framework material to the polymer framework material is 1:(23-25); In the formula, PPO is an isocyanate-terminated polypropylene oxide, and the structural formula is as follows: TPPO is an amine-terminated polypropylene glycol amine, and the structural formula is as follows: 。 2. The flexible energy storage device electrolyte material of claim 1, wherein: The covalent organic framework material is prepared by Schiff base reaction of 1,3,4-tris(aminophenyl)benzene and p-phthalaldehyde.

3. The flexible energy storage device electrolyte material of claim 2, wherein: The molar ratio of 1,3,4-tris(aminophenyl)benzene to p-phthalaldehyde is 7:

4.

4. The flexible energy storage device electrolyte material of claim 1, wherein: In the polymer framework material, PPO is PPO 2300 , Mw = 2300; TPPO is TPPO 440 , Mw = 440; the molar ratio of PPO and TPPO is 3:

2.

5. The method of any one of claims 1 to 4, wherein the flexible energy storage device electrolyte material is prepared by: The method comprises the following steps: S1, preparation of a covalent organic framework material: 1,3,4-tris(aminophenyl)benzene and p-phthalaldehyde are dissolved in tetraethylene glycol dimethyl ether at a predetermined ratio, and then subjected to magnetic stirring at 50-70°C for 0.5-2h, followed by standing for 10-50min, centrifugal washing and vacuum drying at 120-180°C to prepare the covalent organic framework material; S2, preparation of a polymer framework material solution: PPO and TPPO are respectively dissolved in dimethyl carbonate to form a PPO mixed solution and a TPPO mixed solution, and then the TPPO mixed solution is slowly added dropwise into the PPO mixed solution, and magnetic stirring is performed during the dropping process to obtain the polymer framework material solution; S3, preparation of a flexible energy storage device electrolyte material: The covalent organic framework material is added into dimethyl carbonate and subjected to ultrasonic treatment for 6-14h, and then added into the polymer framework material solution, and the blended solution after mixing is poured into a mold, inert gas is introduced for drying for 8-16h, and then vacuum drying is performed at 40-80°C for 8-16h to prepare the flexible energy storage device electrolyte material.

6. The method of claim 5, wherein the method further comprises: In step S1, the molar ratio of 1,3,4-tris(aminophenyl)benzene to p-phthalaldehyde is 7:

4.

7. The method of claim 5, wherein the method further comprises: In step S2, PPO is PPO 2300 , Mw = 2300; TPPO is TPPO 440 , Mw = 440.

8. The method for preparing an electrolyte material for a flexible energy storage device according to claim 5, characterized in that: In step S2, the molar ratio of PPO to TPPO is 3:

2.

9. The method for preparing an electrolyte material for a flexible energy storage device according to claim 5, characterized in that: In step S3, the addition ratio of the covalent organic framework material to the polymer framework material crosslinked based on PPO and TPPO is 1 / 23-1 / 25, and the addition ratio is a mass ratio.

10. A lithium-ion battery, characterized by: The lithium ion battery uses the flexible energy storage device electrolyte material prepared by the preparation method of any one of claims 5 to 9 as a separator.

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