Preparation method of flexible MOF glass quasi-solid electrolyte and lithium battery

Abstract

The invention provides a preparation method of a flexible MOF glass quasi-solid electrolyte and a lithium battery. The preparation method comprises the following steps: carrying out ball milling treatment on MOF glass to decompose part of the MOF glass on the surface into a small molecule form which plays a role of a foaming agent under mechanical acting force to obtain pretreated MOF glass, then mixing the pretreated MOF glass and a polymer, sintering, cooling, soaking in an electrolyte, taking out, and drying to obtain the MOF glass. The flexible MOF glass quasi-solid electrolyte is obtained. The surface of MOF glass particles is locally decomposed into small molecular structures through a ball milling mechanical method, the small molecular structures play a role of a foaming agent in the MOF glass quasi-solid electrolyte firing process, and graded mass transfer pore channels containing macropores, mesopores and micropores can be constructed. The crystal boundary-free MOF glass with the hierarchical porous structure is expected to solve the problems of poor ionic conductivity and easy growth of lithium dendrites at the crystal boundary of the existing MOF-based solid electrolyte.

Description

Technical Field

[0001] The present invention belongs to the technical field of battery electrolytes, and in particular relates to a preparation method of a flexible MOF glass quasi-solid electrolyte and a lithium battery. Background Art

[0002] Metal-organic frameworks (MOFs) have attracted considerable attention due to their exceptionally large surface area and highly ordered porous structure. By rationally selecting different metal centers and organic ligands, the pore size, shape, and functional properties of MOFs can be precisely controlled, endowing MOF materials with a high degree of designability and versatility. This unique property holds great promise for MOF applications in batteries. MOF-based solid electrolytes, fabricated by encapsulating liquid electrolytes within MOF structures, exhibit both excellent ion transport and high safety. However, practical applications of MOF-based solid electrolytes urgently require addressing the negative effects of their grain boundary structure. On the one hand, the activation energy for lithium ion migration at grain boundaries is significantly higher than that within the crystal interior, resulting in poor ionic conductivity in MOF crystals with abundant grain boundaries. On the other hand, due to the electronic conductivity of grain boundaries, lithium dendrites easily grow at MOF grain boundaries, causing irreversible structural damage to the MOF-based solid electrolyte through tip stress and crack propagation, ultimately leading to battery short circuits.

[0003] For a long time, researchers have been committed to using methods such as crystal plane orientation regulation and polymer coating post-treatment to reduce grain boundary defects between MOF crystals, but the grain boundary problem has not been completely solved. As a new type of MOF material, MOF glass inherits the chemical composition and partial network structure of the crystalline precursor, eliminates the grain boundary structure, and presents a long-range disordered and short-range ordered structural feature. The emergence of MOF glass is expected to promote the development of high-performance MOF benchmark solid electrolytes without grain boundary structure. MOF glass is isotropic and highly plastic, and is an excellent ion conductor. Using it as a quasi-solid electrolyte can provide an isotropic transmission pathway for ion conduction, making Li + Rapid and uniform migration effectively inhibits the formation of dendrites and improves the cycle life of the battery.

[0004] The ion transport performance of MOF glass is closely related to factors such as ligands, metal sites, pore size and porosity. Among them, pore size and porosity are the factors that need to be paid attention to in practical applications of MOF glass. On the one hand, because the preparation of MOF glass usually requires heating, pressurization or other mechanical means, the porosity of MOF glass will be reduced due to the collapse of part of the porous framework, thus generating many obstacles to Li +On the other hand, the pore size of MOF glass is in the sub-nanometer range. The smaller pore size reduces the mass transfer efficiency of ions inside it. It is necessary to construct a hierarchical pore structure with better mass transfer to break through the diffusion limitation of ultra-microporous MOF glass.

[0005] For example, the patent application with publication number CN117457980A discloses the formulation technology of glassy MOFs quasi-solid-state sodium ion electrolyte. The formulation is based on an ultra-thin flexible glassy membrane and uses organic liquid electrolytes, ester solvents, ether solvents, ionic liquids and other different additives as fillers to construct a quasi-solid-state sodium ion electrolyte. The ion channel size of the electrolyte is at the sub-nanometer level.

[0006] Therefore, exploring methods to increase the porosity and pore size distribution of MOF glass is beneficial to improving the ionic conductivity of MOF glass. In addition, since MOF glass contains weak coordination bonds, its fracture toughness is low, so enhancing its fracture toughness should also be considered in practical applications. Summary of the Invention

[0007] In order to solve the above technical problems existing in the prior art, the present invention provides a preparation method of a flexible MOF glass quasi-solid electrolyte and a lithium battery.

[0008] The present invention provides a method for preparing a flexible MOF glass quasi-solid electrolyte, comprising the following steps: ball-milling the MOF glass to decompose the surface portion of the MOF glass into small molecules that act as a foaming agent under mechanical force to obtain pretreated MOF glass; then mixing the pretreated MOF glass with a polymer, sintering the mixture, cooling it, and then soaking it in an electrolyte before taking it out to obtain the flexible MOF glass quasi-solid electrolyte.

[0009] Preferably, the ball milling process is performed at a rotation speed of 50-300 rpm for 5-20 minutes. Further preferably, the ball milling process is performed at a rotation speed of 300 rpm for 20 minutes, and the resulting flexible MOF glass quasi-solid electrolyte has better rate performance.

[0010] Preferably, the MOF glass is ZIF-62.

[0011] Preferably, the thermal degradation temperature of the polymer is higher than the sintering temperature used; the polymer is further preferably at least one of polyimide, polybenzimidazole and polyetheretherketone.

[0012] Further preferably, the preparation method of ZIF-62 comprises the following steps: Zn(NO₃)₂·6H₂O, imidazole, and benzimidazole are uniformly mixed in an organic solution at a molar ratio of 1:1.5:13.5, placed in a sealed reactor, and reacted at 120°C-140°C for 48-72 hours. After completion of the reaction, the mixture is washed and dried to obtain the MOF glass. The reaction temperature is more preferably 130°C.

[0013] Preferably, the mass ratio of the MOF glass to the polymer is 1:0.4-2.4. Further preferably, the mass ratio of the MOF glass to the polymer is 7:3. The MOF glass content is higher, and the ionic conductivity of the prepared flexible MOF glass quasi-solid electrolyte is higher.

[0014] Preferably, the sintering temperature is 390-420° C., the sintering time is 20-60 min, and the sintering is performed under an inert atmosphere.

[0015] Preferably, the electrolyte comprises a solute and a solvent, wherein the solute is one of lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl imide), and lithium bis(fluorosulfonyl imide), and the solvent is an ether solvent or an ester solvent. The concentration of the solute is 1-3 mol / L. The concentration of the solute is more preferably 1 mol / L.

[0016] More preferably, the ether solvent is at least one of 1,3-dioxolane, 1,2-dimethoxyethane and diethylene glycol dimethyl ether, and the ester solvent is at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate.

[0017] Preferably, the immersion time in the electrolyte is 12-24 hours. The purpose of immersion in the electrolyte is to allow the electrolyte to enter the pore structure of the mixed matrix membrane obtained after sintering to form an ion-conducting path.

[0018] The present invention also provides a flexible MOF glass quasi-solid electrolyte, which is prepared by adopting the preparation method of the flexible MOF glass quasi-solid electrolyte.

[0019] The present invention also provides a lithium battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the flexible MOF glass quasi-solid electrolyte.

[0020] Compared with the prior art, the present invention has the following beneficial effects: This invention uses a mechanical method called ball milling to locally decompose the surface of MOF glass particles into small molecular structures. These small molecular structures act as foaming agents during the firing process of the MOF glass quasi-solid electrolyte, creating hierarchical mass transfer channels containing macropores, mesopores, and micropores without the need for additional foaming agents. This grain-boundary-free MOF glass with a multi-level pore structure is expected to address the problems of existing MOF-based solid electrolytes, such as poor ionic conductivity and the growth of lithium dendrites at grain boundaries. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is a scanning electron microscope image, where Figure 1 (a) is ZIF-62 before ball milling in Example 1, Figure 1 (b) is the ZIF-62 after ball milling in Example 1. Figure 1 (c) in the figure is ZIF-62 after ball milling in Example 2.

[0022] Figure 2 Digital photos of different quasi-solid electrolytes, among which, Figure 2 (a), (b), and (c) are the quasi-solid electrolytes prepared in Comparative Examples 1, 2, and 3, respectively. Figure 2 (d), (e), and (f) are the quasi-solid electrolytes prepared in Examples 1, 2, and 3, respectively.

[0023] Figure 3 The rate performance of batteries assembled with different quasi-solid-state electrolytes. DETAILED DESCRIPTION

[0024] Example 1 In this embodiment, the mass ratio of ZIF-62 (MOF glass) to polyimide is 3:7.

[0025] (1) In this embodiment, the preparation method of ZIF-62 is as follows: Zn(NO₃)₂·6H₂O, imidazole, and benzoimidazole were mixed in an N,N-dimethylformamide solution at a molar ratio of 1:1.5:13.5 and stirred for 2 hours. The mixture was then transferred to an autoclave and reacted at 130°C for 48 hours. After the reaction, the mixture was washed four times with N,N-dimethylformamide and then dried under vacuum at 150°C for 12 hours.

[0026] (2) In this embodiment, the pretreatment of ZIF-62 is as follows: The ZIF-62 prepared in step (1) was added to a ball mill and ball milled at 50 rpm for 5 min.

[0027] (3) In this embodiment, the MOF glass quasi-solid electrolyte fired embryo was prepared as follows: the pretreated ZIF-62 powder and the polyimide powder were ground and mixed in a mortar at a mass ratio of 3:7, and then poured into a mold and pressed into a disc embryo (the diameter of the embryo was 14 mm and the thickness was 100 μm, the same below).

[0028] (4) In this embodiment, the porous flexible MOF glass quasi-solid electrolyte is prepared as follows: the disc blank prepared in step (3) is placed in a quartz ark and fired at 390°C for 20 minutes under an argon atmosphere. After natural cooling, it is immersed in an electrolyte for 12 hours and then taken out to obtain a porous flexible MOF glass quasi-solid electrolyte. The solute of the electrolyte used is lithium bis(trifluoromethanesulfonylimide) with a solute concentration of 1 mol / L, and the solvent is 1,3-dioxolane and 1,2-dimethoxyethane in a volume ratio of 1:1.

[0029] Application of quasi-solid electrolytes in lithium batteries: LiFePO4 is used as the positive electrode, lithium sheet is used as the negative electrode, and they are assembled into a button battery with porous flexible MOF glass quasi-solid electrolyte.

[0030] Example 2 In this embodiment, the mass ratio of ZIF-62 (MOF glass) to polyimide is 3:7.

[0031] (1) In this embodiment, the preparation method of ZIF-62 is as follows: Zn(NO₃)₂·6H₂O, imidazole, and benzoimidazole were mixed in an N,N-dimethylformamide solution at a molar ratio of 1:1.5:13.5 and stirred for 2 hours. The mixture was then transferred to an autoclave and reacted at 130°C for 72 hours. After the reaction, the mixture was washed four times with N,N-dimethylformamide and then dried under vacuum at 150°C for 12 hours.

[0032] (2) In this embodiment, the pretreatment of ZIF-62 is as follows: The ZIF-62 prepared in step (1) was added to a ball mill and ball milled at 300 rpm for 20 min.

[0033] (3) In this embodiment, the MOF glass quasi-solid electrolyte fired embryo is prepared as follows: the pretreated ZIF-62 powder and the polyimide powder are ground and mixed in a mortar at a mass ratio of 3:7, and then poured into a mold and pressed into a disc embryo.

[0034] (4) In this embodiment, the porous flexible MOF glass quasi-solid electrolyte is prepared as follows: the disc blank prepared in step (3) is placed in a quartz ark and fired at 420°C for 60 minutes under an argon atmosphere. After natural cooling, it is immersed in an electrolyte for 24 hours and then taken out to obtain a porous flexible MOF glass quasi-solid electrolyte. The solute of the electrolyte used is lithium bis(trifluoromethanesulfonyl)imide with a solute concentration of 1 mol / L, and the solvent is 1,3-dioxolane and 1,2-dimethoxyethane in a volume ratio of 1:1.

[0035] Application of quasi-solid electrolytes in lithium batteries: LiFePO4 is used as the positive electrode, lithium sheet is used as the negative electrode, and they are assembled into a button battery with porous flexible MOF glass quasi-solid electrolyte.

[0036] Example 3 In this embodiment, the mass ratio of ZIF-62 (MOF glass) to polyimide is 7:3.

[0037] (1) In this example, the preparation method of ZIF-62 is the same as that in Example 2.

[0038] (2) In this example, the pretreatment of ZIF-62 is the same as that in Example 2.

[0039] (3) In this embodiment, the MOF glass quasi-solid electrolyte fired embryo is prepared as follows: the pretreated ZIF-62 powder and the polyimide powder are ground and mixed in a mortar at a mass ratio of 7:3, and then poured into a mold and pressed into a disc embryo.

[0040] (4) In this embodiment, the porous flexible MOF glass quasi-solid electrolyte is prepared as follows: the disc blank prepared in step (3) is placed in a quartz ark and fired at 420°C for 60 minutes under an argon atmosphere. After natural cooling, it is immersed in an electrolyte for 24 hours and then taken out to obtain a porous flexible MOF glass quasi-solid electrolyte. The solute of the electrolyte used is lithium bis(trifluoromethanesulfonyl)imide with a solute concentration of 1 mol / L, and the solvent is 1,3-dioxolane and 1,2-dimethoxyethane in a volume ratio of 1:1.

[0041] Application of quasi-solid electrolytes in lithium batteries: LiFePO4 is used as the positive electrode, lithium sheet is used as the negative electrode, and they are assembled into a button battery with porous flexible MOF glass quasi-solid electrolyte.

[0042] Comparative Example 1 The quasi-solid electrolyte of this embodiment contains ZIF-62 (MOF glass) and does not contain a polymer.

[0043] (1) In this example, the preparation method of ZIF-62 is the same as that in Example 2.

[0044] (2) In this embodiment, ZIF-62 was not pretreated.

[0045] (3) In this embodiment, the quasi-solid electrolyte fired embryo body is prepared as follows: ZIF-62 powder is ground in a mortar and then poured into a mold and pressed into a disc embryo body.

[0046] (4) In this embodiment, the quasi-solid electrolyte is prepared by placing the wafer blank prepared in step (3) in a quartz ark and firing it at 420°C for 60 minutes under an argon atmosphere. After natural cooling, it is immersed in an electrolyte for 24 hours and then taken out to obtain a porous flexible MOF glass quasi-solid electrolyte. The solute of the electrolyte used is lithium bis(trifluoromethanesulfonyl)imide with a solute concentration of 1 mol / L, and the solvent is 1,3-dioxolane and 1,2-dimethoxyethane in a volume ratio of 1:1.

[0047] Comparative Example 2 In this embodiment, the mass ratio of ZIF-62 (MOF glass) to polyimide is 3:7.

[0048] (1) In this example, the preparation method of ZIF-62 is the same as that in Example 1.

[0049] (2) In this embodiment, ZIF-62 was not pretreated.

[0050] (3) In this embodiment, the MOF glass quasi-solid electrolyte fired embryo is prepared as follows: the pretreated ZIF-62 powder and the polyimide powder are ground and mixed in a mortar at a mass ratio of 3:7, and then poured into a mold and pressed into a disc embryo.

[0051] (4) In this embodiment, the porous flexible MOF glass quasi-solid electrolyte is prepared as follows: the disc blank prepared in step (3) is placed in a quartz ark and fired at 390°C for 20 minutes under an argon atmosphere. After natural cooling, it is immersed in an electrolyte for 12 hours and then taken out to obtain a porous flexible MOF glass quasi-solid electrolyte. The solute of the electrolyte used is lithium bis(trifluoromethanesulfonylimide) with a solute concentration of 1 mol / L, and the solvent is 1,3-dioxolane and 1,2-dimethoxyethane in a volume ratio of 1:1.

[0052] Application of quasi-solid electrolytes in lithium batteries: LiFePO4 is used as the positive electrode, lithium sheet is used as the negative electrode, and they are assembled into a button battery with a quasi-solid electrolyte.

[0053] Comparative Example 3 In this embodiment, the mass ratio of ZIF-62 (MOF glass) to polyimide is 7:3.

[0054] (1) In this example, the preparation method of ZIF-62 is the same as that in Example 2.

[0055] (2) In this embodiment, ZIF-62 was not pretreated.

[0056] (3) In this embodiment, the MOF glass quasi-solid electrolyte fired embryo is prepared as follows: the pretreated ZIF-62 powder and the polyimide powder are ground and mixed in a mortar at a mass ratio of 7:3, and then poured into a mold and pressed into a disc embryo.

[0057] (4) In this embodiment, the preparation of the MOF glass quasi-solid electrolyte is as follows: the disc blank prepared in step (3) is placed in a quartz ark and fired at 420°C for 60 minutes under an argon atmosphere. After natural cooling, it is immersed in an electrolyte for 24 hours and then taken out to obtain a porous flexible MOF glass quasi-solid electrolyte. The solute of the electrolyte used is lithium bis(trifluoromethanesulfonyl)imide with a solute concentration of 1 mol / L, and the solvent is 1,3-dioxolane and 1,2-dimethoxyethane in a volume ratio of 1:1.

[0058] Application of quasi-solid electrolytes in lithium batteries: LiFePO4 is used as the positive electrode, lithium sheet is used as the negative electrode, and they are assembled into a button battery with a quasi-solid electrolyte.

[0059] Test Example 1 1. Experimental Materials The quasi-solid electrolyte and the battery assembled therefrom prepared under the conditions of Example 1, the ZIF-62 and the quasi-solid electrolyte and the battery assembled therefrom prepared under the conditions of Example 2 before and after ball milling, the ZIF-62 and the quasi-solid electrolyte and the battery assembled therefrom prepared under the conditions of Example 3 before and after ball milling, the quasi-solid electrolyte prepared under the conditions of Comparative Example 1, the quasi-solid electrolyte and the battery assembled therefrom prepared under the conditions of Comparative Example 2, and the quasi-solid electrolyte and the battery assembled therefrom prepared under the conditions of Comparative Example 3 were used as experimental materials.

[0060] 2. Experimental methods 1) Scanning electron microscopy: The ZIF-62 before and after ball milling in Example 2 and the ZIF-62 after ball milling in Example 3 were attached to an electron microscope sample stage covered with conductive adhesive and placed in a gold-spraying apparatus. The sample morphology was then observed using a scanning electron microscope (Scios2 Hivac) at a voltage of 10 kV and a magnification of 2000x.

[0061] 2) Optical photos: The quasi-solid electrolytes prepared in Examples 1-3 and Comparative Examples 1-3 were photographed and recorded using a digital camera, and the sample morphology was observed.

[0062] 3) Fracture toughness test: The quasi-solid electrolytes prepared in Comparative Example 1, Example 2, and Example 3 were clamped at the bottom with a clip and at the top with tweezers and slowly bent while measuring the bending angle with a protractor until the quasi-solid electrolyte broke. The bending angle at this time was recorded.

[0063] 4) Battery performance: The button cells assembled with the quasi-solid electrolytes prepared in Examples 1-3 and Comparative Examples 2-3 were installed in the Xinwei battery testing system and cycled for 5 cycles at 0.2 C, 0.5 C, 1 C, 2 C, and 5 C in rate mode.

[0064] 3. Experimental results 1) Scanning electron microscope test: Figure 1 Scanning electron microscopy results show that the surface structure of ZIF-62 crystals is destroyed after ball milling, resulting in the formation of small particles. The degree of destruction and the number of small particles increase with increasing ball milling speed and time. The small molecules contained in these small particles can act as foaming agents.

[0065] 2) Optical photos: Figure 2 These are digital photos of different quasi-solid electrolytes obtained after high-temperature sintering. Figure 2 It can be observed that the MOF glass prepared in Comparative Example 1 is translucent, and the transparency of the quasi-solid electrolyte containing polyimide is greatly reduced. By comparing the surface morphology of the different quasi-solid electrolytes prepared in Comparative Examples 2-3 and Examples 1-3, it can be found that the quasi-solid electrolyte fired by ZIF-62 pretreated by ball milling has a cellular structure, and the number of pores increases with the increase of firing temperature and time. The above results show that the small molecules produced by ball milling pretreatment of ZIF-62 can be used as foaming agents to construct a multi-level pore structure in the quasi-solid electrolyte.

[0066] 3) Fracture Toughness Test: Table 1 shows the bending angles at the moment of fracture for various quasi-solid electrolytes. As can be seen from the table, the MOF glass quasi-solid electrolyte prepared in Comparative Example 1 exhibits extremely poor toughness and is virtually unbendable. Due to the addition of polyimide, the porous flexible MOF glass quasi-solid electrolytes prepared in Examples 2 and 3 exhibit superior toughness and can bend significantly. These results demonstrate that the poor fracture toughness of MOF glass can be addressed by introducing a flexible polymer.

[0067] Table 1 Bending angles at the moment of fracture of different quasi-solid electrolytes

[0068] 4) Electrochemical performance test: Figure 3The figure shows the rate performance of batteries assembled with different quasi-solid electrolytes. As can be seen from the figure, the rate performance of batteries assembled with the porous flexible MOF glass quasi-solid electrolytes prepared in Examples 1-3 is significantly better than that of batteries assembled with the flexible MOF glass quasi-solid electrolytes prepared in Comparative Examples 2 and 3. Among them, the battery assembled with the porous flexible MOF glass quasi-solid electrolyte prepared in Example 3, which has a higher MOF glass content, a higher firing temperature, and a longer firing time, has the best performance.

[0069] In summary, the present invention adopts the strategy of toughening with high-temperature resistant flexible polymer polyimide and ball milling pretreatment of ZIF-62 for high-temperature self-foaming to prepare a porous flexible MOF glass quasi-solid electrolyte with excellent battery performance, solving the problems of poor fracture toughness and low mass transfer efficiency of MOF glass.

Claims

1. A method for preparing a flexible MOF glass quasi-solid electrolyte, characterized in that: The method comprises the following steps: ball milling MOF glass to decompose the surface portion of the MOF glass into small molecules that act as a foaming agent under mechanical force to obtain pretreated MOF glass; then mixing the pretreated MOF glass with a polymer, sintering the mixture, cooling the mixture, and then soaking the mixture in an electrolyte before taking it out to obtain the flexible MOF glass quasi-solid electrolyte.

2. The method for preparing a flexible MOF glass quasi-solid electrolyte according to claim 1, characterized in that: The ball milling treatment is performed at a rotation speed of 50-300 rpm for 5-20 minutes.

3. The method for preparing a flexible MOF glass quasi-solid electrolyte according to claim 2, characterized in that: The ball milling treatment was performed at a rotation speed of 300 rpm for 20 minutes.

4. The method for preparing a flexible MOF glass quasi-solid electrolyte according to claim 1, characterized in that: The MOF glass is ZIF-62; the polymer is at least one of polyimide, polybenzimidazole and polyetheretherketone.

5. The method for preparing a flexible MOF glass quasi-solid electrolyte according to claim 4, characterized in that: The preparation method of ZIF-62 comprises the following steps: Zn(NO3)2·6H2O, imidazole and benzimidazole are uniformly mixed in an organic solution at a molar ratio of 1:1.5:13.5, placed in a closed reactor, and then reacted at 120°C-140°C for 48-72 hours. After the reaction is completed, the mixture is washed and dried to obtain the MOF glass.

6. The method for preparing a flexible MOF glass quasi-solid electrolyte according to claim 1, characterized in that: The mass ratio of the MOF glass to the polymer is 1:0.4-2.

4.

7. The method for preparing a flexible MOF glass quasi-solid electrolyte according to claim 1, characterized in that: The sintering temperature is 390-420° C., the sintering time is 20-60 min, and the sintering is performed under an inert atmosphere.

8. The method for preparing a flexible MOF glass quasi-solid electrolyte according to claim 1, characterized in that: The soaking time in the electrolyte is 12-24 hours; The electrolyte includes a solute and a solvent, the solute is one of lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl imide) and lithium bis(fluorosulfonyl imide), the concentration of the solute is 1-3 mol / L, and the solvent is an ether solvent or an ester solvent.

9. A flexible MOF glass quasi-solid electrolyte, characterized in that: The flexible MOF glass quasi-solid electrolyte is prepared by the preparation method of any one of claims 1 to 8.

10. A lithium battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that: The electrolyte is the flexible MOF glass quasi-solid electrolyte according to claim 9.

Images