A method for integrated construction of a composite solid-state zinc-ion battery

Abstract

The application discloses a kind of integrated construction methods of composite solid zinc ion battery, comprising the following steps: first, with zinc foil as receiver, adopt electrospinning technology to spin the "ant nest type" skeleton structure fiber membrane with dense metal organic framework material: second, in situ impregnation method is combined with zinc salt containing polar polymer, and integrated composite solid zinc ion battery is constructed.The application adopts electrospinning technology to spin the "ant nest type" skeleton structure fiber membrane with dense metal organic framework material on the surface, and the cohesion of nanofiber enhances the mechanical engagement and chemical bonding effect between electrode and electrolyte layer, which truly realizes the construction of electrode / electrolyte layer integrated interface.Not only significantly shorten the ion transmission path, reduce interface impedance, but also effectively prevent the interface slip occurred in the stretching process.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of new energy materials, and particularly relates to an integrated construction method of a composite solid-state zinc ion battery. BACKGROUND

[0002] Zinc ion batteries (AZIBs) have attracted much attention due to their inherent safety, abundant reserves, low Zn / Zn 2+ standard redox potential of-0.76 V vs. standard hydrogen electrode (SHE), and simple manufacturing process. When the liquid electrolyte-based zinc ion battery is subjected to various mechanical deformations, the occurrence of electrolyte leakage may endanger the cycle performance of the battery. In addition, the water-based liquid electrolyte may bring some thorny problems to the equipment, including the formation of zinc dendrites on the anode, the hydrogen evolution reaction, the formation of by-products, and the dissolution of the cathode material, thereby leading to rapid decay of the battery capacity. The solid-state zinc ion battery based on solid-state electrolyte does not contain active water molecules, and the above problems can be alleviated to a certain extent by converting the solid-liquid interface between the electrodes into a solid-solid interface. In recent years, more and more researchers have begun to develop new solid-state electrolytes which can simultaneously act as a separator and an electrolyte, thereby facilitating the battery preparation process and stabilizing the structure of the flexible device. The team of Cui Guanglei of Qingdao Bioenergy and Process Institute of Chinese Academy of Sciences and Zhou Xinhong of Qingdao University of Science and Technology disclosed the preparation of Zn 2+ conductive solid-state electrolyte (ZCE) based on the crystallization of deep eutectic solvent (ZES) of Zn(TFSI)2. The preferential adsorption of TFSI - anions on the Lewis acid surface of the TiO2 nucleating agent weakens the ion combination, thereby accelerating the Zn 2+ migration (Angew. Chem. Int. Ed. 2022, 61, e202113086). The patent application with publication number CN114621408A discloses a polymer electrolyte in which a dynamic coordination group capable of coordinating with zinc ions is introduced into a polyether-based polymer skeleton; the patent application with publication number CN113078372A discloses a sandwich structure hydrophilic zinc ion solid-state electrolyte, its application in quasi-solid-state zinc ion batteries, and a preparation method thereof. Although the above-prepared solid-state electrolytes have a certain flexibility, the reaction kinetics at the interface between the electrode and the solid-state electrolyte is slow and the interface compatibility is poor, resulting in low zinc ion conductivity. In addition, due to the low mechanical strength and complex assembly process and many other problems, the scale production of zinc ion solid-state batteries is limited.

[0003] Patent application with publication number CN118040099A discloses a negative electrode and electrolyte integrated structure, a preparation method and application thereof. The negative electrode and electrolyte integrated structure comprises a zinc powder electrode, an organic electrolyte and a water-based electrolyte layer. The organic electrolyte is distributed in the zinc powder electrode, and the water-based electrolyte layer is arranged on the surface of one side of the zinc powder electrode. The negative electrode and electrolyte integrated structure provided by the application can effectively inhibit dendrite growth, reduce the probability of side reactions, improve the utilization rate of zinc in the negative electrode, and enhance the structural stability of the negative electrode and electrolyte integrated structure during the battery cycle charging and discharging process.

[0004] Patent application with publication number CN114628164A discloses a new strategy for integrated in-situ construction of flexible stretchable supercapacitors. First, an integrated flexible stretchable precursor fiber membrane with a "sandwich" structure is spun layer by layer using electrospinning technology. Then, a conductive polymer is grown in-situ on the electrode precursor fiber containing an oxidizing agent through a gas phase polymerization method. Finally, an integrated flexible stretchable supercapacitor is obtained by impregnating the electrolyte and packaging. The integrated flexible stretchable supercapacitor constructed by the present invention utilizes the mechanical engagement and chemical bonding between nanofibers to achieve a firm interface combination between the electrode and the electrolyte and a low interface impedance, thereby improving the electrochemical stability of the supercapacitor during deformation.

[0005] Based on the above background, the preparation of an integrated composite solid-state zinc ion battery is one of the most effective strategies to simultaneously improve the ion conductivity and deformation capability of energy storage devices by evolving the overall structure from a three-dimensional stacking structure to a two-dimensional dense film. SUMMARY

[0006] The purpose of the present application is to provide a novel integrated construction method of composite solid-state zinc ion battery. First, an "ant nest type" skeleton structure fiber membrane with a dense metal organic framework material is spun on a zinc foil using electrospinning technology. Then, a polar polymer containing zinc salt is compounded by in-situ impregnation method to construct an integrated composite solid-state zinc ion battery, which realizes the close combination between components, significantly reduces the interface impedance, and effectively solves the challenges of current solid-state zinc ion batteries in terms of ion conductivity and mechanical strength.

[0007] To achieve the above purpose, the technical solutions adopted by the present application are as follows:

[0008] In the first aspect of the present application, an integrated construction method of composite solid-state zinc ion battery is provided, comprising the following steps:

[0009] In the first step, a zinc foil is used as a receiver, and an "ant nest type" skeleton structure fiber membrane with a dense metal organic framework material is spun using electrospinning technology:

[0010] The metal salt is dissolved in a first organic solvent, the organic ligand is dissolved in the first organic solvent, the above two solutions are mixed, the molar ratio of the metal salt and the organic ligand is 1:1-8 (preferably 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:8), and after the reaction is complete, washing is performed to obtain a metal organic framework material;

[0011] The metal salt is selected from at least one of zinc nitrate hexahydrate, cobalt nitrate hexahydrate, and zirconium tetrachloride.

[0012] The organic ligand is selected from at least one of terephthalic acid and 2-methylimidazole.

[0013] The metal organic framework material is uniformly dispersed in a mixed organic solvent, the mixed organic solvent is prepared from a second organic solvent and a third organic solvent in a mass ratio of 1:1-4 (preferably 1:1, 1:2, 1:3, 1:4), a fluorine-containing elastomeric polymer is added, a crosslinking agent is added to the above solution, the mass ratio of the fluorine-containing elastomeric polymer to the entire mixed solution is controlled to be 5wt-10wt% (preferably 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%), the mass ratio of the fluorine-containing elastomeric polymer to the metal organic framework material is 1:0.03-0.2 (preferably 1:0.04, 1:0.05, 1:0.06, 1:0.1, 1:0.15, 1:0.2), and the mass ratio of the fluorine-containing elastomeric polymer to the crosslinking agent is 1:0.02-0.06 (preferably 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06) to obtain an “ant nest type” fiber membrane precursor spinning solution A;

[0014] The fluorine-containing elastomeric polymer is selected from at least one of fluoroelastomer and polyvinylidene fluoride.

[0015] The crosslinking agent is selected from at least one of hydrazine, tetraethylenediamine, and triethylenetetramine.

[0016] The zinc foil is used as a receiver, and the spinning solution A is prepared into a zinc foil covered with an “ant nest type” fiber membrane containing a metal organic framework material by an electrospinning technology, and the thickness of the membrane layer is controlled to be 20-70 microns (preferably 20, 30, 40, 50, 60, 70 microns).

[0017] In the second step, a polar polymer containing a zinc salt is compounded by an in-situ impregnation method to construct an integrated composite solid zinc ion battery

[0018] The zinc salt is dissolved into the fourth organic solvent, the polar polymer is added, the content of the polar polymer is 3-7wt% (preferably 3wt%, 4wt%, 5wt%, 6wt%, 7wt%) of the mass percentage of the fourth organic solvent, the mass ratio of the zinc salt to the polar polymer is 1:1-5 (preferably 1:1, 1:2, 1:3, 1:4, 1:5), to obtain an impregnation solution B;

[0019] The zinc salt is at least one of zinc trifluoromethanesulfonate, zinc sulfate, zinc chloride, and zinc bromide.

[0020] The polar polymer is at least one of polyethylene oxide, poly(vinylidene fluoride-co-hexafluoropropylene), and polyacrylonitrile.

[0021] The impregnation solution B is cast on the zinc foil covered with the "ant nest type" fiber membrane with the metal organic framework material, dried at a temperature of 40-70℃ (preferably 40℃, 50℃, 60℃, 70℃) for 4-12 hours (preferably 4, 5, 6, 7, 12 hours), to obtain an integrated composite solid-state zinc ion electrolyte;

[0022] The positive active material, the conductive carbon black, and the binder are mixed and stirred in a mass ratio of 1-10:1-3:1 (preferably 7:2:1) to form a uniform slurry, the slurry is cast on a titanium foil by a doctor blade method, and after drying, the positive electrode material is obtained, the effective mass loading of the positive electrode material is 0.3-0.8mg / cm 2 (preferably 0.3, 0.4, 0.5, 0.6, 0.7, 0.8); the integrated composite solid-state zinc ion electrolyte and the positive electrode material with the same size are combined and packaged to obtain an integrated composite solid-state zinc ion battery.

[0023] The first organic solvent is at least one of methanol, ethanol, acetone, butanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, ethylene glycol, and propylene glycol.

[0024] The second organic solvent is at least one of acetone and butanone.

[0025] The third organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0026] The mass ratio of the metal organic framework material ZIF-8 to the mixed organic solvent is 1:20-800 (preferably 1:190, 1:473.5, 1:263.5, 1:259, 1:99.6, 1:58.7).

[0027] The electrospinning conditions are: voltage 12-20 kV (preferably 12, 13, 14, 16, 18, 19, 20 kV), humidity 10-30% (preferably 10, 20, 30%), distance between the spinning needle and the receiver 9-21 cm (preferably 9, 10, 12, 15, 17, 19, 20 cm).

[0028] The fourth organic solvent is selected from at least one of acetonitrile, ethylene glycol, and propylene glycol.

[0029] The binder is selected from PVDF.

[0030] The positive electrode active material is at least one of vanadium-based oxides, manganese-based oxides, polyaniline, and activated carbon.

[0031] The vanadium-based oxide is selected from vanadium oxide and vanadium pentoxide.

[0032] The manganese-based oxide is selected from manganese dioxide.

[0033] Thanks to the above technical solutions, the present application has the following advantages and beneficial effects:

[0034] The present application adopts electrospinning technology to spin the "ant nest type" skeleton structure fiber membrane with dense metal organic framework material on the surface, and the adhesion of nanofibers enhances the mechanical engagement and chemical bonding effect between the electrode and the electrolyte layer, truly realizing the construction of the electrode / electrolyte layer integrated interface. Not only can the ion transmission path be significantly shortened, the interface impedance can be reduced, but also the interface slip occurring in the stretching process can be effectively prevented.

[0035] The metal organic framework material prepared by the present application has a unique pore structure, can form additional single-ion fast channels, and the fluorine in the fluorine-containing elastomeric polymer can adjust the electron distribution along the porous channel, enhance the capture and dissociation of anions, and synergistically promote the zinc ion migration dynamics, greatly improving the ionic conductivity.

[0036] The strategy of combining electrospinning on the electrode and in-situ impregnation to construct an integrated composite solid-state zinc ion battery proposed by the present application not only provides support and stability for the electrode material, prevents the deformation or peeling of the electrode material during the charging and discharging process, but also simplifies the preparation process, improves the production efficiency, and provides a more effective solution and innovative technology for the large-scale production of integrated flexible energy storage devices.

[0037] The new strategy of integrated construction of the composite solid-state zinc ion battery proposed by the present application first uses zinc foil as the receiver, and adopts electrospinning technology to spin the fiber skeleton with "ant nest" structure, and the dense metal organic framework material on the surface of the skeleton can construct Zn 2+The process involves a rapid channel, followed by impregnation of the aforementioned fiber skeleton in a polymer containing zinc salts. Ion migration is accelerated through coordination of polar groups. Finally, a positive electrode material is prepared, and the mixture is encapsulated to obtain an integrated composite solid-state zinc-ion battery. Utilizing the ultra-high mechanical strength of the fiber skeleton and the rapid ion transport mechanism of anion-locking by active groups, the integrated composite solid-state zinc-ion battery of this invention exhibits higher ionic conductivity and specific capacity retention during cycling. Attached Figure Description

[0038] Figure 1 This is a schematic diagram of the integrated construction process of the composite solid-state zinc-ion battery of the present invention.

[0039] Figure 2 This is a schematic diagram of a field emission scanning electron microscope image of a fiber membrane with a "nest-like" skeleton structure containing a dense metal-organic framework material constructed in Example 1.

[0040] Figure 3 This is a schematic diagram showing the ionic conductivity of the integrated composite solid zinc ion electrolyte constructed in Example 1 at different temperatures.

[0041] Figure 4 This is a schematic diagram showing the specific capacity and coulombic efficiency of the integrated composite solid-state zinc-ion battery constructed in Example 1 during the charge-discharge cycle. Detailed Implementation

[0042] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0043] Example 1

[0044] The construction method of integrated composite solid-state zinc-ion battery, such as Figure 1 As shown, Figure 1 This is a schematic diagram illustrating the integrated construction process of the composite solid-state zinc-ion battery of the present invention. It includes the following steps:

[0045] The first step involves using zinc foil as a receiver and electrospinning technology to spin a "anthill-type" skeletal structure fiber membrane with a dense metal-organic framework material:

[0046] 0.008 mol zinc nitrate hexahydrate was dissolved in 30 mL methanol, and 0.064 mol 2-methylimidazole was dissolved in 60 mL methanol. The two solutions were mixed with a molar ratio of zinc nitrate hexahydrate to 2-methylimidazole of 1:8. The mixture was reacted for 24 h, and the mixture was washed three times by centrifugation with 40 mL methanol each time. 0.65 g of metal-organic framework material ZIF-8 was obtained.

[0047] 0.096 g of metal-organic framework material ZIF-8 was uniformly dispersed in 18.256 g of mixed organic solvent, which was made of acetone and N,N-dimethylformamide in a mass ratio of 1:2. 1.6 g of fluororubber was then dissolved in the above solution. Finally, 0.048 g of hexamethylenediamine was added to the above solution. The mass ratio of fluororubber in the entire mixed solution was controlled to be 8 wt%, the mass ratio of fluororubber to metal-organic framework material ZIF-8 was 1:0.06, and the mass ratio of fluororubber to hexamethylenediamine was 1:0.03, resulting in 20 g of "ant-hole type" fiber membrane precursor spinning solution A.

[0048] Using zinc foil as a receiver, zinc foil covered with a "nest-like" fiber membrane of metal-organic framework material ZIF-8 was prepared by electrospinning with spinning solution A. The membrane thickness was controlled at 40 micrometers. Electrospinning conditions: voltage 18kV, humidity 10%, distance from spinning needle to receiver 17cm.

[0049] Characterization was performed using field emission scanning electron microscopy, and the results are as follows: Figure 2 As shown, Figure 2 This is a schematic field emission scanning electron microscope (FESEM) image of the "anthill-like" framework structure fiber membrane constructed in Example 1 with a dense metal-organic framework material. As can be seen from the image, the nanofibers are intertwined or staggered, a structure that increases the fiber's flexibility and strength, ensuring stable electrochemical performance during deformation. Simultaneously, the well-developed "anthill" structure provides naturally favorable conditions for subsequent in-situ impregnation. More importantly, the uniformly distributed metal-organic framework material on the surface possesses a unique pore structure, enabling the formation of additional rapid zinc single-ion channels.

[0050] The second step involves in-situ impregnation to composite a polar polymer containing zinc salts, thereby constructing an integrated composite solid-state zinc-ion battery.

[0051] Dissolve 0.5g of zinc trifluoromethanesulfonate in 18.5g of acetonitrile, add 1g of polyethylene oxide (PEO), with PEO accounting for 5wt% of the total mass of the mixed solution. The mass ratio of zinc trifluoromethanesulfonate to PEO is 1:2, resulting in 20g of impregnation solution B.

[0052] 5 mL of impregnation solution B was cast onto a zinc foil (3 cm × 3 cm in size) covered with an "anthill-type" fiber membrane containing metal-organic framework material ZIF-8. The foil was dried at 60 °C for 12 hours and then cut into a disc shape with a diameter of 12 mm to achieve the integration of the negative electrode and the composite solid electrolyte, thus obtaining a composite solid zinc ion electrolyte.

[0053] 0.14 g of vanadium oxide, 0.04 g of conductive carbon black, and 0.02 g of binder PVDF were mixed and stirred into a uniform slurry, 5 mL of the slurry was cast on a titanium foil (size 10 cm x 10 cm) by using a doctor blade method, and after drying, it was cut into a disc with a diameter of 12 mm as a positive electrode material, and the effective mass loading of the positive electrode material was 0.5 mg / cm 2 The integrated composite solid-state zinc ion electrolyte and the positive electrode material with the same size were combined and packaged to obtain an integrated composite solid-state zinc ion battery.

[0054] The conductivity test and the charge-discharge cycle test of the integrated composite solid-state zinc ion battery constructed were carried out at different temperatures. The results are shown in Figure 3 , Figure 3 The ion conductivity of the integrated composite solid-state zinc ion electrolyte constructed in Example 1 at different temperatures is shown in the figure. As can be seen from the figure, the conductivity of the integrated composite solid-state zinc ion electrolyte can reach 1.62 x 10 -4 S / cm at 30℃. The results are shown in Figure 4 , Figure 4 The capacity and coulombic efficiency of the integrated composite solid-state zinc ion battery constructed in Example 1 during the charge-discharge cycle process are shown in the figure. As can be seen from the figure, the charge-discharge specific capacity of the integrated composite solid-state zinc ion battery can reach 348 mAh / g at a current density of 0.05 A / g, and the capacity retention rate is about 95.7% after 50 cycles. The coulombic efficiency is close to 100%, which indicates that the battery can still maintain a high energy utilization rate after multiple charge-discharge cycles. This shows that the method of the present application enhances the interface stability between the electrode and the electrolyte, promotes the ion migration dynamics, so that the device can run efficiently and stably, and exhibits excellent electrochemical performance.

[0055] Example 2

[0056] The method for constructing the integrated composite solid-state zinc ion battery comprises the following steps:

[0057] In the first step, a "ant nest type" skeleton structure fiber membrane with a dense metal organic framework material is spun by using an electrospinning technology with a zinc foil as a receiver:

[0058] 0.008 mol of cobalt nitrate hexahydrate was dissolved in 30 mL of ethanol, 0.032 mol of 2-methylimidazole was dissolved in 60 mL of ethanol, the two solutions were mixed, the molar ratio of cobalt nitrate hexahydrate to 2-methylimidazole was 1:4, the reaction was carried out for 24 h, and each time 40 mL of ethanol was used for centrifugal washing, and the washing was carried out for three times, and 0.5 g of metal organic framework material ZIF-67 was obtained.

[0059] 0.04 g metal organic framework material ZIF-67 is uniformly dispersed in 18.94 g mixed organic solvent, the mixed organic solvent is made of acetone and N, N-dimethylacetamide with a mass ratio of 1:1, then 1 g of polyvinylidene fluoride is dissolved into the above solution, finally 0.02 g of tetraethylenepentamine is added into the above solution, the mass ratio of polyvinylidene fluoride to the whole mixed solution is 5wt%, the mass ratio of polyvinylidene fluoride to metal organic framework material ZIF-67 is 1:0.04, and the mass ratio of polyvinylidene fluoride to tetraethylenepentamine is 1:0.02, to obtain 20 g of "ant nest type" fiber membrane precursor spinning solution A.

[0060] A zinc foil is used as a receiver, and the spinning solution A is prepared into a zinc foil covered with "ant nest type" fiber membrane containing metal organic framework material ZIF-67 by electrospinning technology, and the thickness of the membrane layer is controlled at 30 microns. The electrospinning conditions are as follows: the voltage is 19 kV, the humidity is 10%, and the distance between the spinning needle and the receiver is 15 cm.

[0061] In the second step, a polar polymer containing zinc salt is compounded by in-situ impregnation to construct an integrated composite solid-state zinc ion battery.

[0062] 0.3 g of zinc sulfate is dissolved into 18.5 g of acetonitrile, and 1.2 g of polyethylene oxide is added, the mass percentage of polyethylene oxide in the whole mixed solution is 6wt%, and the mass ratio of zinc sulfate to polyethylene oxide is 1:4, to obtain 20 g of impregnating solution B.

[0063] 5 mL of impregnating solution B is cast on the above-mentioned zinc foil covered with "ant nest type" fiber membrane containing metal organic framework material ZIF-67 (size of 3 cm x 3 cm), and dried at a temperature of 50°C for 7 hours, and then cut into a disc shape with a diameter of 12 mm, to realize the integration of the negative electrode and the composite solid-state electrolyte, and obtain a composite solid-state zinc ion electrolyte.

[0064] 0.14 g of vanadium-based oxide vanadium pentoxide, 0.04 g of conductive carbon black, and 0.02 g of binder PVDF are mixed and stirred into a uniform slurry, 5 mL of the slurry is cast on a titanium foil (size of 10 cm x 10 cm) by using a doctor blade method, and after drying, it is cut into a disc with a diameter of 12 mm as a positive electrode material, and the effective mass loading of the positive electrode material is 0.5 mg / cm 2 The same size integrated composite solid-state zinc ion electrolyte and positive electrode material are combined and packaged to obtain an integrated composite solid-state zinc ion battery.

[0065] The conductivity test and the charge-discharge cycle test of the integrated composite solid-state zinc ion battery are carried out at different temperatures.

[0066] Example 3

[0067] A method for constructing an integrated composite solid-state zinc ion battery, comprising the following steps:

[0068] In the first step, a zinc foil is used as a receiver, and an "ant nest type" skeleton structure fiber membrane with a dense metal organic framework material is spun by using an electrospinning technology:

[0069] 0.008 mol of zinc nitrate hexahydrate is dissolved in 30 mL of N,N-dimethylformamide, and 0.024 mol of terephthalic acid is dissolved in 60 mL of N,N-dimethylformamide, the two solutions are mixed, the molar ratio of zinc nitrate hexahydrate to terephthalic acid is 1:3, the reaction is carried out for 24 hours, and the solution is centrifuged and washed with 40 mL of N,N-dimethylformamide each time, and the washing is repeated three times, and 0.75 g of metal organic framework material MOF-5 is obtained.

[0070] 0.07 g of metal organic framework material MOF-5 is uniformly dispersed in 18.446 g of mixed organic solvent, the mixed organic solvent is made of butanone and N-methyl pyrrolidone with a mass ratio of 1:3, 1.4 g of polyvinylidene fluoride is dissolved in the above solution, and finally 0.084 g of hexanediamine is added to the above solution, the mass ratio of polyvinylidene fluoride to the whole mixed solution is 7wt%, the mass ratio of polyvinylidene fluoride to metal organic framework material MOF-5 is 1:0.05, and the mass ratio of polyvinylidene fluoride to hexanediamine is 1:0.06, and 20 g of "ant nest type" fiber membrane precursor spinning solution A is obtained.

[0071] The zinc foil is used as the receiver, and the spinning solution A is prepared by using the electrospinning technology, and the zinc foil covered with the "ant nest type" fiber membrane with the metal organic framework material MOF-5 is prepared, and the thickness of the membrane layer is controlled at 50 microns. The electrospinning conditions are as follows: the voltage is 16 kV, the humidity is 20%, and the distance between the spinning needle and the receiver is 17 cm.

[0072] In the second step, the in-situ impregnation method is used to composite the polar polymer containing zinc salt, and the integrated composite solid-state zinc ion battery is constructed

[0073] 0.8 g of zinc chloride is dissolved in 18.4 g of ethylene glycol, and 0.8 g of polyacrylonitrile is added, the mass percentage of polyacrylonitrile in the whole mixed solution is 4wt%, and the mass ratio of zinc chloride to polyacrylonitrile is 1:1, and 20 g of impregnation solution B is obtained.

[0074] 5 mL of impregnation solution B is cast on the zinc foil covered with the "ant nest type" fiber membrane with the metal organic framework material MOF-5 (the size is 3 cm x 3 cm), and dried at a temperature of 40°C for 12 hours, and cut into a disc shape with a diameter of 12 mm, and the negative electrode and the composite solid-state electrolyte are integrated, and a composite solid-state zinc ion electrolyte is obtained.

[0075] 0.14 g of manganese dioxide, 0.04 g of conductive carbon black, and 0.02 g of a binder PVDF were mixed and stirred into a uniform slurry. 5 mL of the slurry was cast on a titanium foil (10 cm x 10 cm in size) by using a doctor blade method, and after drying, a disc with a diameter of 12 mm was cut out as a positive electrode material. The effective mass loading of the positive electrode material was 0.7 mg / cm 2 The integrated composite solid-state zinc ion electrolyte and the positive electrode material with the same size were combined and packaged to obtain an integrated composite solid-state zinc ion battery.

[0076] The integrated composite solid-state zinc ion battery constructed was subjected to conductivity testing and charge-discharge cycle testing at different temperatures.

[0077] Example 4

[0078] The method for constructing the integrated composite solid-state zinc ion battery comprises the following steps:

[0079] In the first step, a zinc foil was used as a receiver, and an "ant nest type" skeleton structure fiber membrane with a dense metal organic framework material was spun by using an electrospinning technology:

[0080] 0.008 mol of zirconium tetrachloride was dissolved in 30 mL of N,N-dimethylformamide, and 0.008 mol of terephthalic acid was dissolved in 60 mL of N,N-dimethylformamide. The two solutions were mixed, the molar ratio of zirconium tetrachloride to terephthalic acid was 1:1, and the reaction was carried out for 24 h. Each time, 40 mL of N,N-dimethylformamide was used for centrifugal washing, and the washing was performed three times to obtain 0.6 g of a metal organic framework material Uio-66.

[0081] 0.072 g of the metal organic framework material Uio-66 was uniformly dispersed in 18.68 g of a mixed organic solvent, which was prepared from acetone and N-methyl pyrrolidone with a mass ratio of 1:2. Then, 1.2 g of fluoro rubber was dissolved in the above solution, and finally, 0.048 g of triethylenetetramine was added to the above solution. The mass ratio of the fluoro rubber to the entire mixed solution was 6 wt%, the mass ratio of the fluoro rubber to the metal organic framework material Uio-66 was 1:0.06, and the mass ratio of the fluoro rubber to triethylenetetramine was 1:0.04, to obtain 20 g of an "ant nest type" fiber membrane precursor spinning solution A.

[0082] With the zinc foil as the receiver, the spinning solution A was prepared into the zinc foil covered with the "ant nest type" fiber membrane with the metal organic framework material Uio-66 by using the electrospinning technology, and the thickness of the membrane layer was controlled at 20 microns. The electrospinning conditions were as follows: the voltage was 14 kV, the humidity was 30%, and the distance from the spinning needle to the receiver was 20 cm.

[0083] In the second step, a polar polymer containing a zinc salt was compounded by using an in-situ impregnation method to construct an integrated composite solid-state zinc ion battery

[0084] Dissolve 0.16 g of zinc bromide into 19.04 g of propylene glycol, add 0.8 g of poly(vinylidene fluoride-co-hexafluoropropylene), the mass percentage of poly(vinylidene fluoride-co-hexafluoropropylene) in the whole mixed solution is 4 wt%, the mass ratio of zinc bromide to poly(vinylidene fluoride-co-hexafluoropropylene) is 1:5, to obtain 20 g of impregnating solution B.

[0085] Cast 5 mL of impregnating solution B on the zinc foil (size of 3 cm x 3 cm) covered with the "ant nest type" fiber membrane with metal organic framework material Uio-66 described above, dry at a temperature of 60 ℃ for 12 hours, cut into a disc with a diameter of 12 mm, realize the integration of the negative electrode and the composite solid electrolyte, and obtain a composite solid zinc ion electrolyte.

[0086] Mix and stir 0.14 g of polyaniline, 0.04 g of conductive carbon black, and 0.02 g of binder PVDF into a uniform slurry, cast 5 mL of the slurry on a titanium foil (size of 10 cm x 10 cm) by the doctor blade method, and cut into a disc with a diameter of 12 mm after drying, as a positive electrode material, the effective mass loading of the positive electrode material is 0.3 mg / cm 2 . Package the integrated composite solid zinc ion electrolyte and the positive electrode material with the same size to obtain an integrated composite solid zinc ion battery.

[0087] The conductivity test and the charge-discharge cycle test of the integrated composite solid zinc ion battery constructed are carried out at different temperatures.

[0088] Example 5

[0089] The method for constructing the integrated composite solid zinc ion battery comprises the following steps:

[0090] In the first step, the "ant nest type" skeleton structure fiber membrane with dense metal organic framework material is spun by using the electrospinning technology with zinc foil as the receiver:

[0091] Dissolve 0.008 mol of zinc nitrate hexahydrate in 30 mL of ethanol, dissolve 0.048 mol of 2-methylimidazole in 60 mL of ethanol, mix the two solutions, the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole is 1:6, react for 24 h, centrifugal wash with 40 mL of ethanol each time, and wash three times to obtain 0.55 g of metal organic framework material ZIF-8.

[0092] 0.18 g metal organic framework material ZIF-8 is uniformly dispersed in 17.93 g mixed organic solvent, the mixed organic solvent is made of acetone and N, N-dimethylacetamide with a mass ratio of 1:4, then 1.8 g of fluoro rubber is dissolved into the above solution, finally 0.09 g of tetraethylenepentamine is added into the above solution, the mass ratio of fluoro rubber to the whole mixed solution is 9wt%, the mass ratio of fluoro rubber to metal organic framework material ZIF-8 is 1:0.1, and the mass ratio of fluoro rubber to tetraethylenepentamine is 1:0.05, to obtain 20 g of "ant nest type" fiber membrane precursor spinning solution A.

[0093] A zinc foil is used as a receiver, and the spinning solution A is prepared into a zinc foil covered with "ant nest type" fiber membrane containing metal organic framework material ZIF-8 by electrospinning technology, and the thickness of the membrane layer is controlled at 60 microns. The electrospinning conditions are as follows: the voltage is 13 kV, the humidity is 30%, and the distance between the spinning needle and the receiver is 12 cm.

[0094] In the second step, a polar polymer containing zinc salt is compounded by in-situ impregnation to construct an integrated composite solid-state zinc ion battery.

[0095] 0.47 g of zinc bromide is dissolved into 18.13 g of ethylene glycol, and 1.4 g of polyacrylonitrile is added, the content of polyacrylonitrile in the whole mixed solution is 7wt%, and the mass ratio of zinc bromide to polyacrylonitrile is 1:3, to obtain 20 g of impregnating solution B.

[0096] 5 mL of impregnating solution B is cast on the above-mentioned zinc foil covered with "ant nest type" fiber membrane containing metal organic framework material ZIF-8 (size of 3 cm x 3 cm), and dried at a temperature of 70℃ for 6 hours, and then cut into a disc with a diameter of 12 mm, to realize the integration of the negative electrode and the composite solid-state electrolyte, and obtain a composite solid-state zinc ion electrolyte.

[0097] 0.14 g of activated carbon, 0.04 g of conductive carbon black and 0.02 g of binder PVDF are mixed and stirred into a uniform slurry, 5 mL of the slurry is cast on a titanium foil (size of 10 cm x 10 cm) by a doctor blade method, and after drying, it is cut into a disc with a diameter of 12 mm as a positive electrode material, and the effective mass loading of the positive electrode material is 0.8 mg / cm 2 The same size integrated composite solid-state zinc ion electrolyte and positive electrode material are combined and packaged to obtain an integrated composite solid-state zinc ion battery.

[0098] The conductivity test and the charge-discharge cycle test of the integrated composite solid-state zinc ion battery are carried out at different temperatures.

[0099] Example 6

[0100] The method for constructing an integrated composite solid-state zinc ion battery comprises the following steps:

[0101] First step, using zinc foil as receiver, adopt electrospinning technology to spin the "ant nest type" skeleton structure fiber membrane with dense metal organic framework material:

[0102] Dissolve 0.008 mol of zirconium tetrachloride in 30 mL of N,N-dimethylformamide, dissolve 0.016 mol of terephthalic acid in 60 mL of N,N-dimethylformamide, mix the above two solutions, the molar ratio of zirconium tetrachloride to terephthalic acid is 1:2, react for 24 hours, centrifugal wash with 40 mL of N,N-dimethylformamide each time, wash three times, and obtain 0.72 g of metal organic framework material Uio-66.

[0103] Disperse 0.3 g of metal organic framework material Uio-66 uniformly in 17.62 g of mixed organic solvent, the mixed organic solvent is made of butanone and N,N-dimethylformamide with a mass ratio of 1:1, then dissolve 2 g of polyvinylidene fluoride into the above solution, finally add 0.08 g of triethylenetetramine into the above solution, control the mass ratio of polyvinylidene fluoride in the whole mixed solution to be 10 wt%, the mass ratio of polyvinylidene fluoride to metal organic framework material Uio-66 to be 1:0.15, and the mass ratio of polyvinylidene fluoride to triethylenetetramine to be 1:0.04, and obtain 20 g of "ant nest type" fiber membrane precursor spinning solution A.

[0104] Using zinc foil as receiver, prepare the zinc foil covered with "ant nest type" fiber membrane with metal organic framework material Uio-66 by electrospinning technology, and control the thickness of the membrane layer to be 70 microns. The electrospinning conditions are: voltage 20 kV, humidity 20%, and the distance between the spinning needle and the receiver is 9 cm.

[0105] Second step, in-situ impregnation method to composite polar polymer containing zinc salt, to construct integrated composite solid-state zinc ion battery

[0106] Dissolve 0.3 g of zinc triflate into 19.1 g of propylene glycol, and add 0.6 g of polyethylene oxide, the mass percentage of polyethylene oxide in the whole mixed solution is 3 wt%, and the mass ratio of zinc triflate to polyethylene oxide is 1:2, to obtain 20 g of impregnation solution B.

[0107] Cast 5 mL of impregnation solution B on the above zinc foil covered with "ant nest type" fiber membrane with metal organic framework material Uio-66 (size 3 cm x 3 cm), dry at a temperature of 50℃ for 10 hours, and cut into a disc shape with a diameter of 12 mm, to realize the integration of the negative electrode and the composite solid-state electrolyte, and obtain the composite solid-state zinc ion electrolyte.

[0108] 0.14 g of manganese dioxide, 0.04 g of conductive carbon black, and 0.02 g of a binder PVDF were mixed and stirred into a uniform slurry, 5 mL of the slurry was cast on a titanium foil (size 10 cm x 10 cm) by using a doctor blade method, and after drying, it was cut into a disc with a diameter of 12 mm as a positive electrode material, and the effective mass loading of the positive electrode material was 0.4 mg / cm 2 The same size integrated composite solid-state zinc ion electrolyte and positive electrode material were combined and packaged to obtain an integrated composite solid-state zinc ion battery.

[0109] The conductivity test and charge-discharge cycle test of the integrated composite solid-state zinc ion battery constructed were carried out at different temperatures.

[0110] Comparative Example 1

[0111] The construction method of the composite solid-state zinc ion battery comprises the following steps:

[0112] First step, using glass plate casting method to construct polymer skeleton film with dense metal organic framework material on the surface

[0113] 0.008 mol of zinc nitrate hexahydrate was dissolved in 30 mL of methanol, 0.064 mol of 2-methylimidazole was dissolved in 60 mL of methanol, the two solutions were mixed, the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole was 1:8, the reaction was carried out for 24 h, and each time 40 mL of methanol was used for centrifugal washing, and the washing was repeated three times, and 0.65 g of metal organic framework material ZIF-8 was obtained.

[0114] 0.096 g of metal organic framework material ZIF-8 was uniformly dispersed in 18.256 g of mixed organic solvent, the mixed organic solvent was prepared from acetone and N, N-dimethylformamide with a mass ratio of 1:2, 1.6 g of fluoro rubber was dissolved in the above solution, and finally 0.048 g of hexanediamine was added to the above solution, the mass ratio of fluoro rubber to the whole mixed solution was controlled to be 8 wt%, the mass ratio of fluoro rubber to metal organic framework material ZIF-8 was 1:0.06, and the mass ratio of fluoro rubber to hexanediamine was 1:0.03, and 20 g of casting solution A was obtained.

[0115] 10 g of casting solution A was uniformly cast on a flat glass plate (size 6 cm x 6 cm) to form a film, vacuum dried for 8 h, and after the solvent was completely evaporated, the glass plate was removed, and a polymer skeleton film with dense metal organic framework material on the surface was obtained, and the film thickness was controlled to be 40 microns.

[0116] Second step, impregnated in a polar polymer containing zinc salt and packaged to construct a composite solid-state zinc ion battery

[0117] Dissolve 0.5 g zinc trifluoromethanesulfonate into 18.5 g acetonitrile, add 1 g polyethylene oxide, the mass percentage of polyethylene oxide in the whole solution is 5 wt%, the mass ratio of zinc trifluoromethanesulfonate to polyethylene oxide is 1:2, to obtain 20 g of impregnating solution B.

[0118] Dip the prepared polymer skeleton film with dense metal organic framework material on the surface (size of 6 cm x 6 cm) in 10 g of impregnating solution B for 3 min, take it out, dry at a temperature of 60°C for 12 hours, cut into a disc with a diameter of 19 mm, to obtain a composite solid-state zinc ion electrolyte.

[0119] Mix and stir 0.14 g vanadium oxide, 0.04 g conductive carbon black and 0.02 g binder PVDF into a uniform slurry, cast 5 mL of the slurry on a titanium foil (size of 10 cm x 10 cm) by using a doctor blade method, dry and cut into a disc with a diameter of 12 mm as a positive electrode material, the effective mass loading of the positive electrode material is 0.5 mg / cm 2 Assemble and package the composite solid-state zinc ion electrolyte, zinc foil negative electrode (cut into a disc with a diameter of 12 mm) and positive electrode material to obtain a composite solid-state zinc ion battery.

[0120] Test results of the integrated composite solid-state zinc ion battery constructed in examples 1-6 and comparative example 1

[0121]

[0122]

[0123] The integrated composite solid-state zinc ion batteries constructed in examples 1-6 and comparative example 1 were subjected to electrochemical performance tests under dynamic and static conditions, and the specific test results are shown in Table 1. It can be found that the specific capacity of the whole device is basically positively correlated with the size of the ionic conductivity. Compared with comparative example 1, the electrospinning method forms a "ant nest" structure with developed pores, which is beneficial to the rapid segment motion of zinc ions, so that the battery has higher specific capacity and more excellent cycle stability in charge and discharge cycles.

[0124] The above only describes the preferred embodiments of the present application and does not limit the present application in any form. Although the present application has been disclosed as above with the preferred embodiments, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above-mentioned technical content without departing from the technical solution range of the present application, and equivalent embodiments with equivalent changes are equivalent. Any simple modification, equivalent change and modification of the above embodiments based on the technical essence of the present application are still within the scope of the present application.

Claims

1. An integrated construction method for a composite solid-state zinc-ion battery, characterized in that, Includes the following steps: The first step involves dissolving the metal salt and the organic ligand in the first organic solvent, mixing the two solutions (with a molar ratio of metal salt to organic ligand of 1:1 to 8), and washing after complete reaction to obtain the metal-organic framework material. The metal salt is selected from at least one of zinc nitrate hexahydrate, cobalt nitrate hexahydrate, and zirconium tetrachloride; The organic ligand is selected from at least one of terephthalic acid and 2-methylimidazole; Metal-organic framework materials are uniformly dispersed in a mixed organic solvent, which is made of a second organic solvent and a third organic solvent in a mass ratio of 1:1 to 4. A fluorinated elastic polymer is added, and a crosslinking agent is added to the above solution. The mass ratio of the fluorinated elastic polymer to the entire mixed solution is controlled to be 5 wt% to 10 wt%, the mass ratio of the fluorinated elastic polymer to the metal-organic framework material is 1:0.03 to 0.2, and the mass ratio of the fluorinated elastic polymer to the crosslinking agent is 1:0.02 to 0.06, to obtain "ant-like" fiber membrane precursor spinning solution A. The fluorinated elastic polymer is selected from at least one of fluororubber and polyvinylidene fluoride; The crosslinking agent is selected from at least one of diamine, tetraethylenetriamine, and triethylenetetramine; Using zinc foil as a receiver, spinning solution A is electrospinned to produce zinc foil covered with a "anthill-type" fiber membrane with metal-organic framework material, and the membrane thickness is controlled between 20 and 70 micrometers. The second step involves dissolving the zinc salt in a fourth organic solvent, adding a polar polymer, wherein the content of the polar polymer is 3-7 wt% of the mass percentage of the fourth organic solvent, and the mass ratio of the zinc salt to the polar polymer is 1:1-5, to obtain impregnation solution B. The zinc salt is selected from at least one of zinc trifluoromethanesulfonate, zinc sulfate, zinc chloride, and zinc bromide; The polar polymer is selected from at least one of polyethylene oxide, poly(vinylidene fluoride-co-hexafluoropropylene), and polyacrylonitrile; Impregnation solution B is cast onto zinc foil covered with the above-mentioned "ant-like" fiber membrane with metal-organic framework material, and dried at a temperature of 40-70°C for 4-12 hours to obtain an integrated composite solid zinc ion electrolyte. A homogeneous slurry is prepared by mixing positive electrode active material, conductive carbon black, and binder in a mass ratio of 1–10:1–3:

1. The slurry is then cast onto titanium foil using a doctor blade method. After drying, it serves as the positive electrode material, with an effective mass loading of 0.3–0.8 mg / cm³. 2 An integrated composite solid zinc-ion battery is obtained by combining and encapsulating an integrated composite solid zinc-ion electrolyte and a positive electrode material of the same size.

2. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The first organic solvent is selected from at least one of methanol, ethanol, acetone, butanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, ethylene glycol, and propylene glycol.

3. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The second organic solvent is selected from at least one of acetone and butanone.

4. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The third organic solvent is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

5. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The mass ratio of the metal-organic framework material ZIF-8 to the mixed organic solvent is 1:20 to 800.

6. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The conditions for electrospinning are: voltage 12-20kV, humidity 10-30%, and distance from the spinning needle to the receiver 9-21cm.

7. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The fourth organic solvent is selected from at least one of acetonitrile, ethylene glycol, and propylene glycol.

8. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The adhesive is selected from PVDF.

9. The integrated construction method of the composite solid-state zinc-ion battery according to claim 1, characterized in that, The positive electrode active material is at least one of vanadium-based oxide, manganese-based oxide, polyaniline, and activated carbon.

10. The integrated construction method of the composite solid-state zinc-ion battery according to claim 9, characterized in that, The vanadium-based oxide is selected from vanadium oxide and vanadium pentoxide; The manganese-based oxide is selected from manganese dioxide.

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