Regenerated cellulose gel electrolyte membrane and preparation method and application thereof

Abstract

The invention discloses a regenerated cellulose gel electrolyte membrane as well as a preparation method and application thereof. The regenerated cellulose gel electrolyte membrane comprises a regenerated cellulose gel membrane, a loaded zinc salt electrolyte and a cellulose solvent, wherein the cellulose solvent is one of an ionic liquid and a deep eutectic solvent. The preparation method of the regenerated cellulose gel electrolyte membrane comprises the following steps: 1) preparing a cellulose solution; 2) preparing a cellulose gel film; and 3) immersing the cellulose gel membrane in a zinc salt electrolyte solution for soaking regeneration, and taking out the cellulose gel membrane to obtain the regenerated cellulose gel electrolyte membrane. The regenerated cellulose gel electrolyte membrane has the advantages of being capable of effectively inhibiting generation of side reactions and growth of zinc dendrites, capable of improving the volume energy density and reversibility of the zinc ion battery, low in production cost and the like, and the preparation method is simple, wide in raw material source, environmentally friendly and suitable for large-scale industrial production and application.

Description

Technical Field

[0001] The present invention relates to the technical field of zinc ion batteries, and particularly relates to a regenerated cellulose gel electrolyte membrane, a preparation method thereof and an application thereof. Background Art

[0002] Wearable electronic devices can continuously and closely monitor an individual's physical activities and health conditions, opening up new ways for the accuracy of health monitoring and playing a crucial role in the field of personalized medicine. The power source is a key component of wearable electronic devices, and the demand for flexible batteries with high energy density and safety is increasing. Flexible aqueous zinc ion batteries are ideal energy storage devices for wearable electronic devices due to their inherent safety and potential high volumetric energy density, and have very broad application prospects. However, side reactions occur between the electrolyte and the zinc negative electrode in flexible aqueous zinc ion batteries using traditional electrolytes, and there is also the problem of uncontrollable growth of zinc dendrites, which greatly reduces the energy density and operating stability of the battery and limits its practical application in wearable electronic devices.

[0003] Therefore, it is of great significance to develop an electrolyte that can effectively inhibit the occurrence of side reactions and the growth of zinc dendrites and improve the volumetric energy density and reversibility of zinc ion batteries. Summary of the Invention

[0004] The purpose of the present invention is to provide a regenerated cellulose gel electrolyte membrane, a preparation method thereof and an application thereof.

[0005] The technical solution adopted by the present invention is as follows:

[0006] A regenerated cellulose gel electrolyte membrane, the composition of which includes a regenerated cellulose gel membrane, a loaded zinc salt electrolyte and a cellulose solvent; the cellulose solvent is one of an ionic liquid and a deep eutectic solvent.

[0007] Preferably, the mass ratio of the regenerated cellulose gel membrane, the zinc salt electrolyte and the cellulose solvent is 1:8.5-17.1:0.5-1.9.

[0008] Preferably, the regenerated cellulose gel membrane is made of lignocellulose.

[0009] Preferably, the lignocellulose is at least one of microcrystalline cellulose, bacterial cellulose, cotton fiber, bleached softwood pulp, bleached hardwood pulp, and bleached bamboo pulp.

[0010] Preferably, the zinc salt electrolyte is at least one of zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc chloride, and zinc perchlorate.

[0011] Preferably, the ionic liquid is at least one of 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium acetate, N-methylmorpholine-N-oxide, ZnCl 2 in the above.

[0012] Preferably, the deep eutectic solvent is composed of a hydrogen bond donor and a hydrogen bond acceptor in a molar ratio of 1:0.5 to 5.0.

[0013] More preferably, the deep eutectic solvent is composed of a hydrogen bond donor and a hydrogen bond acceptor in a molar ratio of 1:1 to 2.

[0014] Preferably, the hydrogen bond donor is at least one of ethanolamine, 3-amino-1-propanol, and isopropanolamine.

[0015] Preferably, the hydrogen bond acceptor is X - is Cl - , Br - in the above, and R is an alkenyl group of C 2 ~C 6 .

[0016] Preferably, the X - is Cl - .

[0017] Preferably, the R is allyl (-CH 2 CH=CH 2 ).

[0018] Preferably, the deep eutectic solvent is prepared by a preparation method including the following steps: mixing the hydrogen bond donor and the hydrogen bond acceptor, and then heating and stirring at 50°C to 100°C until clear and transparent.

[0019] More preferably, the deep eutectic solvent is prepared by a preparation method including the following steps: mixing the hydrogen bond donor and the hydrogen bond acceptor, and then heating and stirring at 70°C to 90°C until clear and transparent.

[0020] Preferably, the thickness of the regenerated cellulose gel electrolyte membrane is 10 μm to 20 μm.

[0021] A preparation method of the regenerated cellulose gel electrolyte membrane as described above includes the following steps:

[0022] 1) Heating and dissolving the cellulose raw material in a cellulose solvent to obtain a cellulose solution;

[0023] 2) Coating the cellulose solution on a substrate, and then performing defoaming and cooling molding to obtain a cellulose gel membrane;

[0024] 3) Immerse the cellulose gel film in a zinc salt electrolyte solution for soaking and regeneration, then take it out to obtain a regenerated cellulose gel electrolyte membrane.

[0025] Preferably, the heating and dissolution in step 1) are carried out at a temperature of 90 °C to 110 °C, and the time for heating and dissolution is 1 h to 1.5 h.

[0026] Preferably, the degassing in step 2) is carried out at a temperature of 100 °C to 120 °C, and the time for degassing is 5 min to 10 min.

[0027] Preferably, the time for soaking and regeneration in step 3) is 8 h to 12 h.

[0028] A zinc-ion battery, which comprises the above-mentioned regenerated cellulose gel electrolyte membrane.

[0029] The beneficial effects of the present invention are as follows: The regenerated cellulose gel electrolyte membrane of the present invention has the advantages of effectively inhibiting the occurrence of side reactions and the growth of zinc dendrites, improving the volume energy density and reversibility of zinc-ion batteries, and having low production costs. Moreover, its preparation method is simple, the raw materials are widely available, and it is environmentally friendly, making it suitable for large-scale industrial production and application.

[0030] Specifically:

[0031] 1) The regenerated cellulose gel electrolyte membrane of the present invention contains a cellulose solvent, which can not only act as a functional additive to inhibit side reactions occurring in zinc-ion batteries, but also play a role in guiding the uniform deposition of zinc ions, reducing the growth of zinc dendrites, and improving the reversibility of the battery.

[0032] 2) The regenerated cellulose gel electrolyte membrane of the present invention has a porous structure, is thin in thickness, and the thickness can be flexibly adjusted. The ion migration channels are shorter, and zinc ions can migrate quickly.

[0033] 3) The regenerated cellulose gel electrolyte membrane of the present invention can reduce the thickness of soft-pack batteries, improve the volume energy density of the batteries, and broaden the path for the practical application of flexible zinc-ion batteries.

[0034] 4) In the present invention, a zinc salt electrolyte is introduced during the cellulose regeneration process, so that zinc ions can form a coordination interaction with the hydroxyl groups on the cellulose chain to form a double-network structure, thereby improving the mechanical properties of the regenerated cellulose gel electrolyte membrane and well meeting the requirements of battery assembly.

[0035] 5) The preparation method of the regenerated cellulose gel electrolyte membrane of the present invention is simple, the raw materials are widely available, and it is environmentally friendly, making it suitable for large-scale industrial production and application. Description of the Drawings

[0036] Figure 1 It is a physical picture of the regenerated cellulose gel electrolyte membrane in Example 3.

[0037] Figure 2 It is an SEM picture of the regenerated cellulose gel electrolyte membrane in Example 3.

[0038] Figure 3 It is a graph of the ionic conductivity test results of the regenerated cellulose gel electrolyte membranes in Example 3 and Comparative Example 3.

[0039] Figure 4 It is a physical picture of the soft-pack battery assembled with the regenerated cellulose gel electrolyte membrane in Example 3.

[0040] Figure 5 It is the charge-discharge curve of the soft-pack battery assembled with the regenerated cellulose gel electrolyte membrane in Example 3. Specific Embodiments

[0041] The present invention will be further explained and illustrated below in conjunction with specific embodiments.

[0042] Example 1:

[0043] A regenerated cellulose gel electrolyte membrane is prepared as follows:

[0044] 1) Add 0.5 g of bleached softwood pulp to 9.5 g of 1-allyl-3-methylimidazolium acetate, heat to 90 °C and stir to dissolve for 60 min to obtain a cellulose solution;

[0045] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for defoaming for 10 min, and then take it out and cool naturally at room temperature to obtain a cellulose gel membrane;

[0046] 3) Immerse the cellulose gel membrane in 950 g of an aqueous zinc sulfate solution with a concentration of 2 mol / L for 10 h, take it out, and cut it into circular pieces with a diameter of 16 mm to obtain the regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0047] Comparative Example 1:

[0048] A regenerated cellulose gel electrolyte membrane is prepared as follows:

[0049] 1) Add 0.5 g of bleached softwood pulp to 9.5 g of 1-allyl-3-methylimidazolium acetate, heat to 90 °C and stir to dissolve for 60 min to obtain a cellulose solution;

[0050] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly. Then place it in an oven at 100 °C for 10 min to remove air bubbles, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0051] 3) Immerse the cellulose gel film in 200 mL of deionized water for 12 h (for solvent exchange), take it out, soak and wash it repeatedly with deionized water (to completely remove the residual 1-allyl-3-methylimidazolium acetate), cut it into circular pieces with a diameter of 16 mm, and then immerse it in an aqueous solution of zinc sulfate with a concentration of 2 mol / L for 1 h, take it out, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0052] Example 2:

[0053] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0054] 1) Add 0.5 g of bleached bamboo pulp to 9.5 g of 1-allyl-3-methylimidazolium chloride, heat to 90 °C and stir to dissolve for 60 min to obtain a cellulose solution;

[0055] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly. Then place it in an oven at 100 °C for 10 min to remove air bubbles, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0056] 3) Immerse the cellulose gel film in 950 g of an aqueous solution of zinc trifluoromethanesulfonate with a concentration of 2 mol / L for 10 h, take it out, cut it into circular pieces with a diameter of 16 mm, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0057] Comparative Example 2:

[0058] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0059] 1) Add 0.5 g of bleached bamboo pulp to 9.5 g of 1-allyl-3-methylimidazolium chloride, heat to 90 °C and stir to dissolve for 60 min to obtain a cellulose solution;

[0060] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly. Then place it in an oven at 100 °C for 10 min to remove air bubbles, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0061] 3) Immerse the cellulose gel film in 200 mL of deionized water for 12 h, take it out, soak and wash it repeatedly with deionized water, cut it into circular pieces with a diameter of 16 mm, and then immerse it in an aqueous solution of zinc trifluoromethanesulfonate with a concentration of 2 mol / L for 1 h, take it out, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0062] Example 3:

[0063] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0064] 1) Add 0.5 g of bleached hardwood pulp to 9.5 g of a deep eutectic solvent (composed of 3 - aminopropanol and composed according to a molar ratio of 1:1; refer to CN 114105995 A), heat to 90 °C and stir to dissolve for 60 min to obtain a cellulose solution;

[0065] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for defoaming for 10 min, and then take it out and cool naturally at room temperature to obtain a cellulose gel membrane;

[0066] 3) Immerse the cellulose gel membrane in 950 g of an aqueous solution of zinc trifluoromethanesulfonate with a concentration of 2 mol / L for 10 h, take it out, cut it into circular pieces with a diameter of 16 mm, and thus obtain the regenerated cellulose gel electrolyte membrane (with a thickness of 10 μm).

[0067] Comparative Example 3:

[0068] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0069] 1) Add 0.5 g of bleached hardwood pulp to 9.5 g of a deep eutectic solvent (the same as in Example 3), heat to 90 °C and stir to dissolve for 60 min to obtain a cellulose solution;

[0070] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for defoaming for 10 min, and then take it out and cool naturally at room temperature to obtain a cellulose gel membrane;

[0071] 3) Immerse the cellulose gel membrane in 200 mL of deionized water for 12 h, take it out, soak and wash it repeatedly with deionized water, cut it into circular pieces with a diameter of 16 mm, then immerse it in an aqueous solution of zinc trifluoromethanesulfonate with a concentration of 2 mol / L for 1 h, take it out, and thus obtain the regenerated cellulose gel electrolyte membrane (with a thickness of 10 μm).

[0072] Example 4:

[0073] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0074] 1) Add 0.5 g of bacterial cellulose to 9.5 g of a deep eutectic solvent (composed of ethanolamine and Composed in a molar ratio of 1:1; Referring to CN 114105995 A), it is heated to 90 °C and stirred for dissolution for 60 min to obtain a cellulose solution;

[0075] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for degassing for 10 min, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0076] 3) Immerse the cellulose gel film in 950 g of an aqueous zinc acetate solution with a concentration of 2 mol / L for 10 h, take it out, cut it into circular pieces with a diameter of 16 mm, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 10 μm).

[0077] Comparative Example 4:

[0078] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0079] 1) Add 0.5 g of bacterial cellulose to 9.5 g of a deep eutectic solvent (the same as in Example 4), heat it to 90 °C and stir for dissolution for 60 min to obtain a cellulose solution;

[0080] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for degassing for 10 min, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0081] 3) Immerse the cellulose gel film in 200 mL of deionized water for 12 h, take it out, soak and wash it repeatedly with deionized water, cut it into circular pieces with a diameter of 16 mm, then immerse it in an aqueous zinc acetate solution with a concentration of 2 mol / L for 1 h, take it out, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 10 μm).

[0082] Example 5:

[0083] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0084] 1) Add 0.5 g of bacterial cellulose to 9.5 g of (Referring to CN 114105995 A), heat it to 90 °C and stir for dissolution for 60 min to obtain a cellulose solution;

[0085] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for degassing for 10 min, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0086] 3) Immerse the cellulose gel film in 237.5 g of an aqueous zinc chloride solution with a concentration of 15 mol / L for 10 h, take it out, cut it into circular pieces with a diameter of 12 mm, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0087] Comparative Example 5:

[0088] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0089] 1) Add 0.5 g of bacterial cellulose to 9.5 g of and heat to 90 °C, stir and dissolve for 60 min to obtain a cellulose solution;

[0090] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for defoaming for 10 min, and then take it out and naturally cool at room temperature to obtain a cellulose gel film;

[0091] 3) Immerse the cellulose gel film in 200 mL of deionized water for 12 h, take it out, soak and wash it repeatedly with deionized water, cut it into circular pieces with a diameter of 10 mm, then immerse it in an aqueous zinc chloride solution with a concentration of 15 mol / L for 1 h, take it out, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0092] Example 6:

[0093] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0094] 1) Add 1.5 g of microcrystalline cellulose to 8.5 g of a deep eutectic solvent (composed of 3-amino-1-propanol and in a molar ratio of 1:1; refer to CN 114105995 A), heat to 90 °C, stir and dissolve for 60 min to obtain a cellulose solution;

[0095] 2) Place the mold on a glass plate, then inject the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C for defoaming for 10 min, and then take it out and naturally cool at room temperature to obtain a cellulose gel film;

[0096] 3) Immerse the cellulose gel film in 950 g of an aqueous zinc acetate solution with a concentration of 2 mol / L for 10 h, take it out, cut it into circular pieces with a diameter of 16 mm, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 10 μm).

[0097] Comparative Example 6:

[0098] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0099] 1) Add 1.5 g of microcrystalline cellulose to 8.5 g of the eutectic solvent (same as in Example 6), heat to 90 °C and stir to dissolve for 60 min to obtain a cellulose solution;

[0100] 2) Place the mold on a glass plate, then pour the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C to remove bubbles for 10 min, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0101] 3) Immerse the cellulose gel film in 100 mL of deionized water, soak for 12 h, take it out, repeatedly soak and wash with deionized water, cut it into a circular piece with a diameter of 16 mm, and then immerse it in an aqueous solution of zinc acetate with a concentration of 2 mol / L for 1 h, take it out, and obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 10 μm).

[0102] Example 7:

[0103] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0104] 1) Add 0.5 g of cotton fiber to 9.5 g of an aqueous solution of ZnCl with a mass fraction of 65% 2 and heat to 90 °C and stir to dissolve for 90 min to obtain a cellulose solution;

[0105] 2) Place the mold on a glass plate, then pour the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C to remove bubbles for 10 min, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0106] 3) Immerse the cellulose gel film in 475 g of an aqueous solution of zinc sulfate with a concentration of 3 mol / L for 10 h, take it out, cut it into a circular piece with a diameter of 16 mm, and obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0107] Comparative Example 7:

[0108] A regenerated cellulose gel electrolyte membrane, and its preparation method is as follows:

[0109] 1) Add 0.5 g of cotton fiber to 9.5 g of an aqueous solution of ZnCl with a mass fraction of 65% 2 and heat to 90 °C and stir to dissolve for 90 min to obtain a cellulose solution;

[0110] 2) Place the mold on a glass plate, then pour the cellulose solution into the mold and scrape it evenly, then place it in an oven at 100 °C to remove bubbles for 10 min, and then take it out and let it cool naturally at room temperature to obtain a cellulose gel film;

[0111] (3) Immerse the cellulose gel film in 200 mL of deionized water for 12 h, take it out, soak and wash it repeatedly with deionized water, cut it into circular pieces with a diameter of 16 mm, and then immerse it in an aqueous solution of zinc sulfate with a concentration of 3 mol / L for 1 h, take it out, and thus obtain a regenerated cellulose gel electrolyte membrane (with a thickness of 20 μm).

[0112] Performance test:

[0113] (1) The physical picture of the regenerated cellulose gel electrolyte membrane in Example 3 is as Figure 1 (The large picture is in the natural stretching state, and the small picture in the upper right corner is in the state of being folded 180°) shown, and the scanning electron microscope (SEM; the scanning electron microscope test is carried out after freeze-drying) picture is as Figure 2 (The large picture is the cross-section, and the small picture in the upper left corner is the surface) shown.

[0114] It can be seen from Figure 1 that the regenerated cellulose gel electrolyte membrane is colorless and transparent and has good flexibility.

[0115] It can be seen from Figure 2 that the regenerated cellulose gel electrolyte membrane has a thickness of 10 μm and a rich pore structure.

[0116] In addition, through the same test, it is found that the regenerated cellulose gel electrolyte membranes in Examples 1-2 and 4-7 are also colorless and transparent, and also have good flexibility and a rich pore structure.

[0117] (2) The performance test results of the regenerated cellulose gel electrolyte membranes in Examples 1-7 and Comparative Examples 1-7 are shown in the following table (the ion conductivity test results of the regenerated cellulose gel electrolyte membranes in Example 3 and Comparative Example 3 are as Figure 3 shown; the physical picture of the soft-pack battery assembled with the regenerated cellulose gel electrolyte membrane in Example 3 is as Figure 4 shown, and the charge-discharge curve is as Figure 5 shown):

[0118] Table 1 Performance test results of regenerated cellulose gel electrolyte membranes

[0119]

[0120]

[0121] Note:

[0122] Tensile strength: Tested with an electronic universal testing machine.

[0123] Ionic conductivity: Clamp the regenerated cellulose gel electrolyte membrane between two stainless steel sheets, assemble a stainless steel symmetric battery, and at 0.01 Hz - 10 5The impedance test was carried out in the Hz range, and the intrinsic resistance was recorded as R. The thickness of the wet electrolyte film was measured and recorded as l, and the area of the electrolyte membrane was recorded as S. The ionic conductivity σ was calculated by the formula σ = l / (R×S).

[0124] Assembly and testing of the soft-pack battery: The regenerated cellulose gel electrolyte membrane was sandwiched between the metallic zinc anode and the well-coated cathode, and a soft-pack battery was assembled using titanium current collectors and an aluminum-plastic film. At a current density of 1 A / g, cyclic charge-discharge tests were carried out until the battery short-circuited.

[0125] It can be seen from Figure 3 that: compared with the regenerated cellulose gel electrolyte membrane in Comparative Example 3 (without residual cellulose solvent), the regenerated cellulose gel electrolyte membrane in Example 3 (doped with cellulose solvent) has a higher ionic conductivity (29.5 mS / cm).

[0126] It can be seen from Figure 5 that: the soft-pack battery assembled with the regenerated cellulose gel electrolyte membrane in Example 3 has a capacity of more than 400 mAh / g and a cycle life of more than 1000 stable cycles.

[0127] It can be seen from Table 1 that: compared with the regenerated cellulose gel electrolyte membranes in the comparative examples (for example, Example 1 compared with Comparative Example 1; Example 2 compared with Comparative Example 2), the regenerated cellulose gel electrolyte membranes in the examples not only have significantly improved mechanical properties, but also have significantly improved electrochemical properties of the assembled soft-pack batteries.

[0128] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent substitution methods and are all included in the protection scope of the present invention.

Claims

1. A regenerated cellulose gel electrolyte membrane, characterized in that: The composition includes a regenerated cellulose gel membrane, a loaded zinc salt electrolyte and a cellulose solvent; the cellulose solvent is one of an ionic liquid and a low eutectic solvent.

2. The regenerated cellulose gel electrolyte membrane according to claim 1, characterized in that: The mass ratio of the regenerated cellulose gel membrane, the zinc salt electrolyte and the cellulose solvent is 1:8.5-17.1:0.5-1.

9.

3. The regenerated cellulose gel electrolyte membrane according to claim 1 or 2, characterized in that: The regenerated cellulose gel film is made of wood cellulose; the wood cellulose is at least one of microcrystalline cellulose, bacterial cellulose, cotton fiber, bleached coniferous wood pulp, bleached broadleaf wood pulp and bleached bamboo pulp.

4. The regenerated cellulose gel electrolyte membrane according to claim 1 or 2, characterized in that: The zinc salt electrolyte is at least one of zinc sulfate, zinc trifluoromethanesulfonate, zinc acetate, zinc chloride, and zinc perchlorate.

5. The regenerated cellulose gel electrolyte membrane according to claim 1 or 2, characterized in that: The ionic liquid is at least one of 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium acetate, N-methylmorpholine-N-oxide, and ZnCl2; the low eutectic solvent is composed of a hydrogen bond donor and a hydrogen bond acceptor in a molar ratio of 1:0.5 to 5.0; the hydrogen bond donor is at least one of ethanolamine, 3-amino-1-propanol, and isopropanolamine; the hydrogen bond acceptor is X - Cl - Br - One of the above, wherein R is a C2-C6 alkenyl group.

6. The regenerated cellulose gel electrolyte membrane according to claim 1 or 2, characterized in that: The thickness of the regenerated cellulose gel electrolyte membrane is 10 μm to 20 μm.

7. A method for preparing a regenerated cellulose gel electrolyte membrane according to any one of claims 1 to 6, characterized in that: The following steps are involved: 1) heating a cellulose raw material and dissolving it in a cellulose solvent to obtain a cellulose solution; 2) coating the cellulose solution on a substrate, and then degassing and cooling to form a cellulose gel film; 3) Immersing the cellulose gel membrane in a zinc salt electrolyte solution for soaking and regeneration, and taking it out to obtain a regenerated cellulose gel electrolyte membrane.

8. The preparation method according to claim 7, characterized in that: The heating and dissolving in step 1) is carried out at a temperature of 90°C to 110°C, and the heating and dissolving time is 1h to 1.5h; the degassing in step 2) is carried out at a temperature of 100°C to 120°C, and the degassing time is 5min to 10min.

9. The preparation method according to claim 7 or 8, characterized in that: Step 3) The soaking regeneration time is 8h to 12h.

10. A zinc ion battery, characterized in that: A regenerated cellulose gel electrolyte membrane comprising the regenerated cellulose gel electrolyte membrane according to any one of claims 1 to 6.

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