A cellulose-based filled inorganic particle composite gel coating separator, a preparation method thereof and application thereof in aqueous zinc ion batteries

Abstract

This invention belongs to the field of aqueous zinc battery separator technology, and discloses a cellulose-based filled inorganic particle composite gel coating separator, its preparation method, and its application in aqueous zinc-ion batteries. The cellulose-based filled inorganic particle composite gel coating separator comprises a cellulose-based membrane, a nano-alumina / polyethylene glycol layer, and a carboxylated cellulose / graphene oxide composite coating coated on both sides. The aqueous zinc-ion battery separator of this invention, through its layered design, achieves high ion-selective permeability, enhances the separator's ion transport capacity and resistance to zinc dendrite penetration, and features a simple and low-cost preparation process suitable for mass production, providing a novel separator solution for the industrialization of high-performance aqueous zinc-ion batteries.

Description

Technical Field

[0001] This invention belongs to the field of aqueous zinc battery separator technology, specifically relating to a cellulose-based filled inorganic particle composite gel coating separator, its preparation method, and its application in aqueous zinc-ion batteries. Background Technology

[0002] Aqueous zinc-ion batteries are secondary batteries that use aqueous solutions or water-based electrolytes as ion transport carriers. Compared with traditional lithium-ion batteries that use organic electrolytes, they have significant advantages such as superior safety performance, low production cost, and good environmental compatibility. In recent years, they have become a research hotspot in the field of electrochemical energy storage and one of the key directions for industrialization.

[0003] As a core component of the battery structure, the separator plays a crucial role in separating the positive and negative electrodes and allowing ions to pass through. Currently, glass fiber is the most widely used separator material, characterized by high chemical stability, high porosity, and good electrolyte wettability. However, glass fiber separators have significant drawbacks: their large thickness and lack of ion-selective permeability make them prone to shuttle of discharge intermediates, thus reducing battery cycle stability; simultaneously, the large amount of electrolyte adsorbed can accelerate side reactions at the electrode-electrolyte interface, and their low mechanical strength makes them unable to effectively prevent the growth and penetration of zinc dendrites, failing to meet the future development needs of the battery industry.

[0004] Therefore, developing a novel separator that combines ion selectivity with the ability to suppress interfacial side reactions has become a pressing technical problem to be solved in the field of aqueous zinc-ion batteries. Summary of the Invention

[0005] To address the aforementioned shortcomings of existing technologies, the core objective of this invention is to provide a method for preparing a cellulose-based filled inorganic particle composite gel-coated separator and its application in aqueous zinc-ion batteries. This separator can simultaneously suppress interfacial side reactions and achieve ion selective permeation, effectively promoting zinc ion transport and significantly improving the performance of aqueous zinc-ion batteries.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0007] The first aspect of the present invention is to provide a cellulose-based filled inorganic particle composite gel coating membrane, comprising a cellulose-based membrane, a nano-alumina / polyethylene glycol layer filled in the cellulose-based membrane, and a carboxylated cellulose / graphene oxide composite gel coating coated on the surface of the membrane.

[0008] Preferably, the cellulose-based membrane is a medium-speed qualitative filter paper membrane with a pore size range of 15 to 20 μm.

[0009] The pore size of the cellulose membrane determines the cycle life of the battery. Excessively large pore sizes fail to suppress dendrite growth, exacerbating interfacial side reactions and hindering uniform alumina particle packing. Conversely, excessively small pore sizes cause a sharp increase in resistance during zinc ion transport, and reduce the electrolyte's wetting and retention capabilities. Using a medium-speed qualitative filter paper membrane as the cellulose base membrane effectively reduces costs and provides excellent mechanical strength, porous structure, and insulation properties. It offers stable support for the filler and coating layers, ensures unobstructed electrolyte channels, and effectively separates the positive and negative electrodes of the battery.

[0010] Preferably, the nano-alumina particles have a particle size of 10~30 nm and a γ-phase structure.

[0011] By filling cellulose-based membranes with nano-alumina particles, the pore structure of the cellulose membrane can be effectively homogenized. The γ-phase alumina has a large specific surface area, enabling it to further adsorb zinc ions after they are captured by the membrane, thus promoting zinc ion migration.

[0012] Preferably, the amount of nano-alumina filling is 5-7% of the total weight of the cellulose-based membrane.

[0013] By controlling the amount of nano-alumina filling, zinc ions captured by the external gel layer can be effectively adsorbed, promoting zinc ion desolvation and achieving rapid zinc ion transport. The amount of nano-alumina filling should not be too high; appropriate filling is beneficial to improving the stability of the subsequent gel coating and reducing gel layer desorption during battery operation.

[0014] In carboxylated cellulose (CMC), the electrostatic coordination, ion sieving, desolvation, and interfacial regulation of carboxyl groups (-COOH) can achieve uniform zinc deposition, inhibit crystallization, block side reactions, and stabilize the interface. Graphene oxide (GO) is rich in hydroxyl (-OH), carboxyl (-COOH), and epoxy (Ep) groups, which can electrostatically adsorb and coordinate with zinc ions, uniformly dispersing the zinc ion flux, inducing dense zinc deposition, and inhibiting the growth of vertical needle-like dendrites.

[0015] Preferably, the carboxylated cellulose / graphene oxide composite gel coating comprises graphene oxide powder (GO) and carboxylated cellulose (CMC); the degree of substitution of the cellulose hydroxyl groups in the carboxylated cellulose (CMC) with carboxymethyl groups is 0.6 to 0.9. When the degree of substitution of the carboxylated cellulose (CMC) is in the range of 0.6 to 0.9, the dispersion uniformity of graphene oxide can be further improved, and the peel strength between the coating and the base film can be improved.

[0016] Preferably, the graphene oxide (GO) powder is selected from at least one of single-layer graphene oxide, double-layer graphene oxide, and 2-5 layer few-layer graphene oxide.

[0017] A second aspect of the present invention is to provide a method for preparing the above-mentioned cellulose-based filled inorganic particle composite gel-coated separator, the steps of which include: (1) Weigh the required γ-phase alumina particles, polyethylene glycol and deionized water and mix them evenly to prepare a nano alumina suspension; (2) A cellulose-based membrane was laid in a Buchner funnel, and a nano-alumina suspension was poured evenly onto the surface of the cellulose-based membrane. The membrane was then filtered using a vacuum pump until there was no obvious liquid on the surface. The cellulose-based membrane was then removed and dried by blowing air to obtain a cellulose-based filled inorganic particle membrane. (3) Carboxylated cellulose, graphene oxide and deionized water are mixed evenly to prepare carboxylated cellulose / graphene oxide gel coating solution; (4) The carboxylated cellulose / graphene oxide gel coating liquid is coated twice on both sides of the cellulose-based filled inorganic particle membrane using a coating machine, and then dried by blowing air to obtain a cellulose-based filled inorganic particle composite gel coating membrane.

[0018] Preferably, in step (1), the mass ratio of polyethylene glycol, γ-phase nano-alumina particles, and deionized water in the nano-alumina suspension is 1:4:500 to 1:6:500. More preferably, the number-average molecular weight of the polyethylene glycol is 6000.

[0019] Using vacuum filtration to fill alumina particles can effectively improve the uniformity of particle filling and ensure unobstructed ion transport channels.

[0020] Preferably, in step (2), the vacuum pump is a circulating water vacuum pump with a vacuum degree of 0.098 MPa; the single-head pumping capacity of the vacuum pump is 10 L / min.

[0021] Preferably, in step (3), the mass ratio of carboxylated cellulose (CMC) to deionized water is controlled at 1:12.5~1:25, and the amount of graphene oxide added is 0.002~0.005 g / mL. -1 .

[0022] Preferably, in step (3), the coating thickness of the carboxylated cellulose / graphene oxide coating solution on one side is 4~6 μm.

[0023] In step (4), the coating machine is a doctor blade coating machine. The two-coating process involves coating one side of the dried diaphragm and then coating the other side again.

[0024] A third aspect of the present invention is to provide the application of the above-described cellulose-based inorganic particle-filled composite gel coating separator in an aqueous zinc-ion battery.

[0025] A fourth aspect of the present invention is to provide an aqueous zinc-ion battery assembled from the above-described cellulose-based inorganic particle-filled composite gel-coated separator, wherein the aqueous zinc-ion battery is a zinc-vanadium battery, a zinc-manganese battery, a zinc-zinc battery, a zinc-copper battery, or a zinc-titanium battery.

[0026] Compared with the prior art, the present invention has the following beneficial effects: This invention utilizes nano-alumina particles to fill cellulose membranes, effectively homogenizing the pore structure of the cellulose membrane. The large specific surface area of ​​the nano-γ-alumina provides strong adsorption capacity, enabling it to further adsorb zinc ions after they are captured in the membrane, thus promoting zinc ion migration. Carboxylation of the hydroxymethyl groups in the cellulose structure yields carboxylated cellulose (CMC), effectively improving the poor affinity between graphene oxide (GO) powder and the cellulose membrane. Mixing CMC and GO in a specific ratio prepares a carboxymethyl cellulose / graphene oxide colloidal solution, allowing for uniform dispersion of graphene oxide in the colloidal solution. This not only improves the uniformity of the graphene oxide coating but also enhances the bonding force between the cellulose membrane and the graphene oxide coating, significantly increasing the peel strength of the coating and the base membrane. This, in turn, improves the electrochemical safety and performance of the battery, meeting the processing and usage requirements of aqueous zinc-ion batteries. Furthermore, the cellulose-based inorganic particle-filled composite gel coating membrane described in this invention has low production costs, making it suitable for large-scale production applications.

[0027] Compared with the prior art, the beneficial effects of the present invention are also reflected in: The cellulose-based filled inorganic particle composite gel-coated separator of this invention contains a large number of active groups such as hydroxyl, carboxyl, and epoxy groups on its surface. Under the action of electrostatic force, it can effectively separate anions and cations in the electrolyte, significantly improving the ion permeation selectivity of the separator. The nano-alumina filling part promotes zinc ion migration through adsorption, further improving zinc ion transport efficiency. Compared with traditional glass fiber separators, this composite separator can effectively promote the transfer and desolvation process of zinc ions, and has excellent ion selectivity and interfacial side reaction suppression capabilities, thereby greatly improving the cycle stability of aqueous zinc-ion batteries.

[0028] The aqueous zinc battery fabrication process based on a cellulose-based filled inorganic particle composite gel coating membrane of the present invention is simple, reliable, cost-effective, and reproducible, and has broad prospects for industrial application. Attached Figure Description

[0029] Figure 1 This is a SEM image of the diaphragm of the present invention.

[0030] Figure 2 The zinc-zinc aqueous zinc-ion battery prepared for this invention operates at 1 mA·cm⁻¹ -21 mAh·cm -2 The time-voltage curves under the specified conditions are shown in (a), where (a) is the time-voltage curve of the zinc-zinc aqueous zinc-ion battery prepared in Example 1 at 1 mA·cm⁻¹. -2 1mAh·cm -2 The time-voltage curves under the specified conditions are shown in (b), which is the time-voltage curve of the zinc-zinc aqueous zinc-ion battery prepared in Comparative Example 1 at 1 mA·cm⁻¹. -2 1 mAh·cm -2 Time-voltage curve under the given conditions.

[0031] Figure 3 The zinc-copper aqueous zinc-ion batteries prepared in Example 1 and Comparative Example 1 of this invention are used at 1 mA cm⁻¹ -2 0.5mAh cm -2 Cycle number-efficiency plot under given conditions.

[0032] Figure 4 The rate of the zinc-vanadium aqueous zinc-ion battery prepared in Example 1 and Comparative Example 1 of this invention is shown.

[0033] Figure 5 For the zinc-vanadium aqueous zinc-ion batteries prepared in Example 1 and Comparative Example 1 of this invention, at 1 A g -1 Cycle number-specific capacity plot under given conditions.

[0034] Figure 6 This is a SEM image of the zinc negative electrode after operation of the zinc-zinc aqueous zinc-ion battery in Application Example 1 of the present invention.

[0035] Figure 7 The image shows the SEM image of the zinc anode after operation of the zinc-zinc aqueous zinc-ion battery in Comparative Example 1 of this invention.

[0036] Figure 8 The time-voltage diagram of the zinc-zinc aqueous zinc-ion battery used in the comparative example of this invention.

[0037] Figure 9 This is a cycle life-efficiency graph of the zinc-copper aqueous zinc-ion battery used in the comparative example of this invention.

[0038] Figure 10 This is a cycle life-specific capacity diagram of the zinc-vanadium aqueous zinc-ion battery used in the comparative example of this invention. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments, and the advantages and features of the present invention will become clearer with the description. However, the embodiments are merely exemplary and do not constitute any limitation on the scope of the present invention. Those skilled in the art should understand that modifications or substitutions can be made to the details and form of the technical solutions of the present invention without departing from the spirit and scope of the present invention, but all such modifications and substitutions fall within the protection scope of the present invention.

[0040] Unless otherwise specified, the experimental methods used in the embodiments of this invention are all conventional experimental methods; the materials and reagents used can be obtained through commercial channels unless otherwise specified.

[0041] The medium-speed qualitative filter paper membranes used in all embodiments were purchased from Hangzhou Fuyang Beimu Pulp & Paper Co., Ltd., ZX200648 medium-speed qualitative filter paper with a pore size of 15 ~ 20 μm.

[0042] Example 1 A method for preparing a cellulose-based filled inorganic particle composite gel-coated separator, comprising the following steps: (1) 0.5 g of alumina particles with a γ phase particle size of 20 nm, 0.1 g of polyethylene glycol (number average molecular weight of 6000) and 50 mL of deionized water were mixed and stirred for 24 h to prepare a nano alumina suspension. (2) Select a medium-speed qualitative filter paper membrane with a diameter of 7 cm and a membrane basis weight of 0.3113 g. Spread it evenly in a Buchner funnel with the same inner diameter, wet the surface with deionized water, and build a vacuum filtration device using a circulating water vacuum pump with a single-head pumping volume of 10 L / min and a vacuum degree maintained at 0.098 MPa.

[0043] (3) Take 1.89 mL of the prepared nano alumina suspension, dilute it to 20 mL with deionized water and pour it evenly onto the surface of the filter paper membrane. Use a vacuum pump to filter until there is no obvious liquid on the surface. Take out the cellulose membrane and dry it at 60°C to obtain a cellulose-based filled inorganic particle membrane.

[0044] (4) Weigh 0.04 g of bilayer graphene oxide powder, 0.4 g of carboxylated cellulose with a degree of substitution of 0.8 and 10 mL of deionized water and mix them thoroughly to prepare a carboxylated cellulose / graphene oxide coating solution.

[0045] (5) Set the coating thickness of the doctor blade coater to 5 μm, first coat one side of the cellulose-based filled inorganic particle membrane, dry it at 60 ℃, then coat the other side of the cellulose-based filled inorganic particle membrane with a thickness of 5 μm, dry it at 60 ℃, and obtain the cellulose-based filled inorganic particle composite gel coating membrane.

[0046] like Figure 1As shown, the diaphragm of this invention is supported by a fibrous skeleton, forming a continuous three-dimensional interpenetrating network structure, which provides excellent mechanical support properties and effectively suppresses the risk of zinc dendrite puncture. The interior of the diaphragm forms a multi-level pore structure composed of micron-level pores generated by fiber overlap and submicron-level pores between particles. This provides ample storage sites for the electrolyte, increasing electrolyte retention, and also constructs continuous ion transport channels, ensuring uniform and rapid ion migration.

[0047] Example 2 This embodiment provides another cellulose-based filled inorganic particle composite gel coating membrane and its preparation method. In step (3), the amount of nano alumina suspension is 1.56 mL, which is diluted with deionized water and then poured evenly onto the surface of the filter paper membrane. The rest is the same as in Example 1.

[0048] Example 3 This embodiment provides another cellulose-based filled inorganic particle composite gel coating membrane and its preparation method. In step (3), the amount of nano alumina suspension is 2.18 mL, which is diluted with deionized water and then poured evenly onto the surface of the filter paper membrane. The rest is the same as in Example 1.

[0049] Example 4 This embodiment provides another cellulose-based filled inorganic particle composite gel coating membrane and its preparation method. In step (2), the composition of the nano alumina suspension is 0.5 g of alumina particles with a γ phase particle size of 10 nm, 0.1 g of polyethylene glycol (number average molecular weight of 6000) and 50 mL of deionized water, and the rest are the same as in Example 1.

[0050] Example 5 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (2), the composition of the nano alumina suspension is 0.5 g of alumina particles with a γ phase particle size of 30 nm, 0.1 g of polyethylene glycol (number average molecular weight of 6000) and 50 mL of deionized water, and the rest are the same as in Example 1.

[0051] Example 6 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (2), the composition of the nano alumina suspension is 0.4 g of alumina particles with a γ phase particle size of 20 nm, 0.1 g of polyethylene glycol (number average molecular weight of 6000) and 50 mL of deionized water, and the rest are the same as in Example 1.

[0052] Example 7 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (2), the composition of the nano alumina suspension is 0.6 g of alumina particles with a γ phase particle size of 20 nm, 0.1 g of polyethylene glycol (number average molecular weight of 6000) and 50 mL of deionized water, and the rest are the same as in Example 1.

[0053] Example 8 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (4), the component ratio is as follows: 0.04 g of bilayer graphene oxide powder, 0.4 g of carboxylated cellulose with a degree of substitution of 0.6 and 10 mL of deionized water are thoroughly mixed evenly, and the rest are the same as in Example 1.

[0054] Example 9 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (4), the component ratio is as follows: 0.04 g of bilayer graphene oxide powder, 0.4 g of carboxylated cellulose with a degree of substitution of 0.9 and 10 mL of deionized water are thoroughly mixed evenly, and the rest are the same as in Example 1.

[0055] Example 10 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (4), the component ratio is as follows: 0.04 g of bilayer graphene oxide powder, 0.8 g of carboxylated cellulose with a degree of substitution of 0.8 and 10 mL of deionized water are thoroughly mixed evenly, and the rest are the same as in Example 1.

[0056] Example 11 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (4), the component ratio is as follows: 0.04 g of bilayer graphene oxide powder, 0.6 g of carboxylated cellulose with a degree of substitution of 0.8 and 10 mL of deionized water are thoroughly mixed evenly, and the rest are the same as in Example 1.

[0057] Example 12 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (5), the coating thickness of the doctor blade coater is set to 4 μm, and the rest are the same as in embodiment 1.

[0058] Example 13 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (5), the coating thickness of the doctor blade coater is set to 6 μm, and the rest are the same as in embodiment 1.

[0059] Comparative Example 1 This embodiment provides another aqueous zinc-ion battery separator material, which is a commercially available Whatman (CAT No. 1825-110) glass fiber separator, without any treatment.

[0060] Comparative Example 2 This embodiment provides another aqueous zinc-ion battery separator material, which is a medium-speed qualitative filter paper membrane purchased from Hangzhou Fuyang Beimu Pulp & Paper Co., Ltd., ZX200648 medium-speed qualitative filter paper with a pore size of 15 ~ 20 μm, and is not treated.

[0061] Comparative Example 3 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (2), the composition of the nano alumina suspension is 0.8 g of alumina particles with a γ phase particle size of 20 nm, 0.1 g of polyethylene glycol (number average molecular weight of 6000) and 50 mL of deionized water, and the rest are the same as in Example 1.

[0062] Comparative Example 4 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (4), the component ratio is as follows: 0.04 g of bilayer graphene oxide powder, 1.0 g of carboxylated cellulose with a degree of substitution of 0.8 and 10 mL of deionized water are thoroughly mixed evenly, and the rest are the same as in Example 1.

[0063] Comparative Example 5 This embodiment provides another cellulose-based filled inorganic particle composite gel coating film and its preparation method. In step (4), the component ratio is as follows: 0.1 g of bilayer graphene oxide powder, 0.4 g of carboxylated cellulose with a degree of substitution of 0.9 and 10 mL of deionized water are thoroughly mixed evenly, and the rest are the same as in Example 1.

[0064] Application Examples Zinc-zinc aqueous zinc-ion batteries, zinc-copper aqueous zinc-ion batteries, and zinc-vanadium aqueous zinc-ion batteries were prepared using aqueous zinc-ion battery separators from Examples 1 to 13 and Comparative Examples 1 to 5, respectively, and their performance was tested.

[0065] 1. Battery manufacturing method Zinc-zinc aqueous zinc-ion battery: The separator and the 50 μm thick ultrathin zinc foil are cut into discs with a diameter of 12 mm respectively; using the CR2032 type battery case, the zinc-zinc aqueous zinc-ion battery is assembled in the following order: negative electrode shell, zinc foil, separator, 80 μL 2 M zinc trifluoromethanesulfonate electrolyte, zinc foil, gasket, and positive electrode shell.

[0066] Zinc-copper aqueous zinc-ion battery: The separator, 50 μm thick ultrathin zinc foil and copper foil are cut into discs with a diameter of 12 mm respectively; using CR2032 type battery case, the zinc-copper aqueous zinc-ion battery is assembled in the following order: negative electrode shell, zinc foil, separator, 80 μL 2 M trifluoromethanesulfonate zinc electrolyte, copper foil, gasket, and positive electrode shell.

[0067] Zinc-vanadium aqueous zinc-ion battery: Under magnetic stirring, 0.364 g of vanadium pentoxide was dissolved in 150 mL of deionized water, and 0.17 g of 3,4-ethylenedioxythiophene was added. The mixture was kept under reflux at 100 °C for 12 hours, and then cooled to room temperature. The reaction product was centrifuged three times with deionized water, and the centrifuged product was collected. The collected product was freeze-dried to finally obtain poly(3,4-ethylenedioxythiophene) intercalated vanadium pentoxide.

[0068] Poly(3,4-ethylenedioxythiophene) intercalated vanadium pentoxide, acetylene black, and polyvinylidene fluoride were thoroughly mixed at a mass ratio of 7:2:1. The mixture was then mixed with N-methylpyrrolidone at a mass ratio of 1:3 to form a homogeneous slurry. This slurry was poured onto a stainless steel mesh and dried overnight at 60 °C to obtain a poly(3,4-ethylenedioxythiophene) intercalated vanadium pentoxide cathode. The prepared cathode material, composite coated separator, and ultrathin zinc foil were cut into discs with a diameter of 12 mm. Using a CR2032 battery case, a zinc-vanadium aqueous zinc-ion battery was assembled in the following order: negative electrode shell, zinc foil, separator, 80 μL 2 M zinc trifluoromethanesulfonate electrolyte, poly(3,4-ethylenedioxythiophene) intercalated vanadium pentoxide cathode, gasket, and positive electrode shell.

[0069] 2. Performance Test Results Application Example 1 The zinc-zinc aqueous zinc-ion battery assembled in Example 1 exhibits excellent cycle life at 1 mA cm⁻¹. -2 1mAh cm -2 Under these conditions, its time-voltage diagram is as follows: Figure 2 As shown, the zinc-zinc symmetric battery assembled with the separator of this invention exhibits excellent long-term cycle stability, operating stably for over 5000 hours with a consistently stable voltage plateau and no significant increase in polarization voltage. These results demonstrate that the separator of this invention can effectively regulate uniform zinc ion deposition, suppress zinc dendrite growth and interfacial side reactions, constructing a long-term stable zinc anode interface, and significantly improving the battery's cycle life and reversibility. (At 1 mA cm⁻¹) -2 1 mAh cm -2 After running for 60 hours under the specified conditions, the SEM image of the zinc anode is as follows: Figure 6As shown in the figure, the zinc anode surface using the separator of the present invention exhibits a highly ordered layered preferred orientation deposition structure. The layers are densely stacked with smooth edges, and no obvious zinc dendrites, corrosion pits, or by-product accumulation were observed. This result indicates that the separator of the present invention can effectively regulate the uniform distribution of zinc ions, guide zinc to deposit in an orderly layered manner, suppress dendrite growth and interfacial side reactions, and significantly improve the interfacial stability and deposition / dissolution reversibility of the zinc anode.

[0070] Example 1: The assembled zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹ -2 0.5 mAh cm -2 Under the given conditions, its cycle number-efficiency graph is as follows: Figure 3 As shown, the coulombic efficiency rapidly increases and stabilizes at nearly 100% in the initial stage of cycling. Within 300 cycles, the efficiency curve shows no significant fluctuations or decay, with an average coulombic efficiency as high as 98.56%. This result demonstrates that the separator of this invention can effectively guide uniform zinc ion deposition, significantly suppress zinc dendrite growth and interfacial side reactions, greatly reduce irreversible zinc loss and the formation of "dead zinc," and achieve a highly reversible zinc deposition / dissolution process, providing a crucial guarantee for the long-term cycle stability of the battery.

[0071] Example 1: The assembled zinc-vanadium aqueous zinc-ion battery was tested at 3 A g. -1 The cycle number-specific capacity graph at current density is shown below. Figure 5 As shown, the battery using the separator of this invention exhibits excellent long-cycle stability, with a maximum specific capacity of 272.26 mAh g⁻¹. -1 During the first 1000 cycles, the capacity retention rate reached 97.6%, and after 5000 cycles, it still maintained a high specific capacity, with the coulombic efficiency consistently remaining close to 100%. These results demonstrate that the separator of this invention can effectively suppress zinc dendrite growth and interfacial side reactions, maintain a stable electrode / electrolyte interface, and significantly improve the long-cycle reversibility and lifespan of the battery. The rate test results are shown below. Figure 4 As shown, as the current density increases from 0.1 A g 1 Upgraded to 5.0 Ag 1 The battery specific capacity only decreased slightly, remaining at 5.0 A g. 1 It can still maintain about 280 mAh g at high rates 1 It maintains a stable specific capacity, and its coulombic efficiency remains consistently close to 100% across the entire rate range. When the current density drops to 0.1 A g... 1When the battery capacity is almost completely restored to the initial level, it indicates that the separator of the present invention can maintain a stable zinc deposition / dissolution interface over a wide current density range, which significantly improves the rate adaptability and reversibility of the battery.

[0072] Application Example 2 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 2 operates at 1 mA cm⁻¹. -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4500 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.3%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacitance at current density can reach 268.32 mAh g. -1 Furthermore, the capacity retention rate can reach 95.37% in the first 1000 cycles.

[0073] Application Example 3 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 3 at 1 mA cm⁻¹ -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4200 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.5%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum current density discharge specific capacity can reach 266.15 mAh g. -1 Furthermore, the capacity retention rate can reach 95.25% in the first 1000 cycles.

[0074] Application Example 4 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 4 operates at 1 mA cm⁻¹. -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4400 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.2%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum current density-dependent capacitance can reach 254.65 mAh g. -1 Furthermore, the capacity retention rate can reach 96.6% in the first 1000 cycles.

[0075] Application Example 5 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 5 operates at 1 mA cm⁻¹. -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4100 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.6%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacitance at current density can reach 205.57 mAh g. -1 Furthermore, the capacity retention rate can reach 94.92% in the first 1000 cycles.

[0076] Application Example 6 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 6 at 1 mA cm⁻¹ -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4750 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.5%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacitance at current density can reach 247.3 mAh g. -1 Furthermore, the capacity retention rate can reach 95.9% in the first 1000 cycles.

[0077] Application Example 7 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 7 operates at 1 mA cm⁻¹. -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4400 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.4%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacitance at current density can reach 249.3 mAh g. -1 Furthermore, the capacity retention rate can reach 86.6% in the first 1000 cycles.

[0078] Application Example 8 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 8 operates at 1 mA cm⁻¹. -2 1 mAh cm -2Under these conditions, stable cycling can be achieved for over 4720 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.5%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum current density discharge specific capacity can reach 235.63 mAh g. -1 Furthermore, the capacity retention rate can reach 96.4% in the first 1000 cycles.

[0079] Application Example 9 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 9 operates at 1 mA cm⁻¹. -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4680 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.2%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacitance at current density can reach 244.7 mAh g. -1 Furthermore, the capacity retention rate can reach 95.54% in the first 1000 cycles.

[0080] Application Example 10 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 10 at 1 mA cm⁻¹ -2 1 mAh cm -2 Under these conditions, stable cycling can be achieved for over 4910 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.65%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacity at current density can reach 268.37 mAh g. -1 Furthermore, the capacity retention rate can reach 94.91% in the first 1000 cycles.

[0081] Application Example 11 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 11 at 1 mA cm⁻¹ -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4460 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2Under these conditions, the average efficiency for the first 300 cycles is 97.43%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum current density discharge specific capacity can reach 236.62 mAh g. -1 Furthermore, the capacity retention rate can reach 94.49% in the first 1000 cycles.

[0082] Application Example 12 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 12 at 1 mA cm⁻¹ -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4650 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.46%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacity at current density can reach 258.77 mAh g. -1 Furthermore, the capacity retention rate can reach 95.69% in the first 1000 cycles.

[0083] Application Example 13 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Example 13 at 1 mA cm⁻¹ -2 1 mAh cm -2 Under certain conditions, stable cycling can be achieved for over 4220 hours; the zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 Under these conditions, the average efficiency for the first 300 cycles is 97.93%; the zinc-vanadium aqueous zinc-ion battery at 3 A g -1 The maximum specific capacitance at current density can reach 260.12 mAh g. -1 Furthermore, the capacity retention rate can reach 95.24% in the first 1000 cycles.

[0084] Application Comparative Example 1 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Comparative Example 1 at 1 mA cm⁻¹ -2 1 mAh cm -2 Time-voltage diagram under the condition is as follows Figure 2As shown, under the same test conditions, the symmetrical battery assembled with a glass fiber separator exhibited severe voltage fluctuations and polarization anomalies after only about 60 hours of cycling. The initial polarization voltage was high, and the curve showed continuous oscillations, indicating poor interface stability. This suggests that traditional glass fiber separators cannot effectively suppress the disordered growth of zinc dendrites and electrolyte side reactions, making it difficult to maintain a stable zinc deposition / dissolution process. The battery system is prone to rapid failure, highlighting its limitations in long-cycle applications of aqueous zinc-ion batteries.

[0085] At 1 mA cm -2 1 mAh cm -2 After running for 60 hours under the specified conditions, the SEM images of the zinc anode are as follows: Figure 7 As shown in the figure, the zinc anode surface exhibits a severely disordered and porous morphology, forming numerous broken layered structures and porous regions, exhibiting typical moss-like / sponge-like zinc deposition characteristics. This indicates that the glass fiber membrane cannot effectively regulate the uniform deposition of zinc ions, nor can it suppress the disordered growth of zinc dendrites and interfacial side reactions, leading to severe pulverization of the zinc anode interface, the formation of a large amount of "dead zinc," and extremely poor interfacial stability and deposition / dissolution reversibility, making it difficult to support the long-term stable operation of aqueous zinc-ion batteries.

[0086] Zinc-copper aqueous zinc-ion batteries at 1 mA cm -2 0.5 mAh cm -2 The cycle number-efficiency graph under the given conditions is shown below. Figure 3 As shown, under the same test conditions, the coulombic efficiency of the zinc-copper half-cell using a glass fiber separator is poor. The coulombic efficiency fluctuates drastically in the early stages of cycling, with some cycles showing efficiency below 40%, and a stable efficiency plateau is never established. This phenomenon indicates that the glass fiber separator is unable to control the uniform distribution of zinc ions, and cannot effectively suppress side reactions such as disordered zinc dendrite growth, zinc corrosion, and electrolyte decomposition. This results in a large amount of zinc being consumed irreversibly, with poor deposition / dissolution reversibility, making it difficult to support long-term stable operation of aqueous zinc-ion batteries.

[0087] Zinc-vanadium aqueous zinc-ion batteries at 3 A g -1 The cycle number-specific capacity graph at current density is shown below. Figure 5 As shown, the highest specific capacity is less than 175 mAh g. -1 In contrast, batteries using glass fiber separators exhibit poor long-cycle performance. The capacity retention rate after the first 1000 cycles is only 76.6%, and the capacity rapidly declines with each cycle, even showing a significant drop in later stages. This indicates that traditional glass fiber separators cannot effectively suppress zinc dendrite growth and interfacial side reactions, making it difficult to maintain a stable electrode interface. This results in severe irreversible capacity loss during long-cycle operation, and the cycle life is far lower than that of batteries using the separator of this invention.

[0088] Application Comparative Example 2 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Comparative Example 2 operates at 1 mA cm⁻¹. -2 1 mAh cm -2 Time-voltage diagram under the condition is as follows Figure 8 As shown, Comparative Example 2 exhibited severe voltage polarization fluctuations and significant voltage spikes in the early stages of cycling, indicating its inability to effectively control zinc ion deposition behavior. This resulted in severe disordered zinc dendrite growth, poor interface stability, and the battery system nearing failure within a short period. The zinc-copper aqueous zinc-ion battery at 1 mA cm⁻¹... -2 0.5 mAh cm -2 The cycle number-efficiency graph under the given conditions is shown below. Figure 9 As shown, its coulombic efficiency exhibits a fatal flaw, displaying numerous significant outliers and failing to form a stable efficiency plateau. This result indicates that it cannot effectively control zinc ion deposition behavior, resulting in severe disordered zinc dendrite growth, frequent interfacial side reactions and localized short circuits, and an inability to maintain a stable zinc deposition / dissolution process, thus lacking practical application value. The zinc-vanadium aqueous zinc-ion battery at 3 A g... -1 The cycle number-specific capacity graph at current density is shown below. Figure 10 As shown, its long-cycle performance has a fatal flaw: the capacity decays rapidly in a precipitous manner. After 4,000 cycles, the specific capacity is less than half of the initial value, indicating that it cannot effectively suppress zinc dendrites and interfacial side reactions. The battery system continues to deteriorate during cycling and does not have long-cycle stability.

[0089] Application Comparative Example 3 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Comparative Example 3 at 1 mA cm⁻¹ -2 1 mAh cm -2 Time-voltage diagram under the condition is as follows Figure 8 As shown, in the early stages, the polarization fluctuations in Comparative Example 3 were relatively small, but long-term stable operation was still not achieved. With continued cycling, the interfacial polarization continuously increased, indicating limited ability to suppress zinc dendrites and side reactions, and insufficient interfacial stability. The zinc-copper aqueous zinc-ion battery at 1 mA cm⁻¹... -2 0.5 mAh cm -2 The cycle number-efficiency graph under the given conditions is shown below. Figure 9 As shown, the coulombic efficiency is generally low and fluctuates significantly, with the efficiency concentrated between 85% and 95% in the stable phase, indicating significant irreversible zinc loss. This suggests insufficient ability to suppress zinc dendrite growth and interfacial side reactions, poor interfacial stability, and poor reversibility of zinc deposition / dissolution, making it difficult to support long-term stable operation of the battery. The zinc-vanadium aqueous zinc-ion battery at 3 A g... -1 The cycle number-specific capacity graph at current density is shown below. Figure 10As shown, in general, Comparative Example 3 exhibits a faster capacity decay rate, with the highest specific capacity being approximately 265 mAh g⁻¹. -1 The capacity decreased significantly after the first 1000 cycles, and abnormal fluctuations occurred later, indicating that it was not able to protect the electrode interface, the interface continued to deteriorate, and the long-term cycle stability was poor.

[0090] Application Comparative Example 4 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Comparative Example 4 operates at 1 mA cm⁻¹. -2 1 mAh cm -2 Time-voltage diagram under the condition is as follows Figure 8 As shown, it can operate stably for approximately 1500 cycles, but the voltage polarization remains at a low level, indicating that it has a good suppression effect on zinc dendrites and side reactions. The interface stability is significantly improved compared to the previous two methods, but there is still a trend of increasing polarization under long-term cycling. The zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 The cycle number-efficiency graph under the given conditions is shown below. Figure 9 As shown, its coulombic efficiency exhibits significant defects: the efficiency is significantly low and rises slowly in the initial cycling phase, and even after stabilization, it cannot consistently maintain a level close to 100%. This indicates poor interfacial wettability and compatibility, severe irreversible zinc loss in the initial cycling phase, insufficient interfacial microenvironment stability, and defects in the reversibility of zinc deposition / dissolution. The zinc-vanadium aqueous zinc-ion battery at 3 A g... -1 The cycle number-specific capacity graph at current density is shown below. Figure 10 As shown, its initial capacity was insufficient, reaching a maximum of only about 267.3 mAh g. -1 Furthermore, the capacity decays rapidly after the first 1000 cycles, and the overall capacity level is low in the later stages, indicating that its interfacial impedance is high and its ability to suppress zinc dendrites and side reactions is limited. Both its capacity utilization and long-cycle stability have obvious defects.

[0091] Application Comparative Example 5 The zinc-zinc aqueous zinc-ion battery obtained using the separator of Comparative Example 5 at 1 mA cm⁻¹ -2 1 mAh cm -2 Time-voltage diagram under the condition is as follows Figure 8 As shown, the voltage curve of Comparative Example 5 is generally stable, but slight polarization fluctuations still exist, and the polarization voltage is not completely constant. There is still room for improvement in interface regulation capability, and there is a potential risk of interface deterioration under long-term cycling conditions. The zinc-copper aqueous zinc-ion battery operates at 1 mA cm⁻¹. -2 0.5 mAh cm -2 The cycle number-efficiency graph under the given conditions is shown below. Figure 9As shown, although the overall coulombic efficiency of this comparative example is close to 100%, there are still slight fluctuations, and the average efficiency level is slightly lower than that of the separator of this invention. This indicates that although its interface regulation capability is better than other comparative examples, it still does not achieve completely uniform ion transport and zero side reactions, and there is still a potential risk of interface deterioration under long-term cycling or high-rate conditions. Zinc-vanadium aqueous zinc-ion batteries at 3 Ag... -1 The cycle number-specific capacity graph at current density is shown below. Figure 10 As shown, compared to Comparative Examples 2 to 4, Comparative Example 5 has the best performance among the four groups, but its capacity still shows a significant decay after the first 1000 cycles, and the capacity continues to decrease in subsequent cycles. This indicates that its interface control capability is still insufficient, and it cannot achieve stable capacity output under ultra-long cycles. There is still a risk of performance degradation in long-term operation.

[0092] Comparing Comparative Examples 2-4 and Application Examples 1-16, the overall performance comparison shows that the separator of this invention exhibits comprehensive performance advantages compared to Comparative Examples 2-5: First, it has a significantly stronger ability to regulate the zinc anode interface, effectively guiding uniform zinc ion deposition, suppressing dendrite growth and interfacial side reactions, and constructing a long-term stable electrode / electrolyte interface. Second, its long-cycle stability is significantly improved, maintaining high capacity and stable polarization even after 5000 cycles, solving the lifespan limitation caused by interface deterioration in traditional separators. Third, the reversibility of zinc deposition / dissolution is greatly improved, with coulombic efficiency remaining stable at nearly 100% for a long period, significantly reducing irreversible zinc loss. Fourth, it has excellent rate performance, with capacity retention and recovery capabilities at high rates significantly better than the comparative examples, and can adapt to operating conditions over a wide current density range. These advantages collectively demonstrate that the separator of this invention provides key support for the long-life and high-safety operation of aqueous zinc-ion batteries, possessing significant practical application potential.

[0093] 3. Conclusion The electrochemical performance of the aqueous zinc-ion battery assembled with the diaphragm of this invention is far superior to that of the traditional glass fiber diaphragm.

[0094] This invention uses a cellulose-based membrane as a carrier, filling the interior of the cellulose membrane with nano-alumina particles, and coating both sides with a carboxymethyl cellulose / graphene oxide composite gel coating. The cellulose-based membrane possesses high mechanical strength and puncture resistance, is low in cost, and has good biocompatibility. The nano-alumina filling layer can reduce and homogenize the pore size of the cellulose membrane, enhancing the mechanical properties and thermal stability of the separator, reducing interfacial impedance during battery operation, and improving the battery's rate performance. The carboxymethyl cellulose / graphene oxide gel coating can regulate zinc ion transport, uniform ion flux, and suppress side reactions. The graphene oxide component, rich in oxygen-containing functional groups, can rapidly capture zinc ions in the electrolyte, synergistically regulating the uniform migration and deposition of zinc ions.

[0095] In summary, the separator of the present invention can solve the problems of local current concentration caused by uneven pore size of existing aqueous zinc-ion battery separators, short circuit caused by severe zinc dendrite growth, battery bulging and short lifespan caused by intense hydrogen evolution side reactions, as well as poor mechanical properties and easy deformation and damage of the separator. Moreover, the overall preparation process of the separator of the present invention is simple and low in cost, making it suitable for large-scale production.

[0096] The above description is merely a preferred embodiment of the present invention and does not limit the implementation methods and scope of protection of the present invention. Those skilled in the art should recognize that any solutions obtained by making equivalent substitutions and obvious changes based on the content shown in the specification and figures of this invention should be included within the scope of protection of this invention.

Claims

1. A cellulose-based filled inorganic particle composite gel-coated separator, characterized in that, It includes a cellulose-based membrane, a nano-alumina / polyethylene glycol filling layer filled in the cellulose-based membrane, and a carboxylated cellulose / graphene oxide composite gel coating coated on the surface of the membrane.

2. The cellulose-based filled inorganic particle composite gel-coated membrane according to claim 1, characterized in that, The cellulose-based membrane is a medium-speed qualitative filter paper membrane with a pore size range of 15 ~ 20 μm.

3. The cellulose-based filled inorganic particle composite gel-coated membrane according to claim 1, characterized in that, The nano-alumina particles have a particle size of 10~30 nm and a γ-phase structure.

4. The cellulose-based filled inorganic particle composite gel-coated membrane according to claim 1, characterized in that, The amount of nano-alumina filling is 5-7% of the total weight of the cellulose-based membrane.

5. The method for preparing the cellulose-based filled inorganic particle composite gel-coated diaphragm according to claim 1, characterized in that, Includes the following steps: (1) Weigh the required γ-phase alumina particles, polyethylene glycol and deionized water and mix them evenly to prepare a nano alumina suspension; (2) A cellulose-based membrane was laid in a Buchner funnel, and a nano-alumina suspension was poured evenly onto the surface of the cellulose-based membrane. The membrane was then filtered using a vacuum pump until there was no obvious liquid on the surface. The cellulose-based membrane was then removed and dried by blowing air to obtain a cellulose-based filled inorganic particle membrane. (3) Carboxylated cellulose, graphene oxide and deionized water are mixed evenly to prepare carboxylated cellulose / graphene oxide gel coating solution; (4) The carboxylated cellulose / graphene oxide gel coating liquid is coated twice on both sides of the cellulose-based filled inorganic particle membrane using a coating machine, and then dried by blowing air to obtain a cellulose-based filled inorganic particle composite gel coating membrane.

6. The method for preparing the cellulose-based filled inorganic particle composite gel-coated diaphragm according to claim 5, characterized in that, In step (1), the mass ratio of polyethylene glycol, γ-phase nano-alumina particles and deionized water in the nano-alumina suspension is 1:4:500~1:6:500; the number average molecular weight of the polyethylene glycol is 6000.

7. The method for preparing the cellulose-based filled inorganic particle composite gel-coated diaphragm according to claim 5, characterized in that, In step (2), the vacuum pump is a circulating water vacuum pump with a vacuum degree of 0.098 MPa; the single-head pumping capacity of the vacuum pump is 10 L / min.

8. The method for preparing the cellulose-based filled inorganic particle composite gel-coated diaphragm according to claim 5, characterized in that, In step (3), the mass ratio of carboxylated cellulose to deionized water is controlled at 1:12.5~1:25, and the amount of graphene oxide added is 0.002~0.005 g / mL. -1 In step (3), the coating thickness of the carboxylated cellulose / graphene oxide coating solution on one side is 4~6 μm.

9. The application of the cellulose-based filled inorganic particle composite gel-coated separator according to claim 1 in an aqueous zinc-ion battery.

10. The aqueous zinc-ion battery assembled from the cellulose-based filled inorganic particle composite gel-coated separator according to claim 1, characterized in that, The aqueous zinc-ion battery is a zinc-vanadium battery, a zinc-manganese battery, a zinc-zinc battery, a zinc-copper battery, or a zinc-titanium battery.

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