Graphene oxide film-based zinc ion battery negative electrode protection material and preparation method thereof, and aqueous zinc ion battery

Abstract

This invention discloses a zinc-ion battery anode protection material based on graphene oxide film, its preparation method, and an aqueous zinc-ion battery. The graphene oxide film-based zinc-ion battery anode protection material is formed by self-assembly of graphene oxide nanosheets and Triton X-100 through molecular-level intercalation and hydrogen bonding network crosslinking. The preparation method of the graphene oxide film-based zinc-ion battery anode protection material includes five adaptive states: initial dispersion, organic phase spreading, dual-convective self-assembly, film consolidation, and substrate transfer. The states are closed-loop transferred using criteria such as Zeta potential and reflected light inhomogeneity, and the process is based on η. MA ≥5 Reverse adjustment formula. This invention achieves a balance between high modulus, high toughness, and nanoscale thickness, effectively suppressing zinc dendrite growth and hydrogen evolution side reactions, and extending the cycle life of aqueous zinc-ion batteries.

Description

Technical Field

[0001] This invention belongs to the field of aqueous zinc-ion battery anode interface engineering technology, specifically relating to a zinc-ion battery anode protection material based on graphene oxide film and its preparation method, as well as an aqueous zinc-ion battery. Background Technology

[0002] Aqueous zinc-ion batteries are widely regarded as one of the most promising candidates for next-generation grid-scale energy storage due to the intrinsic safety provided by aqueous electrolytes, the high theoretical specific capacity and low redox potential of metallic zinc anodes, and the abundant and inexpensive zinc resources in the Earth's crust. In applications such as large-scale renewable energy generation and distributed energy storage, aqueous zinc-ion batteries are expected to become a powerful supplement or even replacement for lithium-ion batteries in stationary energy storage. However, the long-term electrochemical stability of metallic zinc, the core active material in the electrochemical reaction of aqueous zinc-ion batteries, in aqueous electrolyte environments is far from meeting the requirements for industrial applications. This bottleneck severely restricts the transition of aqueous zinc-ion batteries from laboratory research to large-scale industrial application.

[0003] Specifically, during repeated electrodeposition and stripping processes, zinc anodes are highly susceptible to uncontrolled dendrite growth due to the coupling effects of multiple factors, including uneven surface electric field distribution, gradient differences in ion flux, and localized current density concentration. Once these dendrites break through the separator, they can trigger internal short circuits, leading to thermal runaway or even safety accidents. Simultaneously, hydrogen evolution and self-corrosion continuously occur between zinc and the aqueous electrolyte, consuming active materials, altering electrolyte composition, and accumulating a porous byproduct layer on the zinc anode surface, further deteriorating ion transport channels and interfacial stability. These failure mechanisms reinforce each other, creating a vicious cycle that ultimately results in aqueous zinc-ion batteries failing to meet the cycle life and coulombic efficiency requirements of practical engineering applications.

[0004] To address the aforementioned failure mechanisms, researchers have generally attempted to construct artificial interface protective layers on the surface of the zinc anode, aiming to simultaneously achieve physical blocking of zinc dendrites and chemical isolation from the corrosion of aqueous electrolytes. Theoretically, an ideal artificial interface protective layer should possess the following three properties: First, a sufficiently high mechanical modulus to block the physical penetration of the interface layer by the high-stiffness zinc dendrites; second, sufficiently high mechanical toughness to accommodate the continuous and drastic volume changes of zinc during deposition / stripping cycles, preventing cracking and peeling of the interface layer under repeated strain; and third, a sufficiently thin geometric thickness to maximize the preservation of the original volumetric energy density of the aqueous zinc-ion battery and reduce the impact of interface impedance on the battery's kinetic performance.

[0005] However, existing technologies often compromise on the aforementioned performance requirements by simply combining an inorganic rigid phase with an organic flexible phase. Due to the lack of strong molecular-scale interactions between the inorganic and organic phases, the resulting composite coating is prone to phase separation, defect propagation, and even interface delamination during long-term cycling. Furthermore, to compensate for insufficient film quality, the geometric thickness of the coating often has to be increased to the micrometer level, leading to a significant increase in interfacial impedance and a substantial sacrifice in the volumetric energy density of the full cell. Simultaneously, existing preparation processes mostly employ open coating methods such as blade coating, spin coating, or dip coating. The process parameters lack a quantifiable and feedback-based coupling mapping relationship with the final coating's mechanical properties, making it impossible to monitor and correct film quality in real time during preparation. This results in significant fluctuations in the mechanical and electrochemical properties of different batches of products. How to synergistically regulate the interaction between the organic and inorganic phases at the molecular scale to achieve high modulus and high toughness while maintaining nanometer-scale ultrathin thickness, and how to ensure batch stability of product mechanical properties through a repeatable process path with closed-loop feedback capability, are key technical challenges that urgently need to be overcome in the interface engineering of aqueous zinc-ion battery anodes. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of the aforementioned background technology and provide a zinc-ion battery anode protection material based on graphene oxide film, a method for preparing the graphene oxide film-based zinc-ion battery anode protection material, a zinc metal anode with the graphene oxide film-based zinc-ion battery anode protection material, an aqueous zinc-ion battery including the zinc metal anode, and the application of the graphene oxide film-based zinc-ion battery anode protection material in an aqueous zinc-ion battery.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A zinc-ion battery anode protection material based on graphene oxide film is disclosed. This material is a self-supporting composite film formed by the self-assembly of graphene oxide nanosheets and the nonionic surfactant Triton X-100 through molecular-level intercalation and dynamic hydrogen bonding network crosslinking. Triton X-100 is intercalated between the layers of the graphene oxide nanosheets. The ether oxygen atoms in the polyoxyethylene segments of Triton X-100 are bonded to the hydroxyl and carboxyl groups on the surface of the graphene oxide nanosheets. The formation of a dynamic hydrogen bond network between the substrates increases the interlayer spacing of the 001 crystal planes of the graphene oxide nanosheets from 0.82 nm–0.85 nm to 0.86 nm–0.92 nm. The thickness h of the zinc-ion battery anode protection material based on the graphene oxide film is 30 nm–150 nm, the Young's modulus E is 15 GPa–25 GPa, the elongation at break ε is 8%–15%, and the tensile strength is 10 MPa–16 MPa. Furthermore, the mechanical adaptive index η of the zinc-ion battery anode protection material based on the graphene oxide film is [not specified in the original text]. MA ≥5; the mechanical adaptive index η MA Calculate using the following formula: In the formula, η MA ε is the mechanical adaptive index of the zinc-ion battery anode protection material based on graphene oxide film; k0 is a dimensionless reference constant, k0=1000; E is the Young's modulus of the zinc-ion battery anode protection material based on graphene oxide film, expressed in GPa; ε is the elongation at break of the zinc-ion battery anode protection material based on graphene oxide film, expressed as a percentage; d is the 001 crystal plane interlayer spacing of the zinc-ion battery anode protection material based on graphene oxide film, in nm; d0=0.83nm is the reference interlayer spacing of the 001 crystal plane of pure graphene oxide; Δd=d-d0 is the 001 crystal plane interlayer spacing expansion of the graphene oxide nanosheets, in nm; h is the thickness of the zinc-ion battery anode protection material based on graphene oxide film, in nm; r T The mass ratio of Triton X-100 to graphene oxide nanosheets; g(r) T Let be the hydrogen bond coupling efficiency function, calculated using the following formula: In the above technical solution, graphene oxide nanosheets provide a high-modulus two-dimensional framework, while the nonionic surfactant TritonX-100 forms a dynamic hydrogen bond network with the ether oxygen atoms in its polyethylene oxide segments and the hydroxyl and carboxyl groups on the surface of graphene oxide. This dynamic hydrogen bond network can undergo continuous breakage and recombination under external stress, dissipating external mechanical energy through molecular-scale slip, thereby significantly improving the elongation at break of the composite film without sacrificing Young's modulus. The mechanical adaptive index couples parameters such as Young's modulus, elongation at break, interlayer spacing expansion, thickness, and hydrogen bond coupling efficiency function into a single dimensionless criterion, providing a quantitative evaluation basis for evaluating and screening zinc-ion battery anode protection materials based on graphene oxide films under different formulations, and serving as a criterion for closed-loop feedback preparation processes.

[0008] Furthermore, the zinc-ion battery anode protection material based on graphene oxide film simultaneously satisfies the following conditions: Young's modulus E ≥ 15 GPa, elongation at break ε ≥ 8%, thickness h ≤ 150 nm, and hydrogen bonding coupling efficiency function g(r T ≥0.75. Under this parameter combination, the strength, toughness, thickness, and hydrogen bonding efficiency of the zinc-ion battery anode protection material based on graphene oxide film can still maintain interface stability under high current density impact and repeated volume expansion of the zinc anode.

[0009] Furthermore, the zinc-ion battery negative electrode protection material based on graphene oxide film was tested by Fourier transform infrared spectroscopy at 3500 cm⁻¹. 1 ~3850cm 1 hydroxyl characteristic peaks within the range and 1650 cm⁻¹ 1 ~1800cm 1 The characteristic peaks of the carboxyl group within the range all exhibit a red shift relative to pure graphene oxide; X-ray photoelectron spectroscopy tests on the zinc-ion battery negative electrode protection material based on graphene oxide film show that the O1s core energy level peak of the graphene oxide nanosheets is shifted by 0.1 eV to 0.3 eV towards higher binding energy relative to pure graphene oxide.

[0010] Furthermore, the average degree of polymerization (n) of the polyoxyethylene segments of the TritonX-100 is 8–12, and the hydrophilic-lipophilic balance (HLB) is 12–14; the mass ratio r TThe concentration ranges from 0.1 to 1.0. The limitation on the degree of polymerization of the polyoxyethylene segments and the hydrophilic-lipophilic balance ensures that the hydrogen bonding density between TritonX-100 and the oxygen-containing functional groups on the surface of graphene oxide is at an appropriate level. The limitation on the mass ratio avoids the process abnormalities such as insufficient hydrogen bond network density due to insufficient TritonX-100 addition, or excessive addition leading to excessively low surface tension of the dispersion and thus failure of organic phase spreading.

[0011] Further, the thickness h is 60 nm to 100 nm, the Young's modulus E is 20 GPa to 24 GPa, the elongation at break ε is 10% to 13%, and the mechanical adaptive exponent η... MA ≥6.

[0012] A zinc metal anode with a graphene oxide-based zinc-ion battery anode protection material is disclosed. The zinc metal anode comprises a zinc metal substrate and the aforementioned graphene oxide-based zinc-ion battery anode protection material covering at least one surface of the zinc metal substrate. The graphene oxide-based zinc-ion battery anode protection material is conformally bonded to the zinc metal substrate, and the interface between the two is free of pores and phase separation. The thickness of the zinc metal substrate is 5 μm to 50 μm. The conformal bonding interface and the absence of pores between the graphene oxide-based zinc-ion battery anode protection material and the zinc metal substrate ensure uniform flux distribution of zinc ions during deposition / stripping, effectively suppressing local electric field concentration and dendrite initiation. The limited thickness range of the zinc metal substrate balances machinability, battery energy density, and cycle life, making it suitable for the construction of zinc-poor aqueous zinc-ion batteries.

[0013] A method for preparing the above-mentioned zinc-ion battery negative electrode protection material based on graphene oxide thin film, the preparation method comprising: Initial dispersion: The aqueous dispersion of the graphene oxide nanosheets and Triton X-100 are mixed at the target mass ratio r. T The mixture is mixed and ultrasonically dispersed to obtain a mixed dispersion; when the absolute value of the zeta potential |ζ| ≥ 30 mV and the polydispersity index PDI ≤ 0.3, it enters the organic phase spreading state.

[0014] The organic phase spread state is as follows: according to the coupling relationship of process parameters: The required volume ratio v is calculated. E In the formula, v E The volume ratio of ethyl acetate to the mixed dispersion; r T The meaning is the same as above; h targetThe target thickness of the zinc-ion battery negative electrode protection material is given in nm; h0 = 100 nm, which is the reference thickness; a is a constant coefficient, ranging from 0.15 to 0.25; b is the coefficient of r. T The coefficient for the thickness term ranges from 0.70 to 0.90; c is the coefficient for the thickness term, ranging from 0.25 to 0.35; ethyl acetate is mixed according to a volume ratio v E Slowly add the ethyl acetate along the container wall to the surface of the mixed dispersion, so that the ethyl acetate forms an independent upper organic liquid phase above the mixed dispersion; when the spatial non-uniformity σ of the reflected light of the independent upper organic liquid phase... I / μ I When the value is ≤0.1, it enters the double convection self-assembly state.

[0015] The dual-convective self-assembled state is as follows: the ethyl acetate evaporates from the surface of the independent upper organic liquid phase, inducing Marangoni convection and Rayleigh-Bernard convection at the gas-liquid interface; the graphene oxide nanosheets and the Triton X-100 self-assemble at the gas-liquid interface to form a continuous film; in the dual-convective self-assembled state, the liquid surface temperature gradient dT / dr and the reflected light color shift ΔRGB are monitored in real time, and the ambient temperature T is adjusted according to the following mapping. amb When dT / dr ≥ 0.5℃ / cm and the reflected light color shift ΔRGB changes rapidly, the ambient temperature T is... amb Reduce the ambient temperature by 2℃; when dT / dr ≤ 0.1℃ / cm and the reflected light color shift ΔRGB changes slowly, reduce the ambient temperature T. amb Increase by 2℃; when 0.1℃ / cm < dT / dr < 0.5℃ / cm and the reflected light color shift ΔRGB progresses steadily in a gradient, maintain the ambient temperature T. amb The state remains unchanged; after the continuous film has fully spread at the gas-liquid interface, it enters the membrane solidification state.

[0016] The solidified state of the membrane is as follows: after the ethyl acetate has completely evaporated, the interference fringes of the continuous thin film floating on the liquid surface are observed; when the interference fringes are uniform and the fringe spacing remains stable, the membrane enters the substrate transfer state; when the interference fringes break or become partially transparent, the membrane reverts to the dual convection self-assembly state and ethyl acetate is added to re-trigger self-assembly.

[0017] The substrate transfer state is as follows: the continuous thin film is transferred from the liquid surface to the surface of a zinc metal substrate, and then vacuum dried at 20℃~60℃ for 2h~24h to obtain the zinc-ion battery anode protection material based on graphene oxide film; when the obtained zinc-ion battery anode protection material based on graphene oxide film does not satisfy the above-mentioned mechanical adaptive index η after testing. MA When the value is ≥5, the initial dispersion state is reverted and the mass ratio r is adjusted in the reverse direction. Tand the volume ratio v E The process is repeated until the resulting zinc-ion battery anode protection material based on graphene oxide film satisfies η. MA ≥5.

[0018] The above preparation method divides the complete film formation process into five adaptive states with clear quantitative criteria, and introduces a reverse adjustment link driven by mechanical adaptive exponential criteria at the end of the state machine, so that the preparation process has the characteristics of being quantifiable, feedback-able, and traceable. It overcomes the bottlenecks of existing open coating processes with no feedback and poor batch consistency. The batch stability of the prepared products in terms of mechanical and electrochemical properties is better than that of traditional physical mixing coating processes.

[0019] Furthermore, in the coupling formula of the process parameters, coefficient a = 0.20, coefficient b = 0.80, and coefficient c = 0.30; the mass concentration of the aqueous dispersion of the graphene oxide nanosheets is 0.1 mg / mL to 2 mg / mL, and the diameter of the graphene oxide nanosheets is 1 μm to 5 μm.

[0020] Furthermore, in the dual-convective self-assembled state, the ambient temperature T amb Each adjustment increment does not exceed 2°C, and after each adjustment, the system is allowed to stand for at least 30 seconds. The liquid surface temperature gradient dT / dr and the reflected light color shift ΔRGB are then re-monitored before the next adjustment is performed. This gradual temperature control strategy avoids irreversible damage to the self-assembly process at the gas-liquid interface caused by excessive temperature disturbances, ensuring that the dual-convective system steadily progresses self-assembly under controlled conditions.

[0021] An aqueous zinc-ion battery is disclosed, comprising a positive electrode, an electrolyte, and a negative electrode, wherein the negative electrode is a zinc metal negative electrode having the aforementioned zinc-ion battery negative electrode protection material based on a graphene oxide film. The aqueous zinc-ion battery assembled based on the zinc metal negative electrode of this invention exhibits both excellent cycle stability and high coulombic efficiency, demonstrates outstanding performance in suppressing dendrite penetration and hydrogen evolution side reactions, and exhibits good electrochemical performance under various positive electrode systems.

[0022] Furthermore, the positive electrode is a β-MnO2 positive electrode, and the surface loading of the active material of the positive electrode is 5 mg / cm² to 10 mg / cm²; the electrolyte is an aqueous solution containing 2 mol / L ZnSO4 and 0.1 mol / L MnSO4; the ratio of the negative electrode capacity to the positive electrode capacity of the aqueous zinc-ion battery is 2:1 to 3:1, and the thickness of the zinc metal substrate is 5 μm to 10 μm.

[0023] The above-mentioned zinc-ion battery anode protection material based on graphene oxide film is used to suppress the growth of zinc metal anode dendrites, suppress hydrogen evolution side reactions, improve the coulombic efficiency of aqueous zinc-ion batteries, and extend the cycle life of aqueous zinc-ion batteries.

[0024] The beneficial effects achieved by this invention are as follows: Firstly, the zinc-ion battery anode protection material based on graphene oxide film of this invention draws on the myosin and actin filament sliding mechanism in biological muscle tissue, which achieves coordinated slippage and mechanical energy dissipation through the continuous breaking and recombination of dynamic hydrogen bonds at the interface. A high-density dynamic hydrogen bond network is constructed between graphene oxide nanosheets using the nonionic surfactant TritonX-100. The dynamic hydrogen bond network acts as sacrificial bonds and effectively dissipates external stress through molecular-scale slippage movement, thereby significantly improving the elongation at break of the zinc-ion battery anode protection material without sacrificing Young's modulus. This overcomes the problem of achieving high modulus, high toughness, and ultrathin thickness simultaneously in traditional inorganic-organic composite interface layers.

[0025] Secondly, the zinc-ion battery anode protection material based on graphene oxide film of the present invention is prepared by in-situ dual convection self-assembly. The controllable thickness of the obtained zinc-ion battery anode protection material based on graphene oxide film is in the nanometer range of 30nm to 150nm, which is much smaller than the micrometer thickness of traditional physical hybrid coatings. This reduces the interfacial impedance, improves the ion transport rate, and retains the original volumetric energy density of aqueous zinc-ion batteries. Furthermore, TritonX-100 expands the interlayer spacing of graphene oxide 001 crystal planes from 0.83nm to more than 0.86nm through molecular-level intercalation, realizing the synergistic control of component formulation and microstructure at the molecular scale.

[0026] Third, the preparation method of the present invention sequentially sets up five adaptive states with clear quantitative criteria: initial dispersed state, organic phase spreading state, dual convection self-assembly state, film consolidation state, and substrate transfer state. The transfer between each state is completed through multiple quantifiable indicators such as Zeta potential, polydispersity index, spatial non-uniformity of reflected light, liquid surface temperature gradient, and interference fringes. At the end of the state machine, a mechanical adaptive index criterion is introduced to drive the reverse adjustment of the initial formula and process parameters, breaking the bottleneck of traditional open coating process with no feedback and poor batch consistency. This makes the preparation process quantifiable, repeatable, and traceable, providing a process basis for industrial scale-up.

[0027] Fourth, the zinc metal anode of the present invention, which is a zinc-ion battery anode protection material based on graphene oxide film, exhibits outstanding effects in suppressing zinc dendrite growth, suppressing hydrogen evolution side reactions, reducing the desolvation energy barrier, and homogenizing zinc ion flux. The Zn‖Cu half-cell assembled based on this anode has stable cycling for more than 10,000 cycles at a high current density of 5 mA / cm² with an average coulombic efficiency of up to 99.94%. The Zn‖Zn symmetric cell has stable cycling for more than 4,000 hours at 0.5 mA / cm², and the Zn‖β-MnO2 full cell has stable cycling for more than 3,000 cycles at a current density of 1 A / g. Even under harsh conditions such as zinc deficiency (N / P=2.5), ultra-thin zinc foil (7.8 μm), and high positive electrode loading, the cycle life of this full cell is still more than 3 times longer than that of the bare zinc anode control. Attached Figure Description

[0028] Figure 1 The following are the morphological, structural and interfacial chemical characterization results of Zn@MAL-1 obtained in Example 1 of this invention, wherein (a) is a surface scanning electron microscope image, (b) is a focused ion beam cross-sectional scanning electron microscope image, (c) is a cross-sectional transmission electron microscope image and oxygen element energy spectrum line scan, (d) and (e) are atomic force microscope morphology and surface potential mapping diagrams of bare zinc and Zn@MAL-1, respectively, (f) are X-ray diffraction patterns of MRL and MAL, (g) are Fourier transform infrared spectra of MRL and MAL, (h) is O1s high-resolution X-ray photoelectron spectrum, (i) is AC impedance spectrum, (j) is the Arrhenius fitting curve of desolvation activation energy at different temperatures, and (k) is the linear scanning voltammetric hydrogen evolution curve in 1 mol / L Na2SO4 solution; Figure 2 The mechanical properties characterization results of the zinc-ion battery anode protection material based on graphene oxide film of the present invention are shown in (a) as a schematic diagram of the failure mechanism of bare zinc, weak interface layer and strong interface layer, (b) as stress-strain curves of MRL and MAL self-supporting films, (c) as force-displacement curves of MAL and MRL by atomic force microscopy, (d) and (e) as nanomechanical Young's modulus mapping of Zn@MRL and Zn@MAL respectively, and (f) as the statistical distribution of Young's modulus. Figure 3For in-situ observation and kinetic analysis of the zinc deposition process, (a), (d), and (g) are in-situ optical microscopy time-series images of bare zinc, Zn@MRL, and Zn@MAL deposited at a current density of 5 mA / cm² for 24 min, respectively; (b), (e), and (h) are scanning electron microscope images of the corresponding samples after deposition, respectively; (c), (f), and (i) are three-dimensional white light interference morphology images of the corresponding samples, respectively; (j) is a surface roughness statistical bar chart; (k) is a chronocurrent curve; (l) is a nucleation overpotential curve; and (m) to (o) are contour plots of relaxation time distribution during the cycling process of bare zinc, Zn@MRL, and Zn@MAL symmetric cells, respectively. Figure 4 The electrochemical performance of Zn@MAL-1 obtained in Example 1 of this invention is shown in the figures. (a) is the coulombic efficiency-cycle curve of the Zn‖Cu half-cell under the conditions of 5 mA / cm² current density and 1 mAh / cm² areal capacity. (b) is a horizontal comparison graph of the results of this invention and those reported in the literature. (c) is the long cycle curve of the symmetric cell under the conditions of 0.5 mA / cm² current density and 0.5 mAh / cm² areal capacity. (d) is the long cycle curve of the symmetric cell under the conditions of 5 mA / cm² current density and 1 mAh / cm² areal capacity. (e) is the rate performance curve of the Zn‖β-MnO2 full cell under the current density of 0.2 to 3 A / g. (f) is the long cycle curve of the full cell under the current density of 1 A / g. (g) is the full cell cycle curve under the zinc-poor condition (N / P=2.5, zinc foil thickness 7.8 μm). Detailed Implementation

[0029] The technical solution of the present invention will be described in detail below with reference to specific embodiments. Experimental methods in the following embodiments that do not specify specific conditions shall be performed under conventional conditions or conditions recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, can be purchased commercially. The scope of protection of the present invention is not limited to the following embodiments.

[0030] I. Raw Materials, Reagents and Instruments Graphene oxide aqueous dispersion: prepared by a modified Hummers method, with a mass concentration of 0.1 mg / mL to 2 mg / mL, graphene oxide nanosheet diameter of 1 μm to 5 μm, and a zeta potential absolute value greater than 30 mV. Triton X-100: analytical grade, with an average degree of polymerization (n) of 8–12 for polyoxyethylene segments and a hydrophilic-lipophilic balance (HLB) of 12–14. Ethyl acetate: analytical grade, boiling point 77.1℃, density 0.902 g / cm³. Zinc foil: purity ≥99.99%, thickness 5 μm to 50 μm. β-MnO2 cathode material: nanorod morphology, synthesized by hydrothermal method, then mixed with conductive carbon black and polyvinylidene fluoride at a mass ratio of 7:2:1 and coated onto a stainless steel mesh current collector. Electrolyte: aqueous solution containing 2 mol / L ZnSO4 and 0.1 mol / L MnSO4.

[0031] The main instruments include: a focused ion beam scanning electron microscope (FIB-SEM) for cross-sectional thickness measurement; a high-resolution transmission electron microscope (HRTEM) with an energy dispersive spectroscopy (EDS) instrument for microstructure and elemental distribution analysis; an X-ray diffractometer (XRD, CuKα radiation) for 001 crystal plane interlayer spacing measurement; a Fourier transform infrared spectrometer (FTIR, attenuated total reflection mode) for functional group diagnosis; an X-ray photoelectron spectroscopy (XPS, AlKα monochromatic source) for chemical state analysis; an atomic force microscope (AFM, peak force quantitative nanomechanical mode) for Young's modulus mapping; a micro tensile testing machine for self-supporting membrane mechanical testing; and a CHI760E electrochemical workstation and a LANDCT2001A battery testing system for electrochemical performance evaluation.

[0032] II. Explanation of Calculation Formulas This invention relates to the mechanical adaptive index criterion formula and the coupling relationship of process parameters in the preparation method, as detailed below.

[0033] (1) Mechanical adaptive exponent η of zinc-ion battery anode protection material based on graphene oxide film MA Calculate using the following formula: In the formula: η MAε is the mechanical adaptive index of the zinc-ion battery anode protection material based on graphene oxide film; k0=1000 is a dimensionless reference constant; E is the Young's modulus of the zinc-ion battery anode protection material based on graphene oxide film, expressed in GPa; ε is the elongation at break of the zinc-ion battery anode protection material based on graphene oxide film, expressed as a percentage; d is the 001 crystal plane interlayer spacing of the zinc-ion battery anode protection material based on graphene oxide film measured by X-ray diffraction, in nm; d0=0.83nm is the reference interlayer spacing of the 001 crystal plane of pure graphene oxide; Δd=d-d0 is the expansion of the 001 crystal plane interlayer spacing of the graphene oxide nanosheets, in nm; h is the thickness of the zinc-ion battery anode protection material based on graphene oxide film, in nm; r T The mass ratio of Triton X-100 to the graphene oxide nanosheets; g(r) T ) is the hydrogen bond coupling efficiency function, calculated according to the following formula (2).

[0034] (2) Hydrogen bond coupling efficiency function g(r) T Calculate using the following formula: In the formula: g(r) T ) represents the hydrogen bonding efficiency function; r T The mass ratio of Triton X-100 to graphene oxide nanosheets. Hydrogen bonding efficiency function g(r) T ) in r T When r = 1, it reaches its maximum value of 1. T The decrease when deviating from 1 reflects the nonlinear dependence of the hydrogen bond density between TritonX-100 and graphene oxide on the mass ratio.

[0035] (3) In the preparation method of the present invention, the volume ratio of ethyl acetate added to the organic phase in the spread state is v E Determined according to the following coupling formula of process parameters: In the formula: v E The volume ratio of the ethyl acetate to the graphene oxide-Triton X-100 mixed dispersion; r T h is the mass ratio of the Triton X-100 to the graphene oxide nanosheets. target The target thickness of the zinc-ion battery negative electrode protection material is given in nm; h0 = 100 nm, which is the reference thickness; a is a constant coefficient, ranging from 0.15 to 0.25; b is the coefficient of r. TThe coefficient for the thickness term ranges from 0.70 to 0.90; c is the coefficient for the thickness term, ranging from 0.25 to 0.35. In Examples 1 to 6 below, v E The calculations all use a=0.20, b=0.80, and c=0.30.

[0036] III. Examples Example 1: This embodiment provides a method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide thin film, including the following steps: (1) Take 5 mL of 1 mg / mL graphene oxide aqueous dispersion (containing 5 mg of graphene oxide) and place it in a clean petri dish with a diameter of 10 cm; weigh 2.5 mg of Triton X-100 (mass ratio of r to graphene oxide nanosheets). T =0.5) was added and ultrasonically dispersed at 200W power for 30min at 25℃ to obtain a mixed dispersion; the Zeta potential was measured to be -38mV and the polydispersity index PDI=0.22, which met the transition criterion from the initial dispersed state to the organic phase spread state (|ζ|≥30mV and PDI≤0.3), and thus entered the organic phase spread state.

[0037] (2) The thickness h of the target zinc-ion battery negative electrode protection material target =80nm is the input. Calculate the required volume ratio of ethyl acetate to the mixed dispersion according to the coupling formula: 4.2 mL of ethyl acetate was slowly added dropwise along the wall of the culture dish using a microsyringe. E =4.2 / 5=0.84), so that ethyl acetate forms an independent upper organic liquid phase above the mixed dispersion; the spatial non-uniformity σ of the reflected light intensity is measured by irradiating the liquid surface with narrow-band white light. I / μ I =0.07≤0.1, which satisfies the transition criterion from the organic phase spread state to the double convection self-assembly state, and thus enters the double convection self-assembly state.

[0038] (3) When left to stand at room temperature of 25℃, ethyl acetate evaporates from the liquid surface. Simultaneously, the radial temperature gradient dT / dr of the liquid surface is monitored using an infrared thermometer array, which is approximately 0.3℃ / cm. The color shift ΔRGB of the reflected light is monitored using a digital camera, showing a stable gradient progression. dT / dr falls within the range of 0.1~0.5℃ / cm. Therefore, the ambient temperature T is maintained. amb The reaction remained unchanged; after about 15 minutes, the ethyl acetate completely evaporated, and the graphene oxide nanosheets and Triton X-100 self-assembled at the gas-liquid interface to form a continuous film.

[0039] (4) The continuous thin film interference fringes are uniform, with stable spacing and no breaks or light-transmitting areas. They meet the transfer criterion from the film solidification state to the substrate transfer state and enter the substrate transfer state.

[0040] (5) The continuous film is slowly lifted from below the liquid surface with a zinc foil with a thickness of 10 μm, so that the continuous film is completely transferred to one side of the zinc foil. It is then dried in a vacuum oven at 40°C for 6 hours to obtain a zinc metal anode with a zinc-ion battery anode protection material based on graphene oxide film, denoted as Zn@MAL-1.

[0041] (6) Prepare another continuous film using the same method as steps (1) to (5), transfer it to the surface of a 10 μm thick pure copper foil, and dry it in a vacuum oven at 40 °C for 6 h to obtain a copper foil substrate with the same batch of zinc-ion battery negative electrode protection material based on graphene oxide film, denoted as Cu@MAL-1, for subsequent Zn‖Cu half-cell testing. Cu@MRL-1 (a control sample without Triton X-100) can be prepared using the same method.

[0042] Characterization results: The thickness of the zinc-ion battery anode protection material based on graphene oxide film was measured to be h=80nm by FIB-SEM cross-section; the Young's modulus E=22.4GPa by nanoindentation; the elongation at break ε=12% and the tensile strength 13.8MPa by micro-stretching; the interlayer spacing d=0.87nm of the 001 crystal plane was measured by XRD, and the expansion Δd=0.04nm relative to the pure graphene oxide reference value d0=0.83nm; FTIR at 3500cm 1 ~3850cm 1 The characteristic peak of hydroxyl groups within the range is 3614 cm⁻¹ 1 Redshifted to 3609cm 1 1650cm 1 ~1800cm 1 The characteristic peak of the carboxyl group in the range is from 1730 cm⁻¹ 1 Redshifted to 1721cm 1 The O1s core level peak of XPS shifts by 0.2 eV towards higher binding energies; at 973 cm⁻¹ 1In AFM-IR testing using the characteristic stretching vibration frequency of epoxy group COC as the detection frequency, the Zn@MAL-1 surface exhibited a high-intensity and continuous infrared amplitude signal, while the bare zinc surface showed an extremely weak signal. This confirms that the epoxy-rich graphene oxide-based zinc-ion battery anode protection material achieves uniform and complete molecular-level coverage on the zinc substrate. The contact angle decreased from 91.3° for bare zinc and 72.4° for the Zn@MRL control to 14.3° for Zn@MAL-1, reflecting the strong hydrophilicity of the oxygen-rich MAL surface.

[0043] Calculation of the mechanical adaptive index: The calculation result is significantly higher than the criterion threshold of 5, and is within the mechanical adaptive working window.

[0044] Electrochemical performance: The Cu@MAL-1‖Zn half-cell assembled with Cu@MAL-1 and bare zinc foil achieved stable cycling for over 10,000 cycles at a current density of 5 mA / cm² and an areal capacity of 1 mAh / cm², with a cumulative deposition capacity exceeding 10,000 mAh / cm² (more than 60 times the cumulative deposition capacity of bare copper (150 mAh / cm²) under the same conditions), and an average coulombic efficiency of 99.94%. In contrast, the half-cell assembled with bare copper foil and bare zinc failed after only 150 cycles. The average coulombic efficiency was 99.63%; the half-cell assembled with Cu@MRL-1 and bare zinc failed after 800 cycles, with an average coulombic efficiency of 99.73%; furthermore, under a low current condition of 0.5 mA / cm², the Cu@MAL-1 half-cell could stably cycle for more than 1800 cycles, with an average coulombic efficiency of 99.35%, which is better than the bare copper control (96.99%) and the Cu@MRL-1 control (98.75%); the symmetric cell assembled with Zn@MAL-1, under a low current condition of 0.5 mA / cm² / 0 It exhibited stable cycling for over 4000 hours under 0.5 mAh / cm² conditions (compared to only 84 hours for the bare zinc control and only 120 hours for the Zn@MRL control before short circuits occurred), and stable cycling for over 2000 hours under 5 mA / cm² / 1 mAh / cm² conditions (compared to only 40 hours for the bare zinc control and only 168 hours for the Zn@MRL control before short circuits occurred), with highly symmetrical voltage curves. Using Zn@MAL-1 as the negative electrode, β-MnO2 as the positive electrode, and 2 mol / L ZnSO₄ + 0.1 mol / L MnSO₄... 4. The full cell assembled with electrolyte stably cycled for more than 3000 cycles at a current density of 1A / g (as a control, the full cell assembled with bare zinc of the same thickness only cycled for about 490 cycles before failing due to severe short circuit caused by uncontrolled dendrite growth); the full cell has excellent rate performance in the current density range of 0.2 to 3A / g, and still maintains a specific capacity of 112mAh / g at a high current of 3A / g, which is better than the 85mAh / g of the bare zinc control. When the current is reduced to 0.2A / g, the capacity quickly recovers to 288mAh / g.

[0045] Example 2: This embodiment provides a method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide film. The preparation steps are the same as in Example 1, except that: 5 mL of a 1 mg / mL aqueous dispersion of graphene oxide (5 mg of graphene oxide) is taken, and the amount of Triton X-100 added is adjusted to 1.5 mg (r T =0.3); Target zinc-ion battery negative electrode protection material thickness h target =60nm, the volume ratio of ethyl acetate to the mixed dispersion was calculated according to the coupling formula: The amount of ethyl acetate added was adjusted to 3.1 mL; the vacuum drying conditions were 50 °C for 4 h. The resulting zinc metal anode with zinc-ion battery anode protection material based on graphene oxide film was designated Zn@MAL-2.

[0046] Characterization results: h=60nm, E=24.1GPa, ε=9.2%, tensile strength 15.2MPa, d=0.865nm, Δd=0.035nm. g(0.3)=4×0.3 / 1.69=0.710; The calculation results meet the criteria. The symmetric battery assembled with Zn@MAL-2 cycles stably for more than 800 hours under the conditions of 10 mA / cm² / 2 mAh / cm².

[0047] Example 3: This embodiment provides a method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide film. The preparation steps are the same as in Example 1, except that: 5 mL of a 1 mg / mL aqueous dispersion of graphene oxide (5 mg of graphene oxide) is taken, and the amount of Triton X-100 added is adjusted to 4.0 mg (r). T =0.8); Target zinc-ion battery negative electrode protection material thickness h target =100nm, the volume ratio of ethyl acetate to the mixed dispersion was calculated according to the coupling formula: The amount of ethyl acetate added was adjusted to 5.7 mL; the vacuum drying conditions were 30 °C for 12 h. The resulting zinc metal anode with zinc-ion battery anode protection material based on graphene oxide film was designated Zn@MAL-3.

[0048] Characterization results: h=100nm, E=17.8GPa, ε=14.6%, tensile strength 12.1MPa, d=0.89nm, Δd=0.06nm. g(0.8)=4×0.8 / 3.24=0.988; The calculation result is significantly higher than the criterion threshold.

[0049] Example 4: This embodiment provides a method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide film. The preparation steps are the same as in Example 1, except that: 5 mL of a 0.5 mg / mL aqueous dispersion of graphene oxide (2.5 mg of graphene oxide) is taken, and the amount of Triton X-100 added is adjusted to 0.25 mg (r). T =0.1); Target zinc-ion battery negative electrode protection material thickness h target =30nm, the volume ratio of ethyl acetate to the mixed dispersion was calculated according to the coupling formula: The amount of ethyl acetate added was adjusted to 1.85 mL; the vacuum drying conditions were 60 °C for 2 h. The resulting negative electrode was designated Zn@MAL-4.

[0050] Characterization results: h=32nm, E=21.8GPa, ε=8.4%, tensile strength 10.7MPa, d=0.862nm, Δd=0.032nm. g(0.1)=4×0.1 / 1.21=0.331; η is determined through closed-loop feedback. MA If the value is less than 5, revert to the initial dispersed state and set r... T Fine-tune to 0.12, and correspondingly adjust v. E After adjusting to 0.386, the organic phase spreading state, dual-convection self-assembly state, membrane consolidation state, and substrate transfer state were re-executed sequentially. The final measured values ​​were h = 30 nm, E = 22.1 GPa, ε = 8.6%, Δd = 0.033 nm, and g(0.12) = 0.383. The calculation results meet the criterion ≥5. The resulting Zn@MAL-4 anode assembled symmetrical battery exhibits stable cycling performance exceeding 1500h under conditions of 1mA / cm² / 1mAh / cm².

[0051] Example 5: This embodiment provides a method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide film. The preparation steps are the same as in Example 1, except that: 5 mL of a 1.5 mg / mL aqueous dispersion of graphene oxide (7.5 mg of graphene oxide) is taken, and the amount of Triton X-100 added is adjusted to 7.5 mg (r). T =1.0); Target zinc-ion battery negative electrode protection material thickness h target =150nm, the volume ratio of ethyl acetate to the mixed dispersion was calculated according to the coupling formula: The amount of ethyl acetate added was adjusted to 7.25 mL; the vacuum drying conditions were 35 °C for 10 h. The resulting negative electrode was designated Zn@MAL-5.

[0052] Characterization results: h = 148 nm, E = 15.6 GPa, ε = 14.2%, tensile strength 10.8 MPa, d = 0.915 nm, Δd = 0.085 nm. g(1.0) = 4 × 1.0 / 4 = 1.000; The calculated results are significantly higher than the criterion threshold. The obtained Zn@MAL-5 anode assembled symmetric battery exhibits stable cycling performance exceeding 3500 h under conditions of 0.5 mA / cm² / 0.5 mAh / cm².

[0053] Example 6: This embodiment provides a method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide film. The preparation steps are the same as in Example 1, except that: a graphene oxide aqueous dispersion with a concentration of 2 mg / mL and a center diameter of 5 μm is used, and 5 mL (10 mg of graphene oxide) is taken. The amount of Triton X-100 added is adjusted to 5.0 mg (r). T =0.5); Target zinc-ion battery negative electrode protection material thickness h target =80nm, the volume ratio v of ethyl acetate to the mixed dispersion was calculated according to the coupling formula. E =0.84 (same as in Example 1), ethyl acetate was added in an amount of 4.2 mL; to control the evaporation kinetics of the high-concentration dispersion, the ultrasonic dispersion time was extended to 45 min; the vacuum drying conditions were 40 °C for 8 h. The resulting negative electrode is denoted as Zn@MAL-6.

[0054] Characterization results: h = 85 nm, E = 23.2 GPa, ε = 11.5%, tensile strength 14.6 MPa, d = 0.878 nm, Δd = 0.048 nm. g(0.5) = 0.889; The calculation result satisfies the criterion.

[0055] Example 7: This embodiment provides an aqueous zinc-ion battery and its assembly method: Zn@MAL-1 obtained in Example 1 is used as the negative electrode, and the thickness of the zinc metal substrate of the negative electrode is 7.8 μm; the positive electrode is a β-MnO2 nanorod positive electrode with an areal loading of 7.1 mg / cm²; the electrolyte is a 2 mol / L ZnSO4 + 0.1 mol / L MnSO4 aqueous solution; the ratio of the negative electrode capacity to the positive electrode capacity (N / P ratio) is set to 2.5; after assembly in the CR2032 coin cell configuration, constant current charge-discharge test is performed.

[0056] Electrochemical performance: The full cell was stable for more than 100 cycles at a current density of 1 A / g with a capacity retention of more than 85%. As a control, the full cell assembled with bare zinc foil of the same thickness (7.8 μm) failed after only about 30 cycles. In this example, the Zn@MAL-1 modified negative electrode extended the life of the full cell by more than 3 times compared with the bare zinc control.

[0057] Example 8: This embodiment provides a method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide film. The preparation steps are the same as in Example 1, except that: 10 mL of a graphene oxide aqueous dispersion with a concentration of 0.1 mg / mL and a center diameter of 1 μm (1.0 mg of graphene oxide) is taken, and the amount of Triton X-100 added is adjusted to 0.4 mg (r). T =0.4); to ensure the uniformity of the low-concentration dispersion, the ultrasonic dispersion time was extended to 40 min; the thickness h of the target zinc-ion battery negative electrode protective material. target =50nm, the volume ratio of ethyl acetate to the mixed dispersion was calculated according to the coupling relationship: The amount of ethyl acetate added was adjusted to 6.7 mL; the resulting continuous film was transferred to one side of a 50 μm thick zinc foil and dried in a vacuum oven at 20 °C for 24 h. The resulting zinc metal anode with zinc-ion battery anode protection material based on graphene oxide film is designated Zn@MAL-8.

[0058] Characterization results: h=52nm, E=22.0GPa, ε=9.2%, tensile strength 13.0MPa, d=0.867nm, Δd=0.037nm. g(0.4)=4×0.4 / 1.96=0.816; The calculation results meet the criteria. The symmetric cell assembled with Zn@MAL-8 is stable for more than 1200 hours under the conditions of 1 mA / cm² / 1 mAh / cm²; the full cell assembled with Zn@MAL-8 as the negative electrode and β-MnO2 as the positive electrode is stable for about 1800 cycles at a current density of 1 A / g.

[0059] Example 9: This embodiment provides an aqueous zinc-ion battery and its assembly method: a 5μm thick zinc foil with conformal modification of the zinc-ion battery negative electrode protection material based on graphene oxide film obtained in Example 1 is used as the negative electrode, and the zinc metal substrate thickness is 5μm; the positive electrode is a β-MnO2 nanorod positive electrode with an areal loading of 5mg / cm²; the electrolyte is an aqueous solution containing 2mol / L ZnSO4 and 0.1mol / L MnSO4; the ratio of negative electrode capacity to positive electrode capacity (N / P ratio) is set to 2; after assembly in the CR2032 coin cell configuration, constant current charge-discharge test is performed.

[0060] Electrochemical performance: The full cell can cycle stably for about 550 cycles at a current density of 1 A / g with a capacity retention of about 83%. Under the same conditions, the control full cell assembled with 5 μm bare zinc foil only failed after about 130 cycles due to dendrite puncture and soft short circuit. The modified negative electrode in this embodiment extends the cycle life by more than 3 times compared with the bare zinc control.

[0061] Example 10: This embodiment provides an aqueous zinc-ion battery and its assembly method: a 10μm thick zinc foil with conformal modification of the zinc-ion battery negative electrode protection material based on graphene oxide film obtained in Example 1 is used as the negative electrode, and the zinc metal substrate thickness is 10μm; the positive electrode is a β-MnO2 nanorod positive electrode with an areal loading of 10mg / cm²; the electrolyte is an aqueous solution containing 2mol / L ZnSO4 and 0.1mol / L MnSO4; the ratio of negative electrode capacity to positive electrode capacity (N / P ratio) is set to 3; after assembly in the CR2032 coin cell configuration, constant current charge-discharge test is performed.

[0062] Electrochemical performance: The full cell was stable for more than 1,500 cycles at a current density of 1 A / g with a capacity retention of about 88%; in the rate test of 0.2 to 3 A / g, the specific capacity was maintained at 105 mAh / g at a high current of 3 A / g; under the same conditions, the control full cell assembled with 10 μm bare zinc foil failed after about 400 cycles due to a sharp capacity decay.

[0063] IV. Comparative Examples Comparative Example 1: Without Triton X-100 (r) T=0), the remaining steps are the same as in Example 1, and the control sample Zn@MRL-1 is obtained. Characterization results: h=80nm, E=18.2GPa, ε=5.8%, tensile strength 11.5MPa, d=0.84nm, Δd=0.01nm. Since g(0)=0, η MA =0, which does not meet the criterion at all.

[0064] No redshift of hydroxyl or carboxyl groups or shift of the O1s core level was observed by FTIR or XPS. The Zn‖Cu half-cell in Comparative Example 1 failed after only about 800 cycles due to a sharp drop in coulombic efficiency; the symmetric cell was stable for only about 120 hours at 0.5 mA / cm². This comparative example demonstrates that without the Triton X-100-mediated dynamic hydrogen bond network, it is impossible to form a mechanically adaptive graphene oxide-based zinc-ion battery anode protection material.

[0065] Comparative Example 2: Target r T =2.0 (Triton severely excessive), calculated according to the coupling formula. During the actual preparation process, it was observed that: excessive Triton X-100 significantly reduced the surface tension of the dispersion, causing the upper layer of ethyl acetate to become unstable, and some ethyl acetate to penetrate into the aqueous phase; the spatial non-uniformity σ of the reflected light intensity was measured. I / μ I =0.27>0.1, the closed-loop state machine is judged as abnormal at the transition criterion from the organic phase spread state to the dual-convective self-assembly state and reverts to the initial dispersed state. If the criterion is forcibly ignored and subsequent steps are continued, the resulting film has h=160nm (exceeding the target thickness), E=9.3GPa, ε=18%, Δd=0.05nm. g(2.0)=8 / 9=0.889; The calculation result does not meet the criteria.

[0066] This comparative example shows that: even if the hydrogen bonding efficiency function g(r) T When the value is large, when r T When the values ​​are too high or the matching with the coupling relationship is broken, the deterioration of Young's modulus and Δd / h term will still cause the comprehensive mechanical adaptive index to fail to meet the standard. The Zn‖Cu half-cell fails after only about 1200 cycles.

[0067] Comparative Example 3: Using conventional scraping method: r TA GO / TritonX-100 aqueous dispersion (concentration 2 mg / mL) of 0.5 was directly coated onto a 10 μm thick zinc foil surface and dried at 60 °C under normal pressure for 2 h to obtain the control sample Zn@MRL-3. This method does not include the dual-convective self-assembled state and its monitoring and regulation mechanism of the present invention. Characterization results: h≈10 μm (micrometer-level thickness), E=11.5 GPa, ε=6.2%, d=0.85 nm, Δd=0.02 nm. g(0.5)=0.889; The calculation result is far below the criterion threshold.

[0068] Scanning electron microscopy revealed a significant coffee ring effect and large-area graphene oxide agglomeration on the coating surface, with visible pores at the zinc substrate interface. The Zn‖Cu half-cell in this comparative example failed after only about 150 cycles; the internal resistance of the full cell was approximately 4.5 times higher than that of Example 1. This comparative example demonstrates that without dual-convective self-assembly and thickness constraints, simple physical mixing coating cannot achieve the technical effects of this invention.

[0069] Comparative Example 4: The formula is exactly the same as that in Example 1 (r T =0.5, h target =80nm, v E =0.84), but skipped the real-time monitoring and feedback adjustment of the liquid surface temperature gradient dT / dr and the reflected light color shift ΔRGB in the dual-convective self-assembled state of this invention: the system after adding ethyl acetate was directly placed in a constant temperature environment of 35°C to allow the ethyl acetate to evaporate rapidly in one direction. The resulting negative electrode is denoted as Zn@MRL-4.

[0070] Characterization results: The obtained thin film has an h distribution of 45–135 nm (with a significant gradient along the radial direction), with an average h = 92 nm; E = 13.8 GPa, ε = 7.3%, Δd = 0.025 nm; The calculation result does not meet the criteria.

[0071] Optical microscopy revealed a concentric, non-uniform distribution of the film, corresponding to intense, uncontrolled Marangoni convection. This comparative example demonstrates that even with the component formulation and thickness target of this invention, without feedback regulation of dT / dr and ΔRGB in the dual-convective self-assembly state, graphene oxide nanosheets cannot achieve uniform self-assembly at the gas-liquid interface, resulting in films with non-uniform mechanical parameters and lacking mechanical self-adaptability. The symmetric cell stabilized for only about 200 hours at 0.5 mA / cm² before short-circuiting.

[0072] Comparative Example 5: Formula r T=0.5, but h target Set to 200nm. Calculate based on the coupling relationship. Zn@MRL-5 was prepared by increasing the concentration of graphene oxide dispersion to 2 mg / mL and correspondingly increasing the amount of raw material. Characterization results: h = 205 nm, E = 21.8 GPa, ε = 11.2%, Δd = 0.045 nm, g(0.5) = 0.889; The calculation result does not meet the criteria.

[0073] Although both Young's modulus and elongation at break are within suitable ranges, the excessively large h leads to a significant decrease in the Δd / h term, resulting in an overall index that fails to meet the standard. Electrochemical impedance spectroscopy revealed that its interfacial charge transfer impedance was 3.2 times that of Example 1; correspondingly, the Zn‖MnO2 full cell exhibited rapid capacity decay after only about 650 cycles at 1 A / g. This comparative example demonstrates that excessive thickness of the zinc-ion battery anode protection material based on graphene oxide film is detrimental to achieving the technical effect of this invention, and simply increasing the thickness cannot linearly improve performance.

[0074] V. Testing Methods 1. Thickness measurement: The Zn@MAL cross section was located, cut and observed using focused ion beam cutting combined with field emission scanning electron microscopy (FIB-SEM). The thickness of the zinc-ion battery negative electrode protection material based on graphene oxide film was measured at no less than 5 different locations and the arithmetic mean was taken.

[0075] 2. Microstructure and elemental distribution: The microstructure of the cross section was observed using a high-resolution transmission electron microscope (HRTEM), and a line scan was performed along the normal of the cross section using an energy dispersive spectroscopy (EDS) instrument to quantitatively analyze the distribution of oxygen along the thickness direction.

[0076] 3. Interlayer spacing: The XRD pattern of the self-supporting zinc-ion battery anode protection material based on graphene oxide film was measured using a CuKα radiation X-ray diffractometer. The scanning range was 2θ = 5° to 30° with a step size of 0.02°. The interlayer spacing d was calculated based on the Bragg equation using the position of the (001) diffraction peak.

[0077] 4. Functional group diagnosis: Attenuated total reflectance mode of Fourier transform infrared spectrometer, scanning range 4000 cm⁻¹ 1 ~400cm 1 4cm resolution 1 Comparison of MAL and pure graphene oxide (MRL) at 3500 cm⁻¹ 1~3850cm 1 (hydroxyl) and 1650cm 1 ~1800cm 1 The position of the characteristic peak in the (carboxyl) region.

[0078] 5. Chemical state analysis: The O1s core energy level spectrum was measured using an AlKα monochromatic X-ray photoelectron spectrometer with the contaminating carbon C1s (284.8 eV) as the calibration reference. The binding energy shift was recorded by fitting the Gaussian-Lorentz mixture function.

[0079] 6. Mechanical property testing: On one hand, the self-supporting MAL membrane was cut into 2mm×20mm rectangular strips, and stress-strain tests were performed using a micro tensile testing machine at a tensile rate of 0.1mm / min. The Young's modulus was calculated from the slope of the linear segment, and the elongation at break was calculated using the abscissa of the fracture point. On the other hand, peak force quantitative nanomechanics (PF-QNM) mode of atomic force microscopy was used to scan a 4μm×4μm region on the Zn@MAL surface, obtaining a Young's modulus mapping map of approximately 40,000 sampling points, and its distribution was statistically analyzed.

[0080] 7. Zn‖Cu Half-Cell Test: CR2025 coin cells were assembled using Zn@MAL as the negative electrode and bare copper foil as the working and counter electrodes, respectively. The electrolyte was 2 mol / L ZnSO4. Constant current charge-discharge cycles were performed at a current density of 5 mA / cm² and an areal capacity of 1 mAh / cm². Coulombic efficiency is defined as the ratio of stripped charge to deposited charge.

[0081] 8. Symmetrical cell test: A Zn‖Zn symmetric cell was assembled using two identical Zn@MAL negative electrodes. The electrolyte was 2 mol / L ZnSO4. The cells were subjected to long-term constant current cycling under the conditions of 0.5 mA / cm² / 0.5 mAh / cm² and 5 mA / cm² / 1 mAh / cm², respectively. The voltage curves were recorded until a short circuit occurred.

[0082] 9. Chronoamperometry: Using a three-electrode system, a platinum sheet as the counter electrode, and an Ag / AgCl reference electrode, the current-time curve of Zn@MAL is tested at a constant overpotential of -150mV. The two-dimensional or three-dimensional diffusion behavior is determined based on the shape of the curve.

[0083] 10. Linear sweep voltammetry (LSV) hydrogen evolution test: Using 1 mol / L Na2SO4 aqueous solution as electrolyte, the scan rate was 5 mV / s. The hydrogen evolution onset potential was recorded to evaluate the suppression effect of the zinc-ion battery negative electrode protection material based on graphene oxide film on the hydrogen evolution side reaction.

[0084] 11. Full cell test: Using Zn@MAL as the negative electrode and β-MnO2 (area loading 5-10 mg / cm²) as the positive electrode, with an electrolyte of 2 mol / L ZnSO4 + 0.1 mol / L MnSO4, rate performance was tested at different current densities of 0.2-3 A / g, and long-cycle performance was tested at 1 A / g. The charge / discharge voltage window was 0.8-1.8 V.

[0085] 12. Atomic force microscopy-infrared spectroscopy (AFM-IR) test: at 973 cm⁻¹ 1 To detect the frequency (corresponding to the characteristic stretching vibration of the epoxy group COC in the zinc-ion battery anode protection material based on graphene oxide film), the Zn@MAL surface was scanned, and the spatial distribution of the infrared amplitude signal was recorded. The signal from the bare zinc surface was used as a control to quantitatively evaluate the uniformity and integrity of the zinc-ion battery anode protection material based on graphene oxide film.

[0086] 13. Contact angle test: The seat drop method was used to drop 5 μL of deionized water onto the surface of bare zinc, Zn@MRL and Zn@MAL and the static contact angle after the three-phase contact line stabilized was recorded. At least 3 different positions were tested for each sample and the average value was taken.

[0087] 14. Desolvation activation energy test: Symmetric cells were assembled using bare zinc, Zn@MRL, and Zn@MAL, respectively. Electrochemical impedance spectroscopy was collected at four temperature points: 25℃, 35℃, 45℃, and 55℃. The charge transfer impedance R was extracted. ct According to the Arrhenius relation ln(1 / R) ct )= E a The desolvation activation energy E was obtained by fitting / (RT)+C. a .

[0088] 15. Linear polarization curve corrosion test: A three-electrode system was used, with bare zinc, Zn@MRL and Zn@MAL as working electrodes, a platinum sheet as the counter electrode, and an Ag / AgCl reference electrode. The electrolyte was 2 mol / L ZnSO4, the scan rate was 1 mV / s, and the scan range was ±150 mV relative to the open circuit potential. The corrosion potential E was obtained by Tafel extrapolation. corr With corrosion current density i corr .

[0089] 16. Cyclic voltammetry (CV) test: Using a Zn‖β-MnO2 full cell as the system, with a voltage window of 0.8–1.8 V and a scan rate of 0.2 mV / s, the redox peak positions, peak current densities, and closed integral areas of Zn@MAL and bare zinc anode were compared to evaluate the interfacial kinetics and electrochemical reversibility.

[0090] VI. Test Results and Analysis Table 1 summarizes the key formulations, processes, mechanical parameters, and electrochemical performance data of Examples 1-6 and Comparative Examples 1-5.

[0091] Table 1 Summary of key parameters and performance of the examples and comparative examples Note: The cycle counts of Zn‖Cu half-cells were measured under conditions of 5 mA / cm² / 1 mAh / cm², and the termination criterion was that the average coulombic efficiency dropped below 99%. Comparative Example 3 used a conventional coating process and did not implement the five adaptive states of this invention; therefore, v is not present. E Values; in Comparative Example 4, h exhibits a radial gradient distribution, listed as range values.

[0092] In addition to the mechanical and life data listed in Table 1, the following test data were obtained by conducting tests according to test methods 12 to 16: (i) AFM-IR at 973 cm 1 At the detection frequency, the Zn@MAL-1 surface exhibits a high-intensity continuous infrared amplitude signal, confirming the uniform distribution of epoxy-based COC in the zinc-ion battery anode protection material based on graphene oxide film; (ii) the contact angle decreases from 91.3° of bare zinc to 72.4° of Zn@MRL and then to 14.3° of Zn@MAL-1, confirming the strong hydrophilicity of the oxygen-rich surface of the zinc-ion battery anode protection material based on graphene oxide film; (iii) the desolvation activation energy E obtained by fitting the variable-temperature electrochemical impedance spectroscopy is... a The concentrations were as follows: bare zinc 25.6 kJ / mol, Zn@MRL 29.0 kJ / mol, and Zn@MAL-119.3 kJ / mol, indicating that the polar sites enriched on the MAL surface were reduced [Zn(H2O)6]. 2+ (iv) In the linear scanning voltammetric hydrogen evolution test in 1 mol / L Na2SO4 electrolyte, the hydrogen evolution peak potential shifted negatively from -1.92 V of bare zinc to -1.98 V of Zn@MRL and then to Zn@MAL-1. At 2.05V, the hydrogen evolution overpotential increases by approximately 130mV; (v) In the linear polarization test in 2mol / L ZnSO4 electrolyte, the corrosion current density i of Zn@MAL-1 is... corr The corrosion potential E decreased to 1.18 mA / cm². corr Move to 0.968V, exhibiting the corrosion resistance characteristics of "high potential and low current"; (vi) In the CV curve of the Zn‖β-MnO2 full cell, the oxidation peak of the Zn@MAL-1 anode shifted negatively by 18mV relative to the bare zinc anode, and the two reduction peaks shifted positively by 17mV and 30mV respectively, and the peak current density was higher and the closed integral area was larger, confirming that the zinc-ion battery anode protection material based on graphene oxide film reduced the polarization of the full cell and enhanced the reaction kinetics.

[0093] As shown in Table 1, the mechanical adaptive index η of Examples 1-6 MA All values ​​significantly exceeded the criterion threshold of 5, with Zn‖Cu half-cell cycle lives exceeding 6500 cycles and corresponding average coulombic efficiencies consistently above 99.9%. In contrast, the η values ​​of comparative examples 1–5… MA All less than 5: Comparative Example 1 suffers from g(r) due to the lack of a Triton X-100-mediated hydrogen bond network. T )=0, directly invalid; although in Comparative Example 2 g(r) T Larger but r T After deviating from the coupling range, the correlation between E and Δd / h deteriorates; in Comparative Example 3, the Δd / h term collapses due to the thickness being much larger than the nanometer-scale target; in Comparative Example 4, the mechanical parameters become discretized due to the lack of dual convection monitoring feedback; and Comparative Example 5 demonstrates that simply increasing the thickness will worsen the overall index due to the decrease in the Δd / h term. The above overall patterns indicate that η MA The ≥5 criterion is a closed-loop constraint with multiple parameters, none of which can be omitted.

[0094] Further analysis: Formulas in Example 1 and Example 6 T =0.5, with the same target thickness, only the graphene oxide concentration and sheet diameter differ, the η of both is... MA The values ​​were 7.29 and 8.19 respectively, with cycle lives exceeding 9500 cycles, indicating that the preparation method of this invention is applicable to both graphene oxide raw material concentration and sheet size; Examples 4 and 5 correspond to smaller (r) values. T =0.1, h≈30nm) and larger (r T The parameter values ​​(e.g., h≈150nm) all achieve η under closed-loop feedback. MA ≥5.

[0095] In terms of electrochemical mechanism analysis, Figure 1 The cross-sectional SEM (b) and HRTEM-EDS (c) results show that the MAL layer obtained in Example 1 has a uniform ultrathin thickness of approximately 80 nm and conformally fits the zinc substrate without porosity; the (001) diffraction peak in XRD (f) shifts from 0.84 nm to 0.87 nm, confirming successful intercalation of Triton X-100; and the 3614 cm⁻¹ in FTIR (g) indicates... 1 and 1730cm 1 The characteristic peaks were red-shifted to 3609 cm⁻¹. 1 and 1721cm 1 The 0.2 eV shift of the O1s core level towards higher binding energies confirms the formation of a dynamic hydrogen bond network and the decrease in electron cloud density of ether oxygen atoms; the contact angle decreased from 91.3° to 14.3° in bare zinc, and the LSV hydrogen evolution peak potential in the Na2SO4 system decreased from... 1.92V negative shift to 2.05V further confirms the strong affinity and hydrogen evolution inhibition effect of the zinc-ion battery anode protection material based on graphene oxide film.

[0096] Figure 2 The mechanical characterization data shown indicate that the stress-strain curve of the self-supporting MAL film shows a significant increase in elongation at break compared to the pure graphene oxide film (MRL), rising from 5.8% to 12% and tensile strength from 11.5 MPa to 13.8 MPa. The nanoindentation force-displacement curves of MAL reveal a broad reversible elastic range and a large hysteresis loop area, corresponding to the dynamic stick-slip energy dissipation mechanism of the hydrogen bond network. The statistical distribution of MAL's Young's modulus mapping exhibits a narrow half-peak width-height symmetry, confirming the microscopic uniformity of its composition and mechanical properties.

[0097] Figure 3 The in-situ optical microscopy results show that at a current density of 5 mA / cm², bare zinc and Zn@MRL exhibited obvious dendritic protrusions within 24 min, while Zn@MAL maintained a smooth interface throughout the process. Post-deposition scanning electron microscopy and white light interference three-dimensional morphology images show that the surface roughness Ra of Zn@MAL is only 0.4 μm, far lower than the 3.4 μm of bare zinc and the 2.3 μm of Zn@MRL. Chronocurrent curves show that Zn@MAL transformed zinc deposition from two-dimensional diffusion to steady-state three-dimensional diffusion, inhibiting tip growth. The nucleation overpotential decreased from 59 mV for bare zinc to 31 mV for Zn@MAL. The relaxation time distribution contour plot corresponding to the in-situ electrochemical impedance spectroscopy shows that the interfacial impedance distribution of Zn@MAL remained stable throughout the cycling process.

[0098] Figure 4The electrochemical performance data shown are as follows: Example 1 Zn@MAL-1‖Cu half-cell accumulated over 10,000 cycles under conditions of 5 mA / cm² / 1 mAh / cm², with an average coulombic efficiency of 99.94%, far exceeding that of bare copper (150 cycles, 99.63%) and Cu@MRL (800 cycles, 99.73%). A horizontal comparison with recent literature reports (b) shows that this invention leads in terms of cycle count, average coulombic efficiency, and areal capacity. The symmetric cell achieved a coulombic efficiency of 0.5 mA / cm². The battery exhibits stable operation for over 4000 hours, which is more than 47 times that of bare zinc (84 hours); it is stable for over 2000 hours at 5 mA / cm²; the Zn‖β-MnO2 full cell demonstrates good rate performance in the range of 0.2 to 3 A / g, maintains a specific capacity of 112 mAh / g at a high current of 3 A / g, and is stable for over 3000 cycles at 1 A / g. It also extends the cycle life under zinc-poor conditions with N / P=2.5 and a zinc foil thickness of 7.8 μm, verifying the application potential of this invention in practical energy storage devices.

[0099] Based on the above test results: This invention utilizes Triton X-100 in r T Intercalation within the range of 0.1 to 1.0, v E With r T and h target By synergistically implementing four aspects—deterministic mapping, nanoscale thickness window, criterion transfer from the initial dispersed state to the substrate transfer state, and reverse adjustment from the substrate transfer state to the initial dispersed state—a zinc-ion battery anode protection material based on graphene oxide film was obtained, simultaneously satisfying high modulus, high toughness, nanoscale thickness, and molecular-level uniformity. This suppresses zinc dendrite growth and hydrogen evolution side reactions, thereby improving the cycle life of aqueous zinc-ion batteries. Comparative Examples 1-5, lacking one or more of these elements, all exhibited mechanical adaptive indices below the criterion threshold and significantly degraded electrochemical cycle life. The technical effects of this invention can only be achieved through the synergistic implementation of all four elements.

[0100] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application, and should all be included within the protection scope of this application. Content not described in detail in this specification belongs to the prior art known to those skilled in the art.

Claims

1. A zinc-ion battery negative electrode protection material based on graphene oxide thin film, characterized in that, The zinc-ion battery anode protection material based on graphene oxide film is a self-supporting composite film formed by the self-assembly of graphene oxide nanosheets and the nonionic surfactant Triton X-100 through molecular-level intercalation and dynamic hydrogen bond network crosslinking. Triton X-100 is intercalated between the layers of the graphene oxide nanosheets. The ether oxygen atoms in the polyoxyethylene segments of Triton X-100 form the dynamic hydrogen bond network with the hydroxyl and carboxyl groups on the surface of the graphene oxide nanosheets, thereby increasing the interlayer spacing of the 001 crystal planes of the graphene oxide nanosheets. The mechanical adaptive index η of the zinc-ion battery anode protection material based on graphene oxide film is... MA ≥5; the mechanical adaptive index η MA Calculate using the following formula: In the formula, η MA denoted as the mechanical adaptive index of the zinc-ion battery anode protection material based on graphene oxide film; k0 is a dimensionless reference constant; E is the Young's modulus of the zinc-ion battery anode protection material based on graphene oxide film; ε is the elongation at break of the zinc-ion battery anode protection material based on graphene oxide film; d is the 001 crystal plane interlayer spacing of the zinc-ion battery anode protection material based on graphene oxide film; d0 is the 001 crystal plane reference interlayer spacing of pure graphene oxide. Δd = d - d0, where Δd is the interlayer spacing expansion of the 001 crystal plane of the graphene oxide nanosheet; h is the thickness of the zinc-ion battery anode protection material based on graphene oxide film; g(r T ) represents the hydrogen bonding efficiency function; r T The mass ratio of Triton X-100 to graphene oxide nanosheets.

2. The zinc-ion battery negative electrode protection material based on graphene oxide film according to claim 1, characterized in that, The zinc-ion battery anode protection material based on graphene oxide film simultaneously satisfies the following requirements: the thickness h of the zinc-ion battery anode protection material based on graphene oxide film is 30nm~150nm, the Young's modulus E is 15GPa~25GPa, the elongation at break ε is 8%~15%, and the tensile strength is 10MPa~16MPa.

3. The zinc-ion battery negative electrode protection material based on graphene oxide film according to claim 1, characterized in that, The zinc-ion battery negative electrode protection material based on graphene oxide film is at 3500 cm⁻¹. 1 ~3850cm 1 hydroxyl characteristic peaks within the range and 1650 cm⁻¹ 1 ~1800cm 1 The characteristic peaks of the carboxyl group within the range all exhibit a red shift relative to pure graphene oxide; the O1s core energy level peak of the graphene oxide nanosheets shifts by 0.1 eV to 0.3 eV towards higher binding energy relative to pure graphene oxide.

4. The zinc-ion battery negative electrode protection material based on graphene oxide film according to claim 1, characterized in that, The average degree of polymerization (n) of the polyoxyethylene segments of TritonX-100 is 8–12, and the hydrophilic-lipophilic balance (HLB) is 12–14; the mass ratio (r) of TritonX-100 to graphene oxide nanosheets is... T It ranges from 0.1 to 1.

0.

5. A zinc metal anode having a zinc-ion battery anode protection material based on graphene oxide film, characterized in that, The zinc metal anode includes a zinc metal substrate and a zinc-ion battery anode protection material based on a graphene oxide film as described in any one of claims 1 to 4, which is covered on at least one surface of the zinc metal substrate. The zinc-ion battery anode protection material based on a graphene oxide film is conformally bonded to the zinc metal substrate, and the interface between the two is free of pores and phase separation. The thickness of the zinc metal substrate is 5 μm to 50 μm.

6. A method for preparing a zinc-ion battery negative electrode protection material based on graphene oxide thin film according to any one of claims 1 to 4, characterized in that, The preparation method sequentially includes five adaptive states: initial dispersed state, organic phase spread state, dual-convection self-assembled state, membrane consolidation state, and substrate transfer state. The operation of each state and the transition criteria between states are as follows: The initial dispersion is as follows: an aqueous dispersion of the graphene oxide nanosheets and Triton X-100 are mixed at the target mass ratio r. T The mixture is mixed and ultrasonically dispersed to obtain a mixed dispersion; when the absolute value of the zeta potential |ζ| ≥ 30 mV and the polydispersity index PDI ≤ 0.3, it enters the organic phase spread state. The organic phase spread state is: the required volume ratio v is calculated according to the following process parameter coupling formula. E : In the formula, v E The volume ratio of ethyl acetate to the mixed dispersion; r T The mass ratio of Triton X-100 to graphene oxide nanosheets; h target h0 is the target thickness of the negative electrode protection material for the zinc-ion battery; a is the reference thickness; b is the constant coefficient; and r is the reference thickness. T The term coefficient; c is the thickness term coefficient; ethyl acetate is prepared according to the stated volume ratio v E Ethyl acetate is added along the container wall above the surface of the mixed dispersion, causing it to form an independent upper organic liquid phase above the mixed dispersion; when the spatial non-uniformity σ of the reflected light of the independent upper organic liquid phase... I / μ I When the value is ≤0.1, it enters the dual-convection self-assembly state; The dual-convective self-assembled state is as follows: the ethyl acetate evaporates from the surface of the independent upper organic liquid phase, inducing Marangoni convection and Rayleigh-Bernard convection at the gas-liquid interface; the graphene oxide nanosheets and the Triton X-100 self-assemble at the gas-liquid interface to form a continuous film; in the dual-convective self-assembled state, the liquid surface temperature gradient dT / dr and the reflected light color shift ΔRGB are monitored in real time, and the ambient temperature T is adjusted according to the following mapping. amb When dT / dr ≥ 0.5℃ / cm and the reflected light color shift ΔRGB changes rapidly, the ambient temperature T... amb Lower the ambient temperature by 2℃; when dT / dr ≤ 0.1℃ / cm and the reflected light color shift ΔRGB changes slowly, lower the ambient temperature T. amb Increase by 2℃; when 0.1℃ / cm < dT / dr < 0.5℃ / cm and the reflected light color shift ΔRGB progresses steadily in a gradient, maintain the ambient temperature T. amb Unchanged; after the continuous film has fully spread at the gas-liquid interface, it enters the film solidification state; The solidified state of the film is as follows: after the ethyl acetate evaporates, the interference fringes of the continuous film floating on the liquid surface are observed; when the interference fringes are uniform and the fringe spacing remains stable, the film enters the substrate transfer state; when the interference fringes break or there is local light transmission, the film reverts to the dual convection self-assembly state and ethyl acetate is added to re-trigger self-assembly. The substrate transfer state is as follows: the continuous thin film is transferred from the liquid surface to the surface of a zinc metal substrate, and then vacuum dried at 20℃~60℃ for 2h~24h to obtain the zinc-ion battery anode protection material based on graphene oxide film; when the obtained zinc-ion battery anode protection material based on graphene oxide film does not satisfy the mechanical adaptive exponent η after testing. MA When the value is ≥5, the initial dispersion state is reverted and the mass ratio r is adjusted in the reverse direction. T and the volume ratio v E The process is repeated until the resulting zinc-ion battery anode protection material based on graphene oxide film satisfies η. MA ≥5.

7. The preparation method according to claim 6, characterized in that, In the coupling formula of the process parameters, coefficient a = 0.20, coefficient b = 0.80, and coefficient c = 0.30; the mass concentration of the aqueous dispersion of the graphene oxide nanosheets is 0.1 mg / mL to 2 mg / mL, and the diameter of the graphene oxide nanosheets is 1 μm to 5 μm.

8. The preparation method according to claim 6, characterized in that, In the aforementioned dual-convection self-assembly state, the ambient temperature T amb The single adjustment range shall not exceed 2°C, and after each adjustment, the liquid surface temperature gradient dT / dr and the reflected light color shift ΔRGB shall be monitored again before the next adjustment is carried out.

9. An aqueous zinc-ion battery, characterized in that, The aqueous zinc-ion battery includes a positive electrode, an electrolyte, and a negative electrode, wherein the negative electrode is a zinc metal negative electrode having a zinc-ion battery negative electrode protection material based on a graphene oxide film as described in claim 5.

10. The aqueous zinc-ion battery according to claim 9, characterized in that, The positive electrode is a β-MnO2 positive electrode, and the surface loading of the active material in the positive electrode is 5 mg / cm³. 2 ~10mg / cm 2 .

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