Preparation method of full-solid high-capacity low-temperature vanadium-based rechargeable hydrogen proton battery based on nafion proton exchange membrane integration

Abstract

A method for fabricating a high-capacity, low-temperature vanadium-based rechargeable hydrogen electrochemical battery based on a Nafion proton exchange membrane integration belongs to the field of electrochemical energy storage technology. This method sequentially prepares V... FeCN -VHCF positive electrode, Pt / C negative electrode catalyst, V FeCN A solid-state proton cell was finally assembled from a composite material of VHCF, Nafion proton exchange membrane, and Pt / C catalyst. Among these, VHCF... FeCN The -VHCF positive electrode is prepared by dissolving vanadium pentoxide in hydrochloric acid dilution solution and adding glycerol to prepare a precursor, which is then co-precipitated with potassium ferricyanide solution. The composite material is prepared by loading the positive and negative electrode slurries with DuPont Nafion proton exchange membranes and drying them. The battery can be assembled by using an air-filled button cell. The battery prepared by this invention still exhibits excellent electrochemical performance at ultra-low temperature (0°C).

Description

Technical Field

[0001] This invention relates to the field of electrochemical energy storage technology, and in particular to a method for preparing an all-solid-state high-capacity low-temperature vanadium-based rechargeable hydrogen electrochemical battery based on a Nafion proton exchange membrane. Background Technology

[0002] While novel high-capacity solid-state proton batteries have shown broad application prospects, their fabrication technology still faces many core bottlenecks that urgently need to be overcome, severely hindering industrialization. As a core characteristic of the "solid-state" system, the solid-solid interface contact, ion transport efficiency, and low-temperature adaptability are particularly prominent issues: On the one hand, in low-temperature environments (0°C), the ion migration barrier between the solid electrolyte and the electrode in existing novel high-capacity solid-state proton batteries increases sharply, leading to significant capacity decay. Current fabrication processes mostly focus on optimizing individual components, without considering the overall adaptability of the solid-state system, resulting in a capacity retention rate of less than 60% at 0°C, far from meeting the requirements of extreme environments. On the other hand, the electrode-electrolyte interface compatibility problem in solid-state systems is a common core bottleneck. In existing fabrication processes, the interfacial bonding strength between the positive electrode and the hydrogen anion solid electrolyte is low, easily forming interfacial cracks, leading to a surge in hydrogen anion transport impedance. Furthermore, some fabrication processes rely on high-temperature sintering (≥300°C), which not only damages the ion transport channels of the solid electrolyte but may also cause structural degradation of the electrode materials, as seen in the solid-state hydrogen battery developed by the Japanese team (Science, 2025). While method 389(6766), 1252-1255) achieves high-efficiency operation at 90℃, the high-temperature preparation process used cannot meet the requirements of ultra-low temperature performance and does not solve the core compatibility problem of high-capacity solid-state systems. Furthermore, existing methods generally suffer from the difficulty of synergistically optimizing "high capacity, ultra-low temperature stability, and low preparation cost." For example, improving the low-temperature performance of solid-state batteries through noble metal doping leads to a surge in cost, while solid-state batteries prepared by simple solution methods cannot simultaneously ensure structural integrity and electrochemical activity. Therefore, developing a novel high-capacity solid-state hydrogen gas ion battery preparation method that can simultaneously achieve enhanced interface compatibility of solid-state systems, ensure high-capacity characteristics at low temperatures, and achieve green and low-cost preparation is of crucial significance for promoting its practical application. Summary of the Invention

[0003] To address the problems existing in the prior art, the purpose of this invention is to provide a simple, low-cost, high-capacity, low-temperature hydrogen gas ion battery fabrication method based on Nafion proton exchange membrane integration.

[0004] The solid-state proton battery fabrication steps are as follows:

[0005] Step 1: Preparation of V FeCN -VHCF positive electrode active material;

[0006] Step 2: Preparation of Pt / C anode catalyst;

[0007] Step 3: Preparation of V FeCN -VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material;

[0008] Step 4: Assemble V FeCN -VHCF || Nafion proton exchange membrane || Pt / C catalyst solid-state hydrogen gas-energy cell;

[0009] In step 1, V FeCN The preparation of VHCF positive electrode active material includes the following steps:

[0010] The first step is to prepare the vanadium precursor solution: vanadium pentoxide (V2O5) is added to hydrochloric acid solution and stirred. Then, glycerol is added to the mixture and stirring is continued to obtain the vanadium precursor solution.

[0011] The second step is to prepare vanadium-based Prussian blue analogue V. FeCN -VHCF:

[0012] A certain amount of the vanadium precursor solution from the first step is named solution A. A certain amount of potassium ferricyanide (K3Fe(CN)6) is added to deionized water and stirred until homogeneous, named solution B. Solution B is added dropwise to solution A and reacted for a period of time. V is obtained by co-precipitation. FeCN -VHCF positive electrode active material;

[0013] Furthermore, the dilute hydrochloric acid solution mentioned in the first step is preferably diluted with deionized water to 75 ml per 50 ml of concentrated hydrochloric acid; each 75 ml of dilute hydrochloric acid solution corresponds to 4 g of vanadium pentoxide (V2O5) and 700 μL of glycerol.

[0014] The next step is as follows: First, take 50 ml of concentrated hydrochloric acid and dilute it to 75 ml with deionized water; then, add 4 g of vanadium pentoxide (V2O5) to the diluted hydrochloric acid solution; stir the mixture at 60 °C for 30 minutes to form an orange suspension; then, carefully inject 700 μL of glycerol into the orange suspension and continue the reaction for 30 minutes to obtain a clear, deep blue solution, which should be stored away from air for later use; dilute each 9.4 mL of the clear solution to 50 mL with deionized water to obtain solution A.

[0015] Solution B: 0.6 g potassium ferricyanide (K3Fe(CN)6) per 50 mL of deionized water;

[0016] In the second step, while continuously stirring, solution B was slowly added drop by drop to solution A, and the mixture was reacted at 60°C for 8 hours, then allowed to stand for 8 hours. The mixture was then repeatedly washed with deionized water and alcohol to obtain a dark green precipitate, which, after drying, yielded V. FeCN -VHCF sample;

[0017] When solution B is added dropwise to solution A, every 4 g of vanadium pentoxide (V2O5) corresponds to 0.6 g of potassium ferricyanide (K3Fe(CN)6).

[0018] In step 3, V FeCN Preparation of VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material:

[0019] Step 1, V FeCN -Preparation of VHCF positive electrode: V FeCN A mixture of VHCF positive electrode active material, acetylene black, and polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1 was prepared to obtain a mixed powder. The mixed powder was then dispersed in N-methylpyrrolidone (NMP) and stirred to produce a uniform VHCF. FeCN -VHCF positive electrode slurry was prepared by uniformly coating one side of a Nafion proton exchange membrane with the obtained slurry; subsequently, the Nafion proton exchange membrane with the slurry was placed under vacuum and dried overnight at 60°C to obtain VHCF. FeCN -VHCF positive electrode sheet; wherein the loading of positive active material on each positive electrode sheet is 1.5-2 mg / 2.0096 cm⁻¹. 2 ;

[0020] The second step involves using a composite Pt / C anode catalyst.

[0021] Preferred method: Pt / C and PVDF are mixed in an 8:2 ratio to obtain a mixed powder; then these powders are dispersed in N-methylpyrrolidone (NMP) and stirred to produce a uniform Pt / C negative electrode slurry; the Pt / C negative electrode slurry is coated onto the other side of a Nafion proton exchange membrane and then dried to obtain V FeCN -VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material; wherein the Pt / C loading on each electrode is approximately 2-3 mg / 2.0096 cm⁻¹ 2 ;

[0022] Furthermore, DuPont Nafion proton exchange membrane material was selected and cut into small circular pieces, for example, with an area of ​​2.0096 cm². 2 Small circular pieces, V FeCN- A VHCF positive electrode slurry was loaded onto one side of a Nafion proton exchange membrane and dried at 60°C. After drying, a Pt / C negative electrode slurry was loaded onto the other side of the Nafion proton exchange membrane and dried at 60°C to obtain VHCF. FeCN -VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material; where V FeCN - The loading of VHCF active material on each electrode is 1.5-2 mg / 2.0096 cm⁻¹. 2 The catalyst Pt / C loading on each electrode is approximately 2-3 mg / 2.0096 cm⁻¹. 2 ;

[0023] In step (4), V FeCN -VHCF || Nafion proton exchange membrane || Pt / C catalyst assembly of solid hydrogen gas-energy cell;

[0024] The casing is a commercial air button battery casing, conforming to the specifications of positive electrode casing, carbon paper, and V. FeCN The button cell is assembled in the following order: VHCF || Nafion proton exchange membrane || Pt / C catalyst integrated membrane, carbon paper, gasket, spring sheet, and negative electrode shell, and then compacted (e.g., by using a Kejing press at 50 MPa).

[0025] The application of the all-solid-state vanadium-based rechargeable hydrogen proton battery based on the Nafion proton exchange membrane integrated by this invention can be used at low temperatures of 0°C and at rates of 2.5C-50C.

[0026] The V prepared above FeCN A solid-state hydrogen gas-energy cell using a VHCF-based proton exchange membrane and a Pt / C catalyst can simultaneously achieve enhanced interfacial compatibility in the solid-state system, ensure high capacity at low temperatures, and be prepared in a green and low-cost manner. Furthermore, it can self-drive a commercially viable small windmill through charge and discharge, demonstrating significant application prospects and potential.

[0027] The advantages of this invention are:

[0028] 1. This invention provides a method for preparing an all-solid-state high-capacity low-temperature vanadium-based rechargeable hydrogen gas electron battery based on Nafion proton exchange membrane integration, which has a simple preparation process.

[0029] 2. The assembled proton battery can complete the battery charging and discharging behavior.

[0030] 3. Through the design of V FeCN-VHCF || Nafion proton exchange membrane || Pt / C catalyst solid hydrogen gas electron battery, which can improve battery safety and practical application prospects. Attached Figure Description

[0031] Figure 1 : Physical image of the VFeCN-VHCF || proton exchange membrane || Pt / C catalyst in Example 3 of this invention

[0032] Figure 2 In Example 5 of this invention, V FeCN -VHCF || Proton Exchange Membrane || CV Curve of Solid-State Hydrogen Gas-Quantum Cell with Pt / C Catalyst

[0033] Figure 3 In Example 5 of this invention, V FeCN -VHCF || Proton Exchange Membrane || GCD Curve of Solid-State Hydrogen Gas Cell with Pt / C Catalyst

[0034] Figure 4 In Example 5 of this invention, V FeCN -VHCF || Proton Exchange Membrane || Rate Performance Curve of Solid-State Hydrogen Gas-Quantum Battery with Pt / C Catalyst at 0°C

[0035] Figure 5 In Example 5 of this invention, V FeCN -VHCF || Proton Exchange Membrane || Pt / C Catalyst Solid-State Hydrogen Gas Ton Battery Cycling Performance Curve at 0°C Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0037] Example 1

[0038] V FeCN -VHCF cathode material and its preparation method are as follows:

[0039] The first step is to prepare the vanadium precursor solution: First, take 50 ml of concentrated hydrochloric acid and dilute it to 75 ml with deionized water. Then, add 4 g of vanadium pentoxide (V₂O₅) to the diluted hydrochloric acid solution. Stir the mixture at 60 °C for 30 minutes to form an orange suspension. Subsequently, carefully inject 700 μL of glycerol into the orange suspension and continue the reaction for 30 minutes to obtain a clear, deep blue solution, which should be stored in an airtight environment for later use.

[0040] The second step is to prepare V. FeCN -VHCF: Dilute 9.4 mL of the precursor solution to 50 mL with deionized water, stir well, and name this solution A. Add 0.6 g of potassium ferricyanide (K3Fe(CN)6) to 50 mL of deionized water, stir well, and name the resulting yellow solution B. While stirring continuously, slowly add solution B drop by drop to solution A, react at 60 °C for 8 hours, and let stand for 8 hours. Wash repeatedly with deionized water and alcohol to obtain a dark green precipitate. After drying at 60 °C for 8 hours, obtain VHCF. FeCN- VHCF sample.

[0041] Example 2

[0042] Preparation of Pt / C catalytic negative electrode slurry:

[0043] Pt / C and PVDF were mixed in an 8:2 ratio to obtain a mixed powder; these powders were then dispersed in N-methylpyrrolidone (NMP) and stirred to produce a homogeneous slurry; wherein the loading of active material on each electrode was approximately 2-3 mg / 2.0096 cm⁻¹. 2 .

[0044] V FeCN Preparation of VHCF positive electrode slurry:

[0045] V FeCN A mixture of VHCF positive electrode active material, acetylene black, and polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1 was prepared to obtain a mixed powder. The mixed powder was then dispersed in N-methylpyrrolidone (NMP) and stirred to produce a uniform VHCF. FeCN -VHCF positive electrode slurry.

[0046] Example 3

[0047] V FeCN -VHCF || Nafion proton exchange membrane || Preparation of Pt / C catalyst:

[0048] DuPont Nafion proton exchange membrane material was selected and cut into pieces of 2.0096 cm. 2Small circular pieces were used to load the prepared positive electrode slurry onto one side of a Nafion proton exchange membrane, which was then dried at 60°C. After drying, a Pt / C slurry was loaded onto the other side of the Nafion proton exchange membrane and dried at 60°C. V FeCN - The loading of VHCF active material on each electrode is 1.5-2 mg / 2.0096 cm⁻¹. 2 The loading of Pt / C catalyst on each electrode is approximately 2-3 mg / 2.0096 cm⁻¹. 2 .

[0049] Example 4

[0050] V FeCN -VHCF || Nafion proton exchange membrane || Preparation of solid-state hydrogen gas-energy gas-energy batteries with Pt / C catalyst

[0051] Furthermore, commercial air button cell casings were selected, and the positive electrode casing, carbon paper, and V were used. FeCN The button cell is assembled in the following order: VHCF, Nafion proton exchange membrane, Pt / C catalyst integrated membrane, carbon paper, gasket, spring sheet, and negative electrode shell. It is then compacted at 50 MPa using a Kejing press.

[0052] Example 5

[0053] V prepared in Example 4 above was selected. FeCN Electrochemical performance testing of solid-state hydrogen gas-energy cell with VHCF, Nafion proton exchange membrane, and Pt / C catalyst:

[0054] Figure 2 shows the cyclic voltammetry curves of this Nafion membrane-integrated solid-state hydrogen gas electronic battery, tested at 5, 10, 15, and 20 mV·s. -1 The test was conducted at four gradient scan rates, with a potential window of 0–1.4 V (vs. Ag / AgCl). Two pairs of highly reversible and symmetrical redox characteristic peaks were clearly observed in the curves, corresponding to the proton insertion / deintercalation reaction of the vanadium and iron sites coupled as dual redox centers in the vanadium-based Prussian blue cathode. As the scan rate increased from 5 mV·s... -1 Increased to 20 mV·s -1The redox peaks showed only slight potential shifts, maintaining their integrity and shape without distortion. No significant hydrogen or oxygen evolution side reaction currents were observed, demonstrating that the battery system exhibits extremely low electrochemical polarization, ultrafast proton conduction kinetics, and highly reversible electrochemical reaction characteristics. This superior electrochemical kinetic performance stems from the low-barrier transport channels provided by the open three-dimensional framework and continuous hydrogen bond network of the vanadium-based Prussian blue cathode, and further benefits from the high integration of the Nafion proton exchange membrane with the cathode, creating a continuous and stable proton transport interface. These peaks correspond one-to-one with the two pairs of redox peaks in the CV curve, representing the high-potential main capacity plateau of vanadium sites with two-electron transfer and the low-potential additional capacity plateau of iron sites with single-electron transfer, respectively. This battery achieves a capacity as high as 170 mAh·g⁻¹. -1 The discharge specific capacity fully releases the theoretical capacity of the vanadium-based Prussian blue cathode. The charge-discharge plateau voltage difference is extremely small, exhibiting extremely low reaction polarization and extremely high energy conversion efficiency. Combined with an average discharge voltage of ~0.9 V, it achieves the top mass energy density among similar proton batteries.

[0055] V was characterized by rate and cyclic electrochemical performance testing. FeCN -VHCF || Nafion proton exchange membrane || Pt / C catalyst solid hydrogen gas electron battery performance in terms of rate capability, cycle performance and low temperature capability.

[0056] Figure 4 shows the rate performance test curves of this solid-state hydrogen quantum battery under harsh low-temperature conditions at 0℃. The test covers multiple rate gradients of 2.5C, 5C, 10C, 20C, and 50C. After completing the high-rate impact test, the battery returned to a low rate of 2.5C to complete the capacity recovery test. The test results show that the battery can release approximately 160 mAh·g at a low rate of 2.5C. -1 It exhibits a high discharge specific capacity, maintaining approximately 140 mAh·g even at medium rates of 10C and high rates of 20C. -1 Approximately 120 mAh·g -1The battery exhibits reversible capacity, maintaining effective capacity output even under extreme conditions of ultra-high rate (50C, requiring only 72 seconds to complete charge and discharge). Furthermore, when the rate recovers to the initial 2.5C, the discharge specific capacity almost completely returns to its initial value with no irreversible capacity loss. The coulombic efficiency remains consistently close to 100% across the entire rate range. This superior rate performance and capacity reversibility at 0°C are attributed to the intrinsic Grotthussian ultrafast proton conduction mechanism of the vanadium-based Prussian blue cathode, which overcomes the proton diffusion kinetics bottleneck of traditional intercalation materials at low temperatures. More importantly, the Nafion proton exchange membrane maintains excellent proton conductivity at low temperatures. The continuous proton transport network integrated with the cathode effectively reduces low-temperature interface impedance, ensuring efficient and reversible proton transport under high current at low temperatures. This perfectly demonstrates the core advantage of this Nafion membrane-integrated all-solid-state high-capacity low-temperature vanadium-based rechargeable hydrogen gas ion battery: high rate at low temperatures.

[0057] Figure 5 shows the long-cycle performance test curves of this solid-state proton battery at 0℃ and 20C high current density, with the test period covering 120 complete charge-discharge cycles. The test results show that the battery achieves an initial discharge specific capacity of approximately 120 mAh·g under harsh low-temperature, high-current cycling conditions. -1 After 120 cycles, the capacity retention rate remained as high as 89.9%, with an average single-cycle capacity decay rate of less than 0.01%. Throughout the entire cycle, the coulombic efficiency remained consistently above 98%, with no significant efficiency fluctuations or decay, demonstrating extremely strong long-term cycle stability and interface compatibility. The excellent cycle stability of this battery under low temperature and high current conditions stems from the near-zero strain proton intercalation characteristics of the vanadium-based Prussian blue cathode. This maintains a highly stable crystal framework during cycling, effectively suppressing transition metal dissolution and structural collapse. Simultaneously, the integrated design of the Nafion membrane and the cathode isolates the active material from direct contact with the electrolyte, fundamentally suppressing side reactions during cycling and constructing a long-term stable electrochemical reaction interface. Ultimately, this achieves long-life stable cycling under low temperature and high current conditions, fully validating the low-temperature long-cycle stability and practical application potential of this Nafion membrane-integrated all-solid-state high-capacity low-temperature vanadium-based rechargeable hydrogen gas electrolysis battery.

[0058] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to this embodiment will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A method for preparing an all-solid-state high-capacity low-temperature vanadium-based rechargeable hydrogen gas-electric cell based on a Nafion proton exchange membrane, characterized in that, Includes the following steps: Step 1: Preparation of V FeCN -VHCF positive electrode active material; Step 2: Preparation of Pt / C anode catalyst; Step 3: Preparation of V FeCN -VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material; Step 4: Assemble V FeCN -VHCF || Nafion proton exchange membrane || Pt / C catalyst solid-state hydrogen gas-energy cell; In step 1, V FeCN The preparation of VHCF positive electrode active material includes the following steps: The first step is to prepare the vanadium precursor solution: vanadium pentoxide (V2O5) is added to hydrochloric acid solution and stirred. Then, glycerol is added to the mixture and stirring is continued to obtain the vanadium precursor solution. The second step is to prepare vanadium-based Prussian blue analogue V. FeCN -VHCF: A certain amount of the vanadium precursor solution from the first step is named solution A. A certain amount of potassium ferricyanide (K3Fe(CN)6) is added to deionized water and stirred until homogeneous, named solution B. Solution B is added dropwise to solution A and reacted for a period of time. V is obtained by co-precipitation. FeCN -VHCF positive electrode active material.

2. The method according to claim 1, characterized in that, The dilute hydrochloric acid solution mentioned in the first step is preferably diluted with deionized water to 75 ml from 50 ml of concentrated hydrochloric acid; each 75 ml of dilute hydrochloric acid solution corresponds to 4 g of vanadium pentoxide (V2O5) and 700 μL of glycerol.

3. The method according to claim 1, characterized in that, Dilute each 9.4 mL of clear solution with deionized water to 50 mL to obtain solution A; Solution B: 0.6 g potassium ferricyanide (K3Fe(CN)6) per 50 mL of deionized water; The second step involves slowly adding solution B drop by drop to solution A while continuously stirring. The mixture is reacted at 60°C for 8 hours and then allowed to stand for 8 hours. After repeated washing with deionized water and alcohol, a dark green precipitate is obtained. This precipitate is then dried to obtain V. FeCN -VHCF sample.

4. The method according to claim 1, characterized in that, When solution B is added dropwise to solution A, every 4 g of vanadium pentoxide (V2O5) corresponds to 0.6 g of potassium ferricyanide (K3Fe(CN)6).

5. The method according to claim 1, characterized in that, In step 3, V FeCN Preparation of VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material: Step 1, V FeCN -Preparation of VHCF positive electrode: V FeCN A mixture of VHCF positive electrode active material, acetylene black, and polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1 was prepared to obtain a mixed powder. The mixed powder was then dispersed in N-methylpyrrolidone (NMP) and stirred to produce a uniform VHCF. FeCN -VHCF positive electrode slurry was prepared by uniformly coating one side of a Nafion proton exchange membrane with the obtained slurry; subsequently, the Nafion proton exchange membrane with the slurry was placed under vacuum and dried overnight at 60°C to obtain VHCF. FeCN -VHCF positive electrode plate; The second step involves using a composite Pt / C anode catalyst. Pt / C and PVDF were mixed in an 8:2 ratio to obtain a mixed powder; these powders were then dispersed in N-methylpyrrolidone (NMP) and stirred to produce a homogeneous Pt / C negative electrode slurry; the Pt / C negative electrode slurry was coated onto the other side of a Nafion proton exchange membrane and then dried to obtain V. FeCN -VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material; In step (4), V FeCN -VHCF || Nafion proton exchange membrane || Pt / C catalyst assembly of solid hydrogen gas-energy cell; The casing is a commercial air button battery casing, conforming to the specifications of positive electrode casing, carbon paper, and V. FeCN The button cell is assembled in the following order: VHCF, Nafion proton exchange membrane, Pt / C catalyst integrated membrane, carbon paper, gasket, spring sheet, and negative electrode shell, and then compacted.

6. The method according to claim 5, characterized in that, in, V FeCN - The loading of VHCF positive electrode active material on each positive electrode sheet is 1.5-2 mg / 2.0096 cm⁻¹. 2 The Pt / C loading on each electrode is approximately 2-3 mg / 2.0096 cm⁻¹. 2 .

7. The method according to claim 5, characterized in that, Selecting DuPont Nafion proton exchange membrane material, V FeCN - A VHCF positive electrode slurry was loaded onto one side of a Nafion proton exchange membrane and dried at 60°C. After drying, a Pt / C negative electrode slurry was loaded onto the other side of the Nafion proton exchange membrane and dried at 60°C to obtain VHCF. FeCN -VHCF positive electrode || Nafion proton exchange membrane || Pt / C negative electrode catalyst composite material; Among them, V FeCN - The loading of VHCF active material on each electrode is 1.5-2 mg / 2.0096 cm⁻¹. 2 The catalyst Pt / C loading on each electrode is approximately 2-3 mg / 2.0096 cm⁻¹. 2 .

8. A high-capacity, low-temperature vanadium-based rechargeable hydrogen gas ion battery based on a Nafion proton exchange membrane, prepared according to any one of claims 1-7.

9. The application of the all-solid-state high-capacity low-temperature vanadium-based rechargeable hydrogen gas electron battery based on the Nafion proton exchange membrane integrated according to any one of claims 1-7, for use at low temperature 0°C.

10. The application of the all-solid-state high-capacity low-temperature vanadium-based rechargeable hydrogen gas electron battery based on the Nafion proton exchange membrane integrated according to any one of claims 1-7, using a rate of 2.5C-50C.

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