Hydrogen solid-state secondary battery with manganese-based positive electrode

Abstract

The invention relates to a hydrogen solid secondary battery with a manganese-based positive electrode, which comprises a MnHCF positive electrode, a Pt / C negative electrode and a solid electrolyte, the solid electrolyte comprises an acidic electrolyte and clay, and the MnHCF positive electrode can reversibly deintercalate protons; the hydrogen solid-state secondary battery with the manganese-based positive electrode provided by the invention adopts the MnHCF positive electrode material, the positive electrode material can reversibly deintercalate protons and has relatively high specific capacity, and the hydrogen solid-state secondary battery with the manganese-based positive electrode prepared by the process disclosed by the invention can still keep stable specific capacity and coulombic efficiency close to 100% after being circulated for 600 times under 0.5 Ag # imgabs0 # current density; compared with the prior art, the preparation method has the advantages that the energy density of the battery is improved, the service life of the battery is prolonged, the problem of capacity fading caused by irreversible reaction of the material is solved, and the preparation method has a good application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of battery energy storage, and particularly to a hydrogen solid-state secondary battery with a manganese-based positive electrode. Background Art

[0002] With the continuous growth of energy demand and the promotion of sustainable development, aqueous secondary batteries have become one of the most promising energy storage technology directions due to their high safety, high power density, and environmental friendliness with water-based electrolytes. However, existing aqueous battery technologies, such as lead-acid batteries, nickel-metal hydride batteries, and flow batteries, still face problems such as environmental pollution, resource dependence, and limited cycle life, which restrict their further popularization and application. Since 2018, Wei Chen et al. have reported a series of new aqueous secondary batteries - hydrogen batteries. Due to the use of H+ as the carrier (the smallest ionic radius), it has the fastest conduction rate in the electrolyte, and thus the battery has excellent rate performance. The hydrogen negative electrode can be matched with different positive electrodes, such as the hydrogen negative electrode can be matched with an insertion / extraction type positive electrode.

[0003] In the actual implementation process, there are still some problems:

[0004] In the prior art, nickel-metal hydride (Ni-H2) batteries, Prussian blue (PBA)-H2 batteries, and lithium manganese oxide-hydrogen (LMO-H2) batteries have been developed in alkaline, acidic, and neutral electrolytes respectively. Among them, nickel hydroxide in the positive electrode of the Ni-H2 battery has a low abundance in the earth's crust, and both the positive electrode material PBA in the PBA-H2 battery and lithium manganese oxide in the LMO-H2 battery have low specific capacities, thus limiting the large-scale application of the above batteries. Summary of the Invention

[0005] (I) Technical Problems to be Solved

[0006] In order to solve the above problems of the prior art, the present invention provides a hydrogen solid-state secondary battery with a manganese-based positive electrode to solve the problem of low specific capacity of the existing positive electrode materials.

[0007] (II) Technical Solutions

[0008] To achieve the above object, the main technical solutions adopted by the present invention are as follows:

[0009] A hydrogen solid-state secondary battery with a manganese-based positive electrode, comprising:

[0010] A MnHCF positive electrode, a Pt / C negative electrode, and a solid electrolyte. The solid electrolyte includes an acidic electrolyte and clay. Among them, the MnHCF positive electrode can reversibly insert and extract protons;

[0011] The acidic electrolyte and the clay are configured in a mass ratio of 0.5 to 1.5: 1 to 5, and Pt in the Pt / C negative electrode accounts for 15% to 50% of the total mass of the Pt / C negative electrode.

[0012] The preparation method of the MnHCF positive electrode includes the following steps:

[0013] Potassium ferricyanide, a manganese source, and water are mixed and reacted to obtain the MnHCF positive electrode. Preferably, the mass-volume ratio of potassium ferricyanide, the manganese source, and water is 1200 to 1300 mg: 500 to 700 mg: 50 to 170 mL.

[0014] The manganese source is selected from one or more of MnSO4, MnNO3, and MnCl2.

[0015] The acidic electrolyte is any one of H3PO4 and H2SO4, and its volume concentration is 10% to 85%.

[0016] The clay includes one or more of Mg2H2(SiO3)3·3.0H2O, H2Al2O6Si·1.19H2O, and H4Al2O9Si2·0.32H2O.

[0017] The positive electrode plate is made by mixing the positive electrode active material MnHCF, the conductive agent acetylene black, and the binder PTFE in a mass ratio of 7:2:1 and rolling the film. The current collector is a titanium mesh, and the active material loading is 0.26 mg·cm , and the diameter of the electrode plate is 19 mm.

[0018] The Pt / C negative electrode plate is made by mixing the Pt / C catalyst powder and the binder PTFE in a mass ratio of 8:2 and rolling the film, where the Pt loading is 1 mg·cm , and the current collector is a titanium mesh, and the diameter of the negative electrode plate is 19 mm.

[0019] The solid electrolyte membrane is further prepared by mixing bentonite and a 63% concentration of H3PO4 acidic electrolyte in a mass ratio of 1:1 to form a gel.

[0020] During the first charging process of the battery, protons are inserted into the positive electrode material MnHCF, and the Pt / C negative electrode catalyzes the generation of hydrogen from protons;

[0021] During the discharging process, hydrogen reacts on the surface of the Pt / C negative electrode catalyst to generate protons, which migrate to the positive electrode material through the Grotthuss mechanism.

[0022] A preparation method of a manganese-based positive electrode hydrogen solid-state secondary battery, applied to the hydrogen solid-state secondary battery according to any one of claims 1-9, includes the following steps:

[0023] S1: Prepare the MnHCF cathode material;

[0024] S2: Prepare the cathode electrode sheet by mixing MnHCF, acetylene black, and PTFE in a mass ratio of 7:2:1 to form the electrode sheet;

[0025] S3: Prepare the Pt / C anode electrode sheet by mixing the Pt / C powder and PTFE in a mass ratio of 8:2 to form the electrode sheet;

[0026] S4: Prepare the solid electrolyte membrane by mixing bentonite and 63% concentrated H3PO4 acidic electrolyte in a mass ratio of 1:1 to form a gel membrane;

[0027] S5: Assemble the cathode electrode sheet, solid electrolyte membrane, and Pt / C anode electrode sheet in sequence to form a battery. (III) Beneficial effects

[0028] The beneficial effects of the present invention are as follows:

[0029] 1. The hydrogen solid-state secondary battery with a manganese-based cathode of the present invention uses the MnHCF cathode material. This cathode material can reversibly intercalate and deintercalate protons and has a high specific capacity. The hydrogen solid-state secondary battery with a manganese-based cathode prepared by the process of the present invention can still maintain a stable specific capacity and a Coulomb efficiency close to 100% after 600 cycles at a current density of 0.5 A / g, demonstrating excellent cycle stability and reversibility. Compared with the prior art, the present invention not only improves the energy density and service life of the battery but also reduces the capacity attenuation problem caused by irreversible reactions of the materials, showing good application prospects. 2. The hydrogen solid-state secondary battery with a manganese-based cathode of the present invention uses a solid electrolyte membrane prepared by compounding an acidic electrolyte and clay, which improves the proton conductivity and the overall structural stability of the battery. At the same time, the materials used are rich in resources, low in cost, the preparation method is simple, environmentally friendly and pollution-free, and it is easy to be prepared on a large scale. In addition, the Pt / C anode catalyst loading amount used is reasonable, which not only ensures the catalytic activity of the hydrogen reaction but also effectively controls the cost, providing a feasible path for constructing a new type of high-performance and low-cost hydrogen solid-state secondary battery system.

[0030] 2. The hydrogen solid-state secondary battery with a manganese-based cathode of the present invention uses a solid electrolyte membrane prepared by compounding an acidic electrolyte and clay, which improves the proton conductivity and the overall structural stability of the battery. At the same time, the materials used are rich in resources, low in cost, the preparation method is simple, environmentally friendly and pollution-free, and it is easy to be prepared on a large scale. In addition, the Pt / C anode catalyst loading amount used is reasonable, which not only ensures the catalytic activity of the hydrogen reaction but also effectively controls the cost, providing a feasible path for constructing a new type of high-performance and low-cost hydrogen solid-state secondary battery system. Brief description of the drawings

[0031] Figure 1 is a schematic structural diagram of the present invention;

[0032] Figure 2 is a test chart of the cycle performance and Coulomb efficiency of the present invention;

[0033] Figure 3 is a test chart of the present invention;

[0034] Figure 4 is a schematic diagram of the specific capacity and cycle efficiency of the present invention. Detailed implementation manners

[0035] For better explaining the present invention for easier understanding, the present invention will be described in detail below in conjunction with the accompanying drawings through specific implementation manners.

[0036] Please refer to Figures 1 to 4 As shown, a hydrogen solid-state secondary battery with a manganese-based positive electrode of the present invention includes:

[0037] A MnHCF positive electrode, a Pt / C negative electrode, and a solid electrolyte. The solid electrolyte includes an acidic electrolyte and clay. Among them, the MnHCF positive electrode can reversibly intercalate and deintercalate protons;

[0038] The acidic electrolyte and the clay are configured according to a mass ratio of 0.5 to 1.5:1 to 5, and Pt in the Pt / C negative electrode accounts for 15% to 50% of the total mass of the Pt / C negative electrode.

[0039] Optionally, the preparation method of the MnHCF positive electrode includes the following steps:

[0040] Potassium ferricyanide, a manganese source, and water are mixed and reacted to obtain a MnHCF positive electrode. Preferably, the mass-volume ratio of potassium ferricyanide, the manganese source, and water is 1200 to 1300 mg:500 to 700 mg:50 to 170 mL. In the actual implementation process, potassium ferricyanide, the manganese source, and water are fully mixed according to the specified ratio. By controlling the reaction temperature and time, potassium ferricyanide acts as an oxidant to react uniformly with the manganese source to form a MnHCF positive electrode material with a complete crystal structure and appropriate particle size. This method has mild reaction conditions, a simple and efficient preparation process, is conducive to improving the product purity and material consistency, and thus ensures that the hydrogen solid-state secondary battery with the prepared manganese-based positive electrode has excellent specific capacity and cycle stability.

[0041] Optionally, the manganese source is selected from one or more of MnSO4, MnNO3, and MnCl2. In the actual implementation process, the manganese source can be selected from MnSO4, MnNO3, and MnCl2, and can be used alone or in combination according to different reaction requirements. This material selection flexibility helps to regulate the reaction rate of the synthesis reaction and the crystallization quality of the final product, optimize the electrochemical performance of the MnHCF positive electrode, and improve the overall energy density and cycle life of the battery.

[0042] Optionally, the acidic electrolyte is either H3PO4 or H2SO4, and its volume concentration is 10% - 85%. During the actual implementation process, phosphoric acid (H3PO4) or sulfuric acid (H2SO4) is selected as the acidic electrolyte according to the electrolyte requirements, and its volume concentration is controlled within the range of 10% to 85%. By adjusting the acidity intensity, the proton conduction performance and the interfacial stability of the battery are optimized. The acidic electrolyte is easy to configure and can effectively promote the proton migration inside the battery, improve the charge and discharge reaction rate, thereby endowing the hydrogen solid-state secondary battery with a manganese-based cathode with excellent rate performance and low-temperature adaptability.

[0043] Optionally, the clay includes one or more of Mg2H2(SiO3)3·3.0H2O, H2Al2O6Si·1.19H2O, and H4Al2O9Si2·0.32H2O. During the actual implementation process, one of the above clay materials or a combination thereof is selected. By forming a composite solid electrolyte membrane with the acidic electrolyte, the selected clay material has good ion exchangeability and structural stability, which can enhance the mechanical strength and corrosion resistance of the solid electrolyte membrane, and at the same time provide an effective proton conduction channel, significantly improving the cycle stability and durability of the hydrogen solid-state secondary battery with a manganese-based cathode.

[0044] Optionally, the positive electrode plate is made by mixing the positive electrode active material MnHCF, the conductive agent acetylene black, and the binder PTFE in a mass ratio of 7:2:1 and rolling the film. The current collector is a titanium mesh, and the active material loading is 1.258 g·cm -2 , and the diameter of the electrode plate is 19 mm. During the actual implementation process, the positive electrode active material, the conductive agent, and the binder are uniformly mixed to form a slurry, and a positive electrode plate with uniform thickness and controllable loading is made through the film rolling process. Using a titanium mesh as the current collector can improve the overall conductivity and corrosion resistance of the electrode plate, ensure the rapid transmission of electrons, and thus improve the charge and discharge efficiency and cycle life of the battery.

[0045] Optionally, the Pt / C negative electrode plate is made by mixing the Pt / C catalyst powder and the binder PTFE in a mass ratio of 8:2 and rolling the film, where the Pt loading is 1 mg·cm -2 , and the current collector is a titanium mesh, and the diameter of the negative electrode plate is 19 mm. During the actual implementation process, the Pt / C catalyst and the PTFE binder are uniformly mixed and rolled into shape according to the specified ratio to obtain the negative electrode plate. The Pt / C catalyst provides excellent hydrogen catalytic activity, while the titanium mesh current collector ensures the mechanical strength and conductivity of the electrode plate. The overall structural design is reasonable, making the negative electrode reaction interface stable, promoting the proton reaction kinetics, and significantly improving the discharge efficiency and rate performance of the hydrogen solid-state secondary battery with a manganese-based cathode.

[0046] Optionally, the solid-state electrolyte membrane is further prepared by mixing bentonite with 63% concentrated H3PO4 acidic electrolyte in a mass ratio of 1:1 to form a gel. In the actual implementation process, bentonite and 63% concentrated H3PO4 are fully mixed to form a gel-like material, which is made into a uniform and dense solid-state electrolyte membrane after appropriate treatment. This membrane has excellent proton conductivity and mechanical flexibility, can effectively inhibit the occurrence of side reactions inside the battery, and improve the overall stability and safety of the hydrogen solid-state secondary battery with a manganese-based positive electrode.

[0047] Optionally, during the first charging process of the battery, protons are embedded in the positive electrode material MnHCF, and the negative electrode Pt / C catalyzes the generation of hydrogen from protons.

[0048] During the discharging process, hydrogen reacts on the surface of the Pt / C negative electrode catalyst to generate protons, which migrate to the positive electrode material through the Grotthuss mechanism. In the actual implementation process, the positive electrode material MnHCF undergoes a proton insertion reaction, and at the same time, the negative electrode catalyzes the generation of hydrogen from protons; during the discharging stage, the generated hydrogen is oxidized to protons on the surface of the negative electrode, and the protons rapidly migrate to the positive electrode through the Grotthuss mechanism in the solid-state electrolyte and are re-embedded. This cyclic process has high reversibility, effectively improves the energy utilization efficiency and cycle life of the hydrogen solid-state secondary battery with a manganese-based positive electrode, reduces energy loss at the same time, and ensures that the battery can maintain excellent performance even at high rates and low temperatures.

[0049] Optionally, a method for preparing a hydrogen solid-state secondary battery with a manganese-based positive electrode, applied to the hydrogen solid-state secondary battery according to any one of claims 1-9, includes the following steps:

[0050] S1: Prepare the MnHCF positive electrode material;

[0051] S2: Prepare the positive electrode plate, and mix MnHCF, acetylene black, and PTFE in a mass ratio of 7:2:1 to make the plate;

[0052] S3: Prepare the Pt / C negative electrode plate, and mix the Pt / C powder and PTFE in a mass ratio of 8:2 to make the plate;

[0053] S4: Prepare the solid-state electrolyte membrane, and mix bentonite and 63% concentrated H3PO4 acidic electrolyte in a mass ratio of 1:1 to form a gel membrane;

[0054] S5: Assemble the positive electrode plate, the solid-state electrolyte membrane, and the Pt / C negative electrode plate in sequence to form a battery.

[0055] The working process of the hydrogen solid-state secondary battery with a manganese-based positive electrode of the present invention includes material preparation, plate production, battery assembly, and charge-discharge mechanism. The specific working principle is as follows:

[0056] First, prepare the MnHCF cathode material. Add 4 g of MnO2 to 75 mL of HCl solution and stir evenly. Take 9.4 mL of the obtained solution and dilute it to 50 mL, marked as solution A. Add 3.6 mmol of K3[Fe(CN)6] to 50 mL of deionized water to form a green solution, marked as solution B. Under continuous stirring, slowly add solution B to solution A and react at 60 °C for 9 hours. After the reaction, wash, centrifuge, and dry to obtain the MnHCF cathode material. Then, prepare the electrode and the solid electrolyte membrane. The preparation method of the positive electrode is as follows: Mix the positive electrode active material MnHCF, the conductive agent acetylene black, and the binder PTFE in a mass ratio of 7:2:1 to form a slurry, and make a positive electrode through the film rolling process. The current collector is a titanium mesh, and the active material loading is 1.258 mg·cm , the electrode diameter is 19 mm. The preparation method of the Pt / C negative electrode is as follows: Mix the Pt / C catalyst powder and the binder PTFE in a mass ratio of 8:2 and roll the film to make a negative electrode. The negative current collector is also a titanium mesh, and the Pt loading is 1 mg·cm , the negative electrode diameter is 19 mm, and Pt accounts for 40% of the total mass of the Pt / C negative electrode. The production method of the solid electrolyte membrane is as follows: Mix bentonite H2Al2O6Si·1.19H2O and acidic electrolyte H3PO4 in a mass ratio of 1:1 to make a gel-like solid electrolyte membrane. Finally, assemble the hydrogen solid-state secondary battery with a manganese-based cathode. The assembly order of the battery is as follows: First, place the positive electrode, then lay the solid electrolyte membrane, and finally install the Pt / C negative electrode to form a complete laminated structure. The charge and discharge mechanism of the hydrogen solid-state secondary battery with a manganese-based cathode assembled in this example is as follows: During the first charging process, the proton insertion reaction occurs in the cathode material MnHCF, and at the same time, the protons in the solid electrolyte membrane react to generate hydrogen under the catalysis of the Pt / C negative electrode catalyst; during the discharge process, the hydrogen on the surface of the negative electrode is catalytically oxidized to protons, and the protons migrate to the solid electrolyte and are rapidly conducted through the Grotthuss mechanism, and further de-embed and insert into the MnHCF cathode material to form H-MnHCF. During the second and subsequent charge and discharge cycles, the cathode mainly experiences the reversible insertion (discharge process) and extraction (charging process) of protons in the MnHCF material, and the negative electrode correspondingly undergoes the oxidation and reduction reactions of protons. The entire cycle process is stable and reversible, thus realizing the efficient energy storage and release of the hydrogen solid-state secondary battery with a manganese-based cathode.

[0057] To verify the cycle stability of the hydrogen solid-state secondary battery with a manganese-based cathode described in the present invention, the assembled battery is charged and discharged at 0.5 A·g Long-term cyclic charge-discharge tests were carried out at a current density. By measuring the specific capacity and Coulombic efficiency of the battery at different cycle numbers, the capacity retention rate and reaction reversibility of the battery were evaluated. The test results are shown in Table 1.

[0058] Table 1:

[0059] Cycle Number Specific Capacity (mAh·g#timg#) Coulombic Efficiency (%) 1 114.45 98.5 100 118.74 99.1 200 115.08 99.3 300 111.29 99.2 400 109.61 99.1 500 105.74 99.0 600 103.86 98.9

[0060] As shown in Table 1 and the appendix Figure 2 where Specific capacity is the specific capacity, which refers to the amount of electric charge stored or released by the electrode material per unit mass (or volume) during the charge-discharge process, usually in milliamperes per gram (mAh g ), a key indicator for measuring the performance of the battery electrode material. The higher the value, the stronger the energy storage ability;

[0061] Coulombic efficiency is the Coulombic efficiency, which is the ratio of the amount of electric charge released during discharge to the amount of electric charge injected during charging, usually expressed as a percentage (%), reflecting the reversibility of the battery. A high efficiency (close to 100%) indicates a small energy loss during the charge-discharge process;

[0062] Cycle number is the number of cycles. A complete charge-discharge process of the battery is called a cycle, which is the abscissa in the figure and is used to observe the trend of battery performance changing with the number of uses;

[0063] At a current density of 0.5 A g the hydrogen solid-state secondary battery with a manganese-based positive electrode exhibits excellent cycle stability. The initial specific capacity is about 146.5 mAh·g and remains at about 117.4 mAh·g after 600 cycles . The capacity retention rate is over 80%. At the same time, during the entire charge-discharge process, the Coulombic efficiency always remains above 98.5%, close to 100%, indicating a high reversibility of the battery reaction and good cycle stability, effectively verifying the superiority of the material system and structural configuration designed in the present invention.

[0064] Table 2:

[0065] Current Density (A·g#timg#) Specific Capacity (mAh·g#timg#) 0.5 106.3 1 107.8 2 94.1 3 71.8 5 42.2

[0066] As shown in Table 2 and Figure 3 where Specific capacity / mAh g is the specific capacity, the amount of electric charge stored by the electrode material per unit mass, measuring the energy storage ability of the battery. The abscissa in the figure represents the capacity performance at different current densities;

[0067] Current Density, A·g is the current density, which represents the magnitude of the current passing through per unit mass of the electrode material during charge and discharge. The unit is usually A·g (ampere / gram), that is, the current passing through per gram of the electrode material;

[0068] The hydrogen solid-state secondary battery with a manganese-based cathode exhibits good rate performance at different current densities. When the current density increases from 0.5 Ag to 5 Ag during the process, the specific capacity of the battery decreases from 106.3 mAh·g to 42.2 mAh·g , but still maintains a relatively high available capacity. Moreover, the voltage plateau of the charge-discharge curve is obvious, indicating that the proton transport channel is unobstructed and the polarization phenomenon is small. Even under high-rate discharge conditions, the battery still exhibits excellent kinetic characteristics and fast charge-discharge capabilities, further demonstrating the efficient proton insertion / extraction reaction characteristics of the material system of the present invention.

[0069] Table 3:

[0070] Cyclenumber Specific Capacity (mAhg#timg#) Efficiency (%) Current Density (Ag#timg#) Material 1 114.45 98 0.5 MnHCF 2 116.88 96 0.5 MnHCF ... ... ... ... ... 10 117.16 99 0.5 MnHCF 100 118.74 98 0.5 MnHCF 200 115.08 99 0.5 MnHCF ... ... ... ... ...

[0071] As shown in Table 3 and Figure 4 shown below, where Cyclenumber is the number of cycles,

[0072] The MnHCF material exhibits excellent electrochemical performance in the cycle test: at a current density of 0.5 Ag, its initial specific capacity is 114.45 mAh / g, and it still remains at 117.16 mAh / g after 10 cycles, corresponding to a capacity retention rate of 98%; after 100 cycles, it still remains at 118.74 mAh / g, with good cycle stability. It only slightly decreases to 3.66 mAh / g at the 200th cycle, and the efficiency is 99%. As Figure 3 shown, the MnHCF material exhibits stable charge-discharge platforms at different current densities, indicating its fast proton transport kinetics and low electrochemical polarization. Notably, the material can still maintain a relatively high specific capacity under the condition of doubling the current density, indicating that its crystal structure provides an efficient three-dimensional conduction channel for the insertion and extraction of protons. This characteristic makes it have important potential in the application of high-power solid-state batteries.

[0073] The basic principles, main features and advantages of the present invention have been shown and described above. All standard parts used in the present invention can be purchased from the market. The special-shaped parts can be customized according to the description in the specification and the drawings. The specific connection methods of each part all adopt conventional means such as bolts, rivets and welding which are mature in the prior art. The machines, parts and equipment all adopt conventional models in the prior art. In addition, the circuit connection adopts the conventional connection method in the prior art, which will not be elaborated here.

[0074] The above are only the embodiments of the present invention, and thus do not limit the patent scope of the present invention. All equivalent transformations made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in the relevant technical fields, are similarly included in the patent protection scope of the present invention.

Claims

1. A hydrogen solid-state secondary battery with a manganese-based positive electrode, characterized in that Comprising: An MnHCF positive electrode, a Pt / C negative electrode, and a solid electrolyte. The solid electrolyte includes an acidic electrolyte solution and clay. Among them, the MnHCF positive electrode can reversibly intercalate and deintercalate protons. The acidic electrolyte solution and the clay are configured according to a mass ratio of 0.5 - 1.5:1 - 5, and Pt in the Pt / C negative electrode accounts for 15% - 50% of the total mass of the Pt / C negative electrode.

2. The hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that, The preparation method of the MnHCF positive electrode includes the following steps: Potassium ferricyanide, a manganese source, and water are mixed and reacted to obtain the MnHCF positive electrode. Preferably, the mass - volume ratio of potassium ferricyanide, the manganese source, and water is 1200 - 1300 mg:500 - 700 mg:50 - 170 mL.

3. The hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 2, characterized in that, The manganese source is selected from one or more of MnSO4, MnNO3, and MnCl2.

4. The hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that The acidic electrolyte solution is either H3PO4 or H2SO4, and its volume concentration is 10% - 85%.

5. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that, The clay includes one or more of Mg2H2(SiO3)3·3.0H2O, H2Al2O6Si·1.19H2O, and H4Al2O9Si2·0.32H2O.

6. The hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that The positive electrode plate is made by mixing the positive active material MnHCF, the conductive agent acetylene black and the binder PTFE in a mass ratio of 7:2:1 and rolling the film. The current collector is a titanium mesh, and the active material loading is 0.26 mg·cm , and the diameter of the electrode plate is 19 mm.

7. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that, The Pt / C negative electrode plate is made by mixing Pt / C catalyst powder and binder PTFE in a mass ratio of 8:2 and rolling them into a film, where the Pt loading is 1 mg·cm , the current collector is a titanium mesh, and the diameter of the negative electrode plate is 19 mm.

8. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that The solid electrolyte membrane is further prepared by mixing bentonite and a 63% - concentration H3PO4 acidic electrolyte solution in a mass ratio of 1:1 to form a gel.

9. A hydrogen solid-state secondary battery with a manganese-based positive electrode according to claim 1, characterized in that, During the first charging process of the battery, protons are intercalated into the positive - electrode material MnHCF, and the negative - electrode Pt / C catalyzes the generation of hydrogen from protons. During the discharging process, hydrogen reacts on the surface of the Pt / C negative - electrode catalyst to generate protons, which migrate to the positive - electrode material through the Grotthuss mechanism.

10. A preparation method of a manganese-based positive hydrogen solid-state secondary battery, applied to the hydrogen solid-state secondary battery according to any one of claims 1-9, characterized in that, Including the following steps: S1: Prepare the MnHCF positive - electrode material; S2: Prepare the positive - electrode plate. Mix MnHCF, acetylene black, and PTFE in a mass ratio of 7:2:1 to make the plate. S3: Prepare the Pt / C negative - electrode plate. Mix the Pt / C powder and PTFE in a mass ratio of 8:2 to make the plate. S4: Prepare the solid electrolyte membrane. Mix bentonite and a 63% - concentration H3PO4 acidic electrolyte solution in a mass ratio of 1:1 to form a gel membrane. S5: Assemble the positive - electrode plate, the solid electrolyte membrane, and the Pt / C negative - electrode plate in sequence to form the battery.

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