Lead-oxygen-silicon solid-state storage battery and preparation method thereof

Abstract

The invention belongs to the technical field of new material preparation, and discloses a lead-oxygen-silicon solid-state storage battery and a preparation method thereof. The lead-oxygen-silicon solid-state storage battery comprises a positive electrode layer, an electrolyte layer and a negative electrode layer, the positive electrode layer takes a beta-PbO2 crystal form as a main active substance and is loaded on a lead-calcium alloy plate grid to form a honeycomb porous structure with high porosity; the electrolyte layer takes a silicon-oxygen skeleton as a matrix, nano PbSO4 particles are embedded into pores of the silicon-oxygen skeleton, and gaps of the skeleton are filled with sulfonated PEO chains to form a continuous flexible ion channel; and the negative electrode layer takes porous sponge lead as a main active substance and is attached to the lead-calcium alloy plate grid. According to the solid sulfuric acid-free system disclosed by the invention, the problems of acid mist pollution and waste liquid treatment of the lead-acid battery are avoided, and the environmental friendliness is remarkably improved. The lead-based battery can be widely applied to application scenes such as electric automobiles, unmanned aerial vehicles, photovoltaic power, wind power and communication base station standby power supplies, and the lead-based battery technology is promoted to be upgraded to the high-safety, long-service-life and green directions.

Description

Technical Field

[0001] This application belongs to the field of new material technologies, and particularly relates to a lead-oxygen-silicon solid-state battery and a preparation method thereof. Background Art

[0002] As the most mature secondary battery technology, lead-acid batteries are widely used in energy storage systems and transportation fields due to their low cost and high reliability. However, this system has the following core defects: The liquid sulfuric acid electrolyte has strong corrosiveness, and it is easy to leak when the battery is damaged, causing environmental pollution and human burns; the active substances are prone to irreversible sulfation during charge and discharge, resulting in capacity attenuation. The cycle life of conventional products is only 300 - 500 times; the low-temperature performance is insufficient. When the temperature drops below -20°C, the viscosity of the electrolyte increases sharply, and the ion mobility decreases significantly, leading to a sudden decrease in capacity; there is a lack of an efficient Pb 2 + transmission channel, resulting in poor rate performance.

[0003] The gas-phase silica gel battery developed to address the above problems effectively improves the risk of electrolyte leakage and enhances some electrochemical properties by dispersing nanoscale SiO2 in sulfuric acid to form a gel electrolyte. However, this technology still faces multiple bottlenecks: 1. Insufficient mechanical stability. The colloid is prone to generate microcracks under the volume change of the electrode and temperature fluctuations, resulting in an increase in the contact resistance at the electrode / electrolyte interface. After 100 cycles, the internal resistance increase is 40% - 60% higher than that of liquid batteries; 2. Complex preparation process. The addition ratio of gas-phase SiO2 needs to be precisely controlled at 5% - 8%, and the high-speed shear dispersion process increases the energy consumption by 30%; 3. The problem of material homogeneity. Nanoparticles are prone to agglomeration under the action of van der Waals forces, resulting in local concentration gradients in the electrolyte, leading to a decrease in the consistency of battery packs, seriously restricting its large-scale application in large energy storage systems. Summary of the Invention

[0004] Object of the Invention: Aiming at the pain points that it is difficult to simultaneously improve safety, energy density, and cycle life in the prior art, the present invention provides a lead-oxygen-silicon solid-state battery and a preparation method thereof. By innovatively adopting a lead-oxygen-silicon composite solid electrolyte system, on the premise of completely eliminating liquid components, double breakthroughs in high ionic conductivity and electrode compatibility are achieved, while simplifying the preparation process, providing a new technical path for high-safety and long-life energy storage systems.

[0005] Technical solution: The present invention provides a lead-oxygen-silicon solid-state battery, and the lead-oxygen-silicon solid-state battery includes a positive electrode layer, an electrolyte layer, and a negative electrode layer. The positive electrode layer uses β-PbO2 crystal form as the main active material, which is loaded on a lead-calcium alloy grid to form a honeycomb-like porous structure with a high porosity (>80%). The electrolyte layer uses a silicon-oxygen skeleton as the matrix, and nano-PbSO4 particles are embedded in its pores, and the skeleton gaps are filled with sulfonated PEO chains to form continuous flexible ion channels. The negative electrode layer uses porous sponge lead with a porosity of ≥60% and a pore diameter of 50-200 nm as the main active material, which is attached to a lead-calcium alloy grid.

[0006] Specifically, the electrolyte layer is obtained by in-situ constructing a silicon-oxygen skeleton through sol preparation, lead salt doping, and gel cross-linking, and then realizing ion channel functionalization through sulfonated PEO penetration and thermal-initiated polymerization to obtain the solid electrolyte layer.

[0007] More specifically, the electrolyte layer is obtained by the following method: In the first stage, in-situ construct a silicon-oxygen skeleton: Using tetraethyl orthosilicate (TEOS) and aminopropyltriethoxysilane (APTES) as precursors, a hydrolysis and polycondensation reaction occurs under the catalysis of nitric acid to form a three-dimensional -Si-O-Si- network structure. Nano-PbSO4 is uniformly embedded in the skeleton pores through ultrasonic dispersion to enhance the mechanical strength of the electrolyte and provide ion transport sites. In the second stage, ion channel functionalization: Sulfonated polyethylene oxide (PEO) fills the gaps in the silicon-oxygen skeleton, and cross-linking is initiated by ammonium persulfate (APS) to form continuous ion channels. The Pb in PbSO4 2+ forms a coordination bond with the sulfonate group (SO3 - ) to promote ion dissociation and improve conductivity.

[0008] More specifically, the electrolyte layer is obtained by the following method: Mix TEOS, APTES, and absolute ethanol, and then add HNO3 to catalyze hydrolysis, and stir at 40-45 °C to form a transparent sol. Add nano-PbSO4 to the above sol and disperse it ultrasonically to form a uniform suspension. Inject the above suspension into a mold and dry it under vacuum to form a shape; Immerse the above-formed skeleton in a sulfonated PEO solution and infiltrate it under a vacuum state to fill the gaps in the silicon-oxygen skeleton, and initiate cross-linking of PEO chains by APS at 75-85 °C to form continuous ion transport channels, that is, the solid electrolyte layer is obtained.

[0009] Specifically, the calcium content of the lead-calcium alloy grid in the positive electrode layer is 0.03-0.06%, and the calcium content of the lead-calcium alloy grid in the negative electrode layer is 0.06-0.10%.

[0010] The present invention also provides a preparation method for the electrolyte of the above lead-oxygen-silicon solid-state battery, including steps such as the preparation of the electrolyte layer, the preparation of the positive and negative electrode layers, and lamination and encapsulation.

[0011] Specifically, step 1, preparation of the electrolyte layer:

[0012] In-situ construction of the silicon-oxygen skeleton: Mix TEOS, APTES, and absolute ethanol, then add HNO3 for catalytic hydrolysis, stir at 40 - 45 °C for 4 - 6 hours to form a transparent sol. Add nano-PbSO4 to the above sol, disperse ultrasonically to form a uniform suspension, inject the above suspension into a mold, and vacuum dry at 60 - 65 °C for 10 - 12 hours to form a shape. TEOS and APTES condense to form a -Si-O-Si- three-dimensional network, and PbSO4 is embedded in the pores of the skeleton as an ion source (Pb 2+ and SO4 2- ). Through the subsequent formation of coordination bonds with the sulfonic acid groups (-SO3 - ) of sulfonated PEO, ion dissociation is promoted.

[0013] Functionalization of ion channels: Immerse the above-formed skeleton in a sulfonated PEO solution, infiltrate under vacuum for 2 - 3 hours to fill the gaps in the silicon-oxygen skeleton. Initiate APS cross-linking of PEO chains at 75 - 85 °C to form a continuous ion transport channel, obtaining a solid electrolyte layer. Ammonium persulfate (APS) decomposes at high temperature (75 - 85 °C) to generate free radicals, initiating cross-linking between PEO chains to form a three-dimensional polymer network, enhancing the mechanical strength of the electrolyte. Acetonitrile solvent promotes the disentanglement of PEO chains, and a 5% sulfonation degree can provide a -SO 3- group density of 0.3 - 0.5 mmol / g. Vacuum infiltration ensures a pore filling rate > 95%. Ammonium persulfate thermally decomposes at 75 °C to generate free radicals, initiating cross-linking between PEO chains to form a three-dimensional network. The best ionic conductivity is achieved when the cross-linking density is about 10 - 15%.

[0014] Specifically, step 2, preparation of the positive and negative electrode layers:

[0015] Take a lead-calcium alloy grid (calcium content is 0.03 - 0.06%) and coat it with PbO2 paste, with a coating thickness of 1.5 - 2.0 mm, and cure at 45 - 55 °C and humidity > 95% for 70 - 80 hours to obtain a positive electrode layer. In a high-temperature and high-humidity environment, it promotes the formation of a β-PbO2 (porous, highly active) composite structure between PbO2 and the grid, improving the discharge capacity.

[0016] Take a lead-calcium alloy grid (calcium content is 0.06 - 0.10%) and coat it with porous sponge lead, with a coating thickness of 1.0 - 1.2 mm, and dry and cure to obtain a negative electrode layer. The porous sponge lead coating enlarges the reaction surface area.

[0017] After the above electrodes are cured, they are subjected to plasma treatment for 5-6 minutes to form a 2-3 nm microporous oxide layer on the surface, reducing the interfacial impedance. The surface is cleaned and a microporous layer is formed to reduce the interfacial resistance and improve the charge transfer efficiency.

[0018] Specifically, in step 3, lamination and encapsulation:

[0019] The positive electrode, solid electrolyte (thickness 200-300 μm), and negative electrode are stacked in sequence, hot-pressed into shape under a pressure of 5 MPa and a temperature of 80 °C. An ABS plastic shell is used, and it is sealed by laser welding and an explosion-proof valve is installed. The solid electrolyte (glass transition temperature is about 60 °C) is softened to make it closely fit with the positive and negative electrodes, eliminating the interfacial air gap and reducing the interfacial impedance.

[0020] Specifically, in step 1, TEOS, APTES, and absolute ethanol are configured and mixed at a molar ratio of 1:0.3-0.5:4-5.

[0021] Specifically, in step 1, the concentration of HNO3 is 0.1-0.2 M.

[0022] Specifically, in step 1, the amount of nano-PbSO4 added is 8-10% of the mass of the aforementioned sol.

[0023] Specifically, in step 1, for the ultrasonic dispersion, the power is 300±1 W and the time is 30-40 min. The 300 W high-power ultrasound breaks the agglomeration of PbSO4, making it evenly embedded in the pores of the framework and avoiding uneven local ion concentration.

[0024] Furthermore, in step 1, the composition of the sulfonated PEO solution is as follows: sulfonated poly(ethylene oxide) (sulfonated PEO) 6-7 wt%, ammonium persulfate (APS) 0.8-1 wt%, and the solvent acetonitrile as the balance. The sulfonated PEO in this composition accounts for 6-7% of the total mass of the solution to ensure that the polymer chains are fully disentangled in acetonitrile. The sulfonated PEO used is a modified poly(ethylene oxide) with a sulfonic acid group substitution degree of 5% (that is, 5 sulfonic acid groups are grafted onto every 100 ethylene oxide units), and the molecular weight range is 500,000-800,000 daltons. This sulfonation degree can provide a -SO3 - group density of 0.3-0.5 mmol / g for forming dynamic coordination bonds with Pb 2+

[0025] Furthermore, in step 2, for the plasma treatment: 100 W radio frequency plasma (Ar / O2 = 4:1 mixed gas) generates high-energy particles to bombard the surface for 5-6 minutes, removing organic impurities and forming a 2-3 nm microporous oxide layer (porosity 15-20%), reducing the interfacial charge transfer impedance.

[0026] ​Beneficial effects: The present invention uses a "silicon-oxygen framework - lead ion channel" composite gel electrolyte, and constructs a three-dimensional ion transport network through an in-situ sol-gel crosslinking + nano-lead salt doping technology, solving the problems of high interfacial impedance and low lead ion mobility of traditional solid electrolytes.

[0027] The solid electrolyte obtained by the method of the present invention has stable low-temperature viscosity, unrestricted ion migration, and can maintain charge and discharge performance in a low-temperature environment. The electrode interface treated by oxygen-containing plasma is combined with a thermocompression interlocking structure to inhibit the growth of lead dendrites and interfacial peeling, and improve the capacity retention rate after multiple cycles.

[0028] The solid sulfuric acid-free system of the present invention avoids the problems of acid mist pollution and waste liquid treatment of lead-acid batteries, and significantly improves environmental friendliness. It can be widely applied to application scenarios such as electric vehicles, drones, photovoltaics, wind power, and backup power supplies for communication base stations, promoting the upgrading of lead-based battery technology towards high safety, long life, and greenness. Description of the Drawings

[0029] Figure 1 It is the capacity curve of the battery obtained in Example 1 at different temperatures.

[0030] Figure 2 It is the discharge depth and cycle life curve of the battery obtained in Example 1. Detailed Embodiments

[0031] The technical solutions of the present application will be described in detail below through examples, but the protection scope of the present application is not limited to the described examples. The parts described in the present invention are all in parts by mass.

[0032] Example 1

[0033] 1. In-situ construction of the silicon-oxygen framework: TEOS, APTES, and absolute ethanol were configured and mixed at a molar ratio of 1:0.3:4, and then 0.1M HNO3 was added for catalytic hydrolysis, and stirred at 40°C for 4 hours to form a transparent sol. Nano PbSO4 was added to the above sol, and the addition amount was 10% of the mass of the above sol, and ultrasonic dispersion was carried out with a power of 300W for 30 min to form a uniform suspension. It was injected into a mold and vacuum dried at 60°C for 12 hours to form.

[0034] Functionalization of ion channels: The above-formed framework was impregnated in a sulfonated PEO solution (6 wt% sulfonated polyethylene oxide, 1 wt% ammonium persulfate, and the balance being solvent acetonitrile), and permeated under a vacuum state for 2 hours to fill the gaps of the silicon-oxygen framework. APS was used to crosslink the PEO chains at 80°C to form a continuous ion transport channel, and a solid electrolyte layer was obtained.

[0035] 2. Preparation of positive and negative electrode plates

[0036] Take a lead-calcium alloy grid (calcium 0.05%) and coat it with PbO2 paste. The coating thickness is 1.5 - 2.0 mm, and it is cured for 72 hours in an environment of 45 - 55°C and humidity > 95% to obtain the positive electrode layer.

[0037] Take a lead-calcium alloy grid (calcium 0.08%) and coat it with porous sponge lead. The coating thickness is 1.0 - 1.2 mm, which is used as the negative electrode plate, dried and cured to obtain the negative electrode layer.

[0038] After the above electrodes are cured, they are subjected to plasma treatment. 100W radio frequency plasma (Ar / O2 = 4:1 mixed gas) generates high-energy particles to bombard the surface for 6 minutes, and a 2 - 3 nm microporous oxide layer is formed on the surface.

[0039] 3. Laminated packaging:

[0040] Stack the positive electrode, solid electrolyte membrane (thickness 200 - 300 μm), and negative electrode in sequence, and hot press them into shape under a pressure of 5 MPa and a temperature of 80°C. Use an ABS plastic shell, laser weld and seal it, and install an explosion-proof valve.

[0041] The capacity curves of the battery obtained in Example 1 at different temperatures are as Figure 1 shown; the discharge depth and cycle life curves are as Figure 2 shown.

[0042] Example 2

[0043] 1. In-situ construction of the silicon-oxygen framework: Configure and mix TEOS, APTES, and absolute ethanol according to a molar ratio of 1:0.3:4, then add 0.1M HNO3 for catalytic hydrolysis, and stir at 40°C for 4 hours to form a transparent sol. Add nano PbSO4 to the above sol, and the addition amount is 10% of the mass of the above sol. Ultrasonic disperse it with a power of 300W for 30 min to form a uniform suspension. Inject it into a mold and vacuum dry it at 60°C for 10 hours to form a shape.

[0044] Ion channel functionalization: Immerse the above-formed framework in a sulfonated PEO solution (sulfonated polyethylene oxide 6wt%, ammonium persulfate 0.8wt%, and the balance is solvent acetonitrile), and infiltrate it under vacuum for 2 hours to fill the gaps of the silicon-oxygen framework. Initiate the cross-linking of PEO chains by APS at 75°C to form a continuous ion transport channel, and obtain the solid electrolyte layer.

[0045] 2. Preparation of positive and negative electrode plates

[0046] Take a lead-calcium alloy grid (calcium 0.05%) and coat it with PbO2 paste. The coating thickness is 1.5 mm, and it is cured for 70 hours in an environment of 45°C and humidity > 95% to obtain the positive electrode layer.

[0047] Take a lead-calcium alloy grid (calcium 0.08%) and coat it with porous sponge lead. The coating thickness is 1.0 mm to serve as the negative electrode plate, and then dry and cure it to obtain the negative electrode layer.

[0048] After the above electrodes are cured, they are subjected to plasma treatment. 100 W radio frequency plasma (Ar / O2 = 4:1 mixed gas) generates high-energy particles to bombard the surface for 6 minutes, and a 2-3 nm microporous oxide layer is formed on the surface.

[0049] 3. Stacking and encapsulation:

[0050] Stack the positive electrode, solid electrolyte membrane (thickness 200 - 300 μm), and negative electrode in sequence, and hot press them into shape under a pressure of 5 MPa and a temperature of 80°C. Use an ABS plastic shell, seal it by laser welding and install an explosion-proof valve.

[0051] Example 3

[0052] 1. In-situ construction of the silicon-oxygen framework: Configure and mix TEOS, APTES, and absolute ethanol according to a molar ratio of 1:0.3:4, then add 0.1 M HNO3 for catalytic hydrolysis, stir at 45°C for 6 hours to form a transparent sol. Add nano-PbSO4 to the above sol, and the addition amount is 10% of the mass of the above sol. Ultrasonic disperse it at a power of 300 W for 30 min to form a uniform suspension. Inject it into a mold and vacuum dry it at 65°C for 12 hours to form a shape.

[0053] Functionalization of ion channels: Immerse the above-formed framework in a sulfonated PEO solution (sulfonated polyethylene oxide 7 wt%, ammonium persulfate 1 wt%, and the balance is solvent acetonitrile), and infiltrate it under a vacuum state for 3 hours to fill the gaps of the silicon-oxygen framework. Initiate the cross-linking of PEO chains by APS at 85°C to form a continuous ion transport channel and obtain the solid electrolyte layer.

[0054] 2. Preparation of positive and negative electrode plates

[0055] Take a lead-calcium alloy grid (calcium 0.05%) and coat it with PbO2 paste. The coating thickness is 2.0 mm, and cure it in an environment of 55°C and humidity > 95% for 80 hours to obtain the positive electrode layer.

[0056] Take a lead-calcium alloy grid (calcium 0.08%) and coat it with porous sponge lead. The coating thickness is 1.2 mm to serve as the negative electrode plate, and then dry and cure it to obtain the negative electrode layer.

[0057] After the above electrodes are cured, they are subjected to plasma treatment. 100 W radio frequency plasma (Ar / O2 = 4:1 mixed gas) generates high-energy particles to bombard the surface for 6 minutes, and a 2-3 nm microporous oxide layer is formed on the surface.

[0058] 3. Stacking and encapsulation:

[0059] Stack the positive electrode, solid electrolyte membrane (thickness 200 - 300 μm), and negative electrode in sequence, and perform hot pressing to form, with a pressure of 5 MPa and a temperature of 80 °C. Use an ABS plastic shell, seal it by laser welding and install an explosion-proof valve.

[0060] The capacities and cycling performances of the batteries obtained in Examples 1 - 3 are shown in the following table

[0061]

[0062] It can be seen that the technical solution provided by the present invention is superior to traditional lead-acid batteries in terms of energy density, cycle life, and low-temperature capacity retention.

[0063] Comparative Example 1

[0064] The basic steps of Comparative Example 1 are substantially the same as those of Example 1, except that the sulfonated PEO solution is: 6 wt% of sulfonated polyethylene oxide, 0.5 wt% of ammonium persulfate, and the balance is solvent acetonitrile.

[0065] Comparative Example 2

[0066] The basic steps of Comparative Example 2 are substantially the same as those of Example 1, except that the sulfonated PEO solution is: 18 wt% of sulfonated polyethylene oxide, 1 wt% of ammonium persulfate, and the balance is solvent acetonitrile.

[0067] Comparative Example 3

[0068] The basic steps of Comparative Example 3 are substantially the same as those of Example 1, except that the sulfonated PEO solution is: 6 wt% of sulfonated polyethylene oxide, and the balance is solvent acetonitrile.

[0069] The data comparison of Example 1 and Comparative Examples 1 - 3 is shown in the following table

[0070]

[0071] It can be seen from the data that in Example 1, which has the best effect, through the -SO3 - group of sulfonated PEO dissociating from the coordination with Pb 2+ the activation energy of ion migration is reduced, and the ionic conductivity can be effectively improved.

[0072] The above are only the preferred embodiments of the present application and are not used to limit the present application.

Claims

1. A lead-oxygen-silicon solid-state storage battery, characterized in that, The described lead-oxygen-silicon solid-state battery includes a positive electrode layer, an electrolyte layer, and a negative electrode layer; the positive electrode layer uses β-PbO₂ crystal form as the main active material, which is loaded on a lead-calcium alloy grid to form a honeycomb-like porous structure with a high porosity; the electrolyte layer uses a silicon-oxygen skeleton as the matrix, and nano-PbSO₄ particles are embedded in its pores, and the skeleton gaps are filled with sulfonated PEO chains to form a continuous flexible ion channel; the negative electrode layer uses porous sponge lead as the main active material and is attached to the lead-calcium alloy grid.

2. The lead-oxygen-silicon solid-state storage battery according to claim 1, wherein The calcium content of the lead-calcium alloy grid in the positive electrode layer is 0.03-0.06%, and the calcium content of the lead-calcium alloy grid in the negative electrode layer is 0.06-0.10%.

3. The lead-oxygen-silicon solid-state storage battery according to claim 1, characterized in that, The electrolyte layer is obtained by the following method: In-situ construction of a silicon-oxygen skeleton: Mix TEOS, APTES, and absolute ethanol, then add HNO₃ for catalytic hydrolysis, and stir at 40-45 °C to form a transparent sol; add nano-PbSO₄ to the above sol and disperse it by ultrasonic waves to form a uniform suspension; inject the above suspension into a mold and dry it under vacuum to form a shape; immerse the above-formed skeleton in a sulfonated PEO solution and permeate it under a vacuum state to fill the gaps in the silicon-oxygen skeleton, and initiate APS cross-linking of PEO chains at 75-85 °C to form a continuous ion transport channel, that is, the electrolyte layer is obtained.

4. The preparation method of the lead-oxygen-silicon solid-state storage battery according to claim 1, characterized in that, It includes the following steps: Step 1, preparation of the electrolyte layer: In-situ construction of a silicon-oxygen skeleton: Mix TEOS, APTES, and absolute ethanol, then add HNO₃ for catalytic hydrolysis, and stir at 40-45 °C for 4-6 hours to form a transparent sol. Add nano-PbSO₄ to the above sol and disperse it by ultrasonic waves to form a uniform suspension. Inject the above suspension into a mold and dry it under vacuum at 60-65 °C for 10-12 hours to form a shape. TEOS and APTES are polycondensed to form a -Si-O-Si- three-dimensional network, and PbSO₄ is embedded in the skeleton pores; Functionalization of the ion channel: Immerse the above-formed skeleton in a sulfonated PEO solution with acetonitrile as the solvent and permeate it under a vacuum state for 2-3 hours to fill the gaps in the silicon-oxygen skeleton; initiate APS cross-linking of PEO chains at 75-85 °C to form a continuous ion transport channel, that is, the solid electrolyte layer is obtained; Step 2, preparation of the positive and negative electrode layers: Take a lead-calcium alloy grid and coat it with PbO₂ paste with a coating thickness of 1.5-2.0 mm, and cure it at 45-55 °C and a humidity > 95% environment for 70-80 hours to obtain the positive electrode layer; take a lead-calcium alloy grid and coat it with porous sponge lead with a coating thickness of 1.0-1.2 mm, dry and cure it to obtain the negative electrode layer; perform plasma treatment after curing; Step 3, stacking and encapsulation: Stack the positive electrode, the solid electrolyte, and the negative electrode in sequence, and hot-press them into a shape with a pressure of 5 MPa and a temperature of 80 °C. Use an ABS plastic shell, seal it by laser welding and install an explosion-proof valve.

5. The preparation method of the lead-oxygen-silicon solid-state storage battery according to claim 4, characterized in that, In Step 1, the TEOS, APTES, and absolute ethanol are configured and mixed according to a molar ratio of 1:0.3-0.5:4-5.

6. The preparation method of the lead-oxygen-silicon solid-state storage battery according to claim 4, wherein In Step 1, the concentration of the HNO₃ is 0.1-0.2 M.

7. The preparation method of the lead-oxygen-silicon solid-state storage battery according to claim 4, wherein, In step 1, the addition amount of the nano-PbSO4 is 8-10% of the mass of the aforementioned sol.

8. The preparation method of the lead-oxygen-silicon solid-state storage battery according to claim 4, characterized in that, In step 1, for the ultrasonic dispersion, the power is 300±1W and the time is 30-40 min.

9. The preparation method of the lead-oxygen-silicon solid-state storage battery according to claim 4, characterized in that, In step 1, the composition of the sulfonated PEO solution is: 5 wt% of sulfonated polyethylene oxide, 1 wt% of ammonium persulfate, and the balance is the solvent acetonitrile.

10. The preparation method of the lead-oxygen-silicon solid-state storage battery according to claim 4, wherein In step 2, for the plasma treatment: use 100W radio frequency plasma to drive an argon-oxygen mixture to generate high-energy particles to bombard the surface for 5-6 minutes.

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