A stable strong anti-corrosion three-dimensional structure lead grid coupling nanosolid electrolyte interfacial material and its preparation method and application

Abstract

This invention relates to a robust and corrosion-resistant three-dimensional lead grid coupled with a nano-solid electrolyte interphase material, its preparation method, and its application. The invention employs a simple and scalable constant current electro-etching method to form a three-dimensional structure on the lead grid surface while simultaneously generating a uniform and stable nano-solid electrolyte interphase in situ on the surface of the structure. The combination of the three-dimensional lead grid structure and the in-situ grown solid electrolyte interphase effectively overcomes the problems of lead grid corrosion and active material shedding in lead-acid batteries. The two work synergistically to extend the cycle stability of the battery, providing a new strategy for the development of lead-acid batteries.

Description

Technical Field

[0001] This invention relates to a robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interphase material, its preparation method, and its application, belonging to the field of lead-acid battery technology. Background Technology

[0002] In the process of low-carbon transformation by replacing traditional fossil fuels with new energy sources, there is an urgent need for safe, reliable, and economical electrochemical energy storage. Lead-acid batteries, with their low cost, high safety, mature recycling system, and low-temperature adaptability, have become the mainstream choice in military tanks, traditional automobiles, electric bicycles, and UPS systems. In 2024, the market size of China's lead-acid battery industry exceeded 160 billion yuan, a year-on-year increase of 3.9%, and it is considered one of the most reliable energy storage technologies.

[0003] In lead-acid batteries, current and ion conduction during charging and discharging primarily rely on the lead grid, which plays a crucial role in the battery's charge acceptance, discharge performance, and cycle life. However, corrosion failure of the positive lead grid is one of the core issues leading to shortened battery life. Shorter battery life increases the cost of battery replacement and lead material recycling. Furthermore, due to the replacement of lead-acid batteries with lithium batteries, the market share of lead-acid batteries in the new energy vehicle sector has been gradually shrinking in recent years. Therefore, technological innovation and improvement are urgently needed to enhance the corrosion resistance of the lead grid and thereby improve the competitiveness of lead-acid battery products.

[0004] To address these issues, strategies such as alloying, the construction of three-dimensional lead grids, and the construction of artificial protective layers have been proposed. Among these, the construction of three-dimensional lead grids and artificial protective layers are considered crucial strategies for effectively improving the corrosion resistance of lead grids. Constructing three-dimensional lead grids for lead-acid batteries can effectively increase the specific surface area, reduce the current density on the grid surface, and release internal stress, promoting the bonding of active materials with the grid. Constructing artificial protective layers for lead-acid battery grids can block direct contact between the electrolyte and electrodes, reducing the corrosion rate. However, even with a simple three-dimensional lead grid, direct contact between the electrolyte and electrodes still exists, failing to fundamentally inhibit corrosion. Furthermore, the construction of artificial protective layers often suffers from inhomogeneity and instability, and may even break or detach due to their inability to adapt to changes in ion volume. In addition, existing methods for constructing three-dimensional lead grids and artificial protective layers suffer from drawbacks such as process complexity, high manufacturing costs, and environmental unfriendliness.

[0005] For example, patent document CN222483408U discloses a novel reinforced and stable lead grid for batteries. This lead grid effectively increases the contact area between the active material and the lead grid through the combination of horizontal and vertical reinforcing ribs, limiting grooves, through holes, and positioning grooves, thereby effectively enhancing the stability of the connection between the active material and the lead grid. Although it reduces the possibility of the lead grid detaching from the interface of the positive electrode material, the manufacturing process is complex and cannot fundamentally inhibit lead grid corrosion. Patent document CN108987678A discloses a lead-acid battery electrode containing a lead-tin / graphene composite coating and its preparation method. This method uses electrodeposition technology to prepare a lead grid with a lead-tin / graphene composite coating. It utilizes the idea of ​​forming an artificial protective layer in situ, overcoming the problem of easy detachment of traditional artificial protective layers. However, the two-dimensional artificial protective layer has problems such as large thickness, insufficient mechanical properties, and inability to release the stress on the lead grid surface during charging and discharging in a timely manner, leading to cracking. Its long-term corrosion resistance remains to be considered.

[0006] Therefore, developing a "two birds with one stone" strategy—a three-dimensional structure that can increase the specific surface area of ​​the lead grid in contact with the active material and release internal stress, and a three-dimensional lead grid coupled with a highly stable artificial interface protective layer that can isolate the lead grid from direct contact with the electrolyte—is of great significance for improving the competitiveness of lead-acid battery products. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interphase material, its preparation method, and its application.

[0008] This invention achieves a stable and corrosion-resistant three-dimensional lead grid coupled with a nano-solid electrolyte interphase by forming a three-dimensional structure on the surface of the lead grid through constant current electro-etching. When used in lead-acid battery lead grids, it not only increases corrosion resistance but also releases internal stress, significantly improves the bonding between the lead grid and the positive electrode material, homogenizes the electric field / ion concentration, and promotes uniform charging and discharging at the battery plate interface, providing a new strategy for the development of lead-acid battery energy storage systems.

[0009] Terminology Explanation:

[0010] In this invention, room temperature has a meaning known in the art, referring to 25±5 °C.

[0011] The technical solution of the present invention is as follows:

[0012] In a first aspect, the present invention provides a method for in-situ generating a robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interface phase.

[0013] A method for in-situ generation of a robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interface phase includes the following steps:

[0014] (1) Add anion donor material to sulfuric acid solution to obtain electro-etching solution;

[0015] (2) The lead grid is pretreated, and the pretreated lead grid, Ag / AgCl electrode and carbon rod counter electrode are assembled into a three-electrode system. The system is placed in the electro-etching solution of step (1) and a constant current is applied for electro-etching. After that, the lead grid is taken out, cleaned and dried, and a stable and highly corrosion-resistant three-dimensional structure lead grid coupled nano solid electrolyte interphase material is obtained on the lead grid.

[0016] According to a preferred embodiment of the present invention, in step (1), the concentration of the sulfuric acid solution is 1-3 mol / L, the anion donor material is sodium sulfide, and the concentration of the anion donor material in the electro-etching solution is 0.05-0.1 mol / L.

[0017] According to a preferred embodiment of the present invention, in step (2), the pretreatment of the lead grid is specifically as follows: ultrasonic cleaning with deionized water and anhydrous ethanol for 5-10 minutes to remove inorganic and organic impurities on the surface of the lead grid, and drying in a vacuum oven at 50-70°C for 4-8 hours.

[0018] According to a preferred embodiment of the present invention, in step (2), the electro-etching is performed by etching the pretreated lead gate surface with electrons, specifically by applying current to the three-electrode system using a Princeton electrochemical workstation to cause a reaction on the lead gate surface: Pb-2e - =Pb 2+ This process etches the lead grid surface to form a three-dimensional structure. During the etching process, lead ions combine with sulfur ions or sulfate ions in the electro-etching solution to generate a solid electrolyte interphase material at the electrode / solution interface.

[0019] According to a preferred embodiment of the present invention, in step (2), the current density of the electro-etching is 50-70 mA cm⁻¹. -2 The total capacity of the electro-etching is 4-6 mAh cm⁻¹. -2 .

[0020] In a second aspect, the present invention provides a robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interphase material.

[0021] A robust and highly corrosion-resistant three-dimensional lead-grid coupled nano-solid electrolyte interphase material was prepared using the method described above.

[0022] A third aspect of this invention provides the application of the aforementioned robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interphase material.

[0023] The aforementioned robust and corrosion-resistant three-dimensional lead grid coupled with nano-solid electrolyte interphase material is used as a lead grid in lead-acid batteries.

[0024] The working principle of the in-situ generation of three-dimensional lead grid coupled nano-solid electrolyte interphase material in this invention is as follows:

[0025] When the lead grid comes into contact with the electrolyte, an electrical double layer forms on the electrode / electrolyte surface, specifically including a Helmholtz layer and a diffusion layer. The Helmholtz layer further comprises an inner Helmholtz layer and an outer Helmholtz layer. The inner Helmholtz layer consists of specifically adsorbed anions and polar water molecules, while the outer Helmholtz layer is generally composed of solvated ions. The diffusion layer is a region where various anions, cations, and water molecules are randomly distributed. When a bias current is applied, the lead grid loses electrons, and the surface is etched to form a three-dimensional structure. Simultaneously, under the influence of the electric field, more anions are attracted to the lead grid side. The lead ions stripped of electrons combine with anions (such as sulfide or sulfate ions) and form solid electrolyte nuclei in situ on the etched three-dimensional structure. Subsequently, a film is gradually formed during the etching process, eventually forming a solid electrolyte interface phase on the three-dimensional lead grid structure.

[0026] A method for preparing lead-acid batteries based on three-dimensional lead grid coupled nano-solid electrolyte interphase materials includes the following steps:

[0027] 1) Preparation of lead-acid battery electrode: The robust and corrosion-resistant three-dimensional lead grid coupled nano solid electrolyte interphase material prepared above was successively subjected to surface filling with lead paste and curing and drying treatment to obtain a lead-acid battery electrode containing a three-dimensional lead grid coupled nano solid electrolyte interphase.

[0028] 2) Assembly of lead-acid batteries: The lead-acid battery electrodes containing a three-dimensional lead grid coupled with a nano solid electrolyte interphase are assembled in a stacked manner. The assembled lead-acid battery is placed in a sulfuric acid solution for static activation.

[0029] According to a preferred embodiment of the present invention, in step 1), the lead paste components are: (PbO)4(Pb(SO4), PbO and Pb, and the weight ratio of (PbO)4(Pb(SO4):PbO:Pb is 70:29:1.

[0030] According to a preferred embodiment of the present invention, in step 1), the temperature of the lead paste application is 40-50°C and the thickness of the application is 1-5 mm.

[0031] According to a preferred embodiment of the present invention, in step 1), the drying and curing temperature is 70-75°C, the relative humidity is >90%, the curing time is 20-30h, and then the product is dried at 60-65°C for 35-40h.

[0032] According to a preferred embodiment of the present invention, in step 2), three positive plates and four negative plates are stacked together, the battery model is L2400, and the theoretical capacity is 30 Ah.

[0033] According to a preferred embodiment of the present invention, in step 2), the concentration of the sulfuric acid solution is 1-5 mol / L.

[0034] Technical features and advantages of the present invention:

[0035] 1. The method of this invention forms a three-dimensional structure on the lead grid surface while simultaneously generating a uniform and stable nano-solid electrolyte interphase in situ on the surface of the structure. On the one hand, the three-dimensional structure increases the specific surface area of ​​the lead grid, reduces internal stress and current density, and improves the bonding between the lead grid and the positive electrode material. However, the simple three-dimensional lead grid is still in direct contact with the electrolyte, which cannot fundamentally delay the corrosion problem. The nano-solid electrolyte interphase grown in situ in this invention isolates the three-dimensional structure from the electrolyte, fundamentally delaying the reduction in battery life caused by lead grid corrosion. On the other hand, traditional two-dimensional solid electrolyte interphases are prone to detachment or breakage during the continuous insertion / extraction of positive electrode active materials. The solid electrolyte interphase generated by this invention can effectively reduce corrosion on the lead grid surface, and the construction of the three-dimensional structure can effectively release internal stress and enhance the stability of the solid electrolyte interphase. This two-pronged strategy of combining the three-dimensional lead grid structure with the in-situ grown solid electrolyte interphase effectively overcomes the problems of lead grid corrosion and active material detachment in lead-acid batteries. The two work synergistically to extend the cycle stability of the battery, providing a new strategy for the development of lead-acid batteries.

[0036] 2. This invention uses electrons as an etchant. Compared with other etching methods such as acid etching, alkaline etching, and other gas phase and solid phase etching methods, the etchant of this invention uses green and pollution-free electrons, and the etchant utilization rate is as high as 100%. Moreover, as a mild etchant, electrons can effectively control the degree of etching, making the three-dimensional etched structure on the lead grid surface more uniform, oriented, and controllable.

[0037] 3. The electro-etching solution system of the present invention is green and recyclable. By adding sulfuric acid and anion donor materials to the electro-etching solution after electro-etching, the electro-etching solution can be reused. Attached Figure Description

[0038] Figure 1 The XRD patterns of the three-dimensional lead grid coupled nano-solid electrolyte interphase material prepared in Example 1 and the untreated lead grid in Comparative Example 1 are shown.

[0039] Figure 2The figures show the EDX spectra of the three-dimensional lead-grid coupled nano-solid electrolyte interface material prepared in Example 1 and the untreated lead grid in Comparative Example 1. The upper part of the figures shows the elemental distribution map and elemental content table of the untreated lead grid interface, while the lower part shows the elemental distribution map, elemental energy level map, and elemental content table of the three-dimensional lead-grid coupled nano-solid electrolyte interface material prepared in Example 1.

[0040] Figure 3 The images show scanning electron microscope (SEM) images of the three-dimensional lead-grid coupled nano-solid electrolyte interphase material prepared in Example 1 and the untreated lead grid of Comparative Example 1. The upper half of the images shows SEM images of the untreated lead grid of Comparative Example 1 at different magnifications, and the lower half shows SEM images of the three-dimensional lead-grid coupled nano-solid electrolyte interphase material prepared in Example 1 at different magnifications.

[0041] Figure 4 This is a photograph of a lead-acid battery assembled using the three-dimensional lead grid coupled nano-solid electrolyte interphase material prepared in Example 1.

[0042] Figure 5 The voltage drop of the lead-acid batteries assembled for Example 1 and Comparative Example 1 after discharging for 30 s at -18 °C and 330 A.

[0043] Figure 6 Voltage-capacity curves of the lead-acid batteries assembled in Example 1 and Comparative Example 1 under three charge-discharge conditions at 25 °C and 3 A.

[0044] Figure 7 The charge acceptance capability of the lead-acid batteries assembled in Example 1 and Comparative Example 1 at 14.4V. Detailed Implementation

[0045] To make the above-mentioned mechanisms, features, and advantages of the present invention more readily understood, the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. It should be noted that the specific embodiments described are explanations of the present invention and not limitations thereof.

[0046] Unless otherwise specified, all reagents and instruments used are commercially available products. Experiments not specifying particular conditions were conducted under standard conditions. All other experimental examples obtained by those skilled in the art based on the embodiments of this invention without inventive effort are within the scope of protection of this invention.

[0047] In this embodiment, the pretreatment method for the lead grid is as follows: the inorganic and organic impurities on the surface of the lead grid are removed by ultrasonic cleaning with deionized water and anhydrous ethanol for 5-10 minutes, and then dried in a vacuum oven at 60°C for 6 hours.

[0048] Example 1

[0049] A method for in-situ generation of a robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interface phase, comprising the following steps:

[0050] (1) At room temperature, prepare 3 L of a mixed solution containing 2 mol / L sulfuric acid and 0.05 mol / L sodium sulfide using a volumetric flask to obtain an electroetching solution.

[0051] (2) The lead grid was ultrasonically cleaned with deionized water and anhydrous ethanol for 6 min to remove inorganic and organic impurities from its surface. It was then dried in a vacuum oven at 60℃ for 6 h to obtain a pretreated lead grid. The pretreated lead grid, Ag / AgCl electrode, and carbon rod counter electrode were assembled into a three-electrode system and placed in an electro-etching apparatus containing an electro-etching solution. A 50 mA cm⁻¹ etching solution was applied using a Princeton electrochemical workstation. -2 Constant current electro-etching was performed, and the total etching capacity was 5 mAh cm⁻¹. -2 .

[0052] (3) The lead grid was removed by electro-etching and then cleaned with deionized water and anhydrous ethanol to remove the soluble ions and impurities remaining on the surface. After that, it was vacuum dried at 60°C for 6 hours to obtain a three-dimensional lead grid coupled in-situ nano solid electrolyte interphase material, denoted as 3D Pb@SEI, also known as S-treated grid.

[0053] The XRD pattern of the 3D Pb@SEI material prepared in this embodiment is as follows: Figure 1 As shown in the figure, the lead gate surface after electro-etching treatment shows an increase of multiple characteristic peaks at 20-30° and 40-50° compared to the untreated lead gate. These characteristic peaks confirm the formation of SEI, while the change in the intensity of the main peak confirms the formation of the three-dimensional structure. The EDX spectrum of the 3D Pb@SEI material prepared in this embodiment is shown in the figure. Figure 2 As shown in the figure, a uniformly distributed SEI was formed on the lead gate surface after electro-etching, and the elemental composition spectrum showed an increase in the proportion of sulfur and oxygen, with the Pb, O, and S ratio being approximately 1:2:1. This indicates that in addition to lead sulfate formation, lead sulfide also forms within the SEI. The scanning electron microscope image of the 3D Pb@SEI material prepared in this embodiment is shown in the figure. Figure 3 As shown. Electron microscopy results indicate that the lead grid interface forms a uniform three-dimensional structure, and the surface is uniformly covered by SEI.

[0054] Preparation of lead-acid batteries:

[0055] 1) At 45°C, lead paste was applied to the surface of the 3D Pb@SEI prepared above. The lead paste composition was (PbO)4(Pb(SO4), PbO and Pb, and the weight ratio of (PbO)4(Pb(SO4):PbO:Pb was 70:29:1. The coating thickness was 2 mm. After coating, the electrode was cured at 72°C and relative humidity >90% for 25 h, and then dried at 62°C for 35 h to obtain a lead-acid battery electrode containing a three-dimensional lead grid coupled nano solid electrolyte interphase.

[0056] 2) Using the lead-acid battery electrodes prepared in step 2), assemble a lead-acid battery in a stacked manner. A picture of the assembled lead-acid battery is shown below. Figure 4 As shown, the assembled lead-acid battery was placed in a 3 mol / L sulfuric acid solution for static activation.

[0057] Comparative Example 1

[0058] Commercially available lead grids are recorded as untreated grids.

[0059] The XRD pattern of the unprocessed grid in Comparative Example 1 is as follows: Figure 1 As shown. The EDX spectrum of the unprocessed grid is as follows. Figure 2 As shown, the main component of the lead gate surface without the electro-etching treatment of Example 1 is lead. The scanning electron microscope image of the untreated gate is shown below. Figure 3 As shown, the surface of the lead grid without electro-etching is covered with uneven scratches.

[0060] Preparation of lead-acid batteries:

[0061] 1) At 45℃, lead paste was applied to the surface of a commercially available lead grid. The lead paste composition was (PbO)4(Pb(SO4), PbO and Pb, with a weight ratio of (PbO)4(Pb(SO4):PbO:Pb of 70:29:1. The coating thickness was 2mm. After coating, the surface was cured at 72℃ and relative humidity >90% for 25h, and then dried at 62℃ for 35h to obtain an unmodified lead grid electrode for a lead-acid battery.

[0062] 2) Using the lead-acid battery electrodes prepared in step 2), assemble a lead-acid battery in a stacked manner, and place the assembled lead-acid battery in a 3 mol / L sulfuric acid solution for static activation.

[0063] Experimental example:

[0064] 1. After allowing the batteries to stand for 48 hours, the CCA (cold start current) and internal resistance of the two lead-acid batteries assembled in Example 1 and Comparative Example 1 were measured. The results showed that the lead-acid battery in Example 1 had a higher CCA value (435 A vs. 405 A) and lower internal resistance (7.19 mΩ vs. 7.99 mΩ). This means that the treated lead grid, through its three-dimensional structure coupling with the nano-solid electrolyte interface, increases the utilization rate of the positive electrode material, thereby increasing the released charge. Furthermore, the lower internal resistance implies better conductivity and stronger corrosion resistance.

[0065] 2. The voltage drop of the two lead-acid batteries assembled in Example 1 and Comparative Example 1 was measured under constant current (330 A) discharge conditions at low temperature (-18 °C) for 30 s. The results are as follows: Figure 5 As shown, the lead-acid battery of Example 1 has a lower voltage drop within 30 seconds compared to the lead-acid battery of Comparative Example 1 (0.829 V vs. 1.226 V), indicating that the modified lead grid of Example 1 can effectively reduce the corrosion of the plates.

[0066] 3. The charge-discharge capacity of the two lead-acid batteries assembled in Example 1 and Comparative Example 1 was measured in the first three cycles at room temperature. The results are as follows: Figure 6 As shown, the lead-acid battery of Example 1 exhibits higher capacity, higher energy density, and more uniform charge-discharge in the first three charge-discharge cycles compared to the lead-acid battery of Comparative Example 1. This indicates that the modified lead grid of Example 1, with its three-dimensional structure, increases the bonding between the lead paste active material and the lead grid, thereby improving the utilization rate of the lead paste active material; simultaneously, the nano-solid electrolyte interfacial phase can increase the corrosion resistance of the lead grid, facilitating stable charge-discharge.

[0067] 4. The charge acceptance of the two lead-acid batteries assembled in Example 1 and Comparative Example 1 was measured under a 14.4 V condition, and the results are as follows: Figure 7 As shown, the lead-acid battery of Example 1 has a smaller charging current (5.081 A vs. 5.781 A) under constant voltage conditions compared to Comparative Example 1. While a larger charging current allows for faster charging, it also leads to internal heating. Excessive temperature can accelerate the instability of internal chemical reactions and may even damage the battery. A gentler charging current reduces the risk of overheating, minimizes lead grid corrosion, and increases battery life and safety, further demonstrating the performance improvement of modified lead grids for lead-acid batteries.

[0068] The improved performance is attributed to the synergistic effect of the in-situ generated three-dimensional lead grid coupled with a nano-solid electrolyte interfacial phase, achieving a synergistic effect between the structure and the protective layer. On one hand, the three-dimensional structure formed on the lead grid increases the specific surface area, thereby increasing the contact area between the active material and the lead grid and improving the utilization rate of the active material in the battery lead paste. On the other hand, the in-situ grown solid electrolyte interfacial phase isolates the three-dimensional structure from the electrolyte, fundamentally compensating for the corrosion problems faced by the three-dimensional lead grid. Simultaneously, the formation of the three-dimensional structure effectively releases internal stress, overcoming the defects of traditional two-dimensional solid electrolyte interfacial phases, such as easy detachment or fracture, and enhancing the stability of the solid electrolyte interfacial phase. The three-dimensional lead grid and the nano-solid electrolyte interfacial phase complement each other, synergistically improving the performance of lead-acid batteries.

Claims

1. A method for in-situ generation of a robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interface phase, comprising the following steps: (1) Add anion donor material to sulfuric acid solution to obtain an electro-etching solution; (2) The lead grid is pretreated, and the pretreated lead grid, Ag / AgCl electrode and carbon rod counter electrode are assembled into a three-electrode system. The system is placed in the electro-etching solution of step (1) and a constant current is applied for electro-etching. After that, the lead grid is taken out, cleaned and dried, and a stable and highly corrosion-resistant three-dimensional structure lead grid coupled nano solid electrolyte interphase material is obtained on the lead grid.

2. The method according to claim 1, characterized in that, In step (1), the concentration of the sulfuric acid solution is 1-3 mol / L, and the anion donor material is sodium sulfide; the concentration of the anion donor material in the electro-etching solution is 0.05-0.1 mol / L.

3. The method according to claim 1, characterized in that, In step (2), the pretreatment of the lead grid is as follows: ultrasonic cleaning with deionized water and anhydrous ethanol for 5-10 minutes to remove inorganic and organic impurities on the surface of the lead grid, and drying in a vacuum oven at 50-70℃ for 4-8 hours.

4. The method according to claim 1, characterized in that, In step (2), the electroetching is to use electrons to etch the surface of the pretreated lead grid, specifically: using a Princeton electrochemical workstation to apply current to a three-electrode system to make the surface of the lead grid react: Pb-2e - = Pb 2+ , so that the surface of the lead grid is etched to form a three-dimensional structure, and in the etching process, lead ions combine with sulfur ions or sulfate ions in the electroetching solution at the electrode / solution interface to generate a solid electrolyte interphase material.

5. The method according to claim 1, characterized in that, In step (2), the current density of the electro-etching is 50-70 mA cm⁻¹. -2 The total capacity of the electro-etching is 4-6 mAh cm⁻¹. -2 .

6. A robust and highly corrosion-resistant three-dimensional lead grid coupled nano-solid electrolyte interphase material, prepared by the preparation method described in claims 1-5.

7. The application of the robust and highly corrosion-resistant three-dimensional structure lead grid coupled with nano-solid electrolyte interphase material as described in claim 6, used as a lead grid in lead-acid batteries.

8. A method for preparing a lead-acid battery based on a three-dimensional lead grid coupled nano-solid electrolyte interphase material, comprising the following steps: 1) Preparation of lead-acid battery electrode: The robust and corrosion-resistant three-dimensional lead grid coupled nano solid electrolyte interphase material obtained in claim 1 is subjected to surface filling with lead paste and curing and drying treatment to obtain a lead-acid battery electrode containing a three-dimensional lead grid coupled nano solid electrolyte interphase. 2) Assembly of lead-acid batteries: The lead-acid battery electrodes containing a three-dimensional lead grid coupled with a nano-solid electrolyte interphase are assembled in a stacked manner. The assembled lead-acid battery is placed in a sulfuric acid solution for static activation.

9. The method according to claim 8, characterized in that, In step 1), the lead paste components are: (PbO)4(Pb(SO4), PbO and Pb, with a weight ratio of (PbO)4(Pb(SO4):PbO:Pb of 70:29:

1. The lead paste application temperature is 40-50℃, the application thickness is 1-5mm, the drying and curing temperature is 70-75℃, the relative humidity is >90%, the curing time is 20-30h, and then it is dried at 60-65℃ for 35-40h.

10. The method according to claim 8, characterized in that, In step 2), three positive plates and four negative plates are stacked together. The battery model is L2400, the theoretical capacity is 30 Ah, and the sulfuric acid solution concentration is 1-5 mol / L.

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