A self-agitating water circulation liquid-rich lead-carbon battery

Abstract

The application relates to the field of lead-carbon batteries, in particular to a self-stirring water circulation rich-liquid lead-carbon battery, which comprises flat plate-shaped electrodes arranged in a closed battery box, the flat plate-shaped electrodes are arranged vertically to the bottom surface in the battery box, and plate carbon material is arranged above the flat plate-shaped electrodes in the battery box; the flat plate-shaped electrodes are supported by flat plate-shaped grids with through holes; carbon material is filled and coated on the lower part of a vertically arranged grid, negative active material is filled and coated on the grid above the carbon material to form a negative electrode; and positive active material is filled and coated on another grid to form a positive electrode.

Description

Technical Field

[0001] This invention relates to the field of lead-carbon batteries, and particularly to a technology for eliminating acid stratification in lead-carbon batteries with rich electrolyte. Background Technology

[0002] Lead-acid batteries have attracted much attention for their application in hybrid electric vehicles (HEVs) due to their low cost, high safety, and good low-temperature performance. However, HEVs require lead-acid batteries to operate at a high-rate partial state of charge (HRPSoC), which can significantly shorten battery cycle life due to accelerated negative electrode sulfation. Adding appropriate carbon materials to the negative electrode active material to construct lead-carbon batteries (LCBs) is one effective way to solve the negative electrode sulfation problem.

[0003] Lead-carbon batteries not only possess the same safety, low cost, and stability as traditional lead-acid batteries, but also exhibit long cycle life and high specific power, similar to supercapacitors. Adding porous carbon materials to the negative electrode plate can extend the cycle life under HRPSoC conditions. Carbon additives primarily function as capacitor buffers and conductive networks, thereby improving electrochemical kinetics. However, the introduction of carbon additives also introduces certain problems, such as increasing the hydrogen evolution rate during charging and reducing the contact between the sponge lead active material and the carbon material. Furthermore, the generated hydrogen bubbles cause carbon particles to separate from the electrode active material, leading to the destruction of the negative electrode plate's structural stability. Since lead has a high hydrogen evolution overpotential, combining Pb with carbon materials can effectively suppress the hydrogen evolution reaction. There are reports of using Pb / C composite materials as additives in lead-carbon batteries. Hao Zhang et al. confirmed that the functional groups on the carbon surface affect the electrodeposition of nano-lead and hydrogen evolution. Tong et al. studied the electrochemical properties of activated carbon materials containing divalent lead and their cycle performance in lead-carbon batteries under HRPSoC conditions. Yang Jiakuan et al. pointed out that nanostructured lead oxide formed by the pyrolysis of lead citrate precursor can be directly used as an additive in lead-carbon batteries.

[0004] Lead-carbon batteries can be categorized into two types based on the amount of electrolyte injected: lean-electrode and rich-electrode. Lean-electrode lead-carbon batteries are energy storage devices, using AGM separators, and are suitable for backup power, distributed, and large-scale energy storage applications. Rich-electrode lead-carbon batteries, on the other hand, are power storage devices, generally using PE separators, and are suitable for start-stop vehicles and hybrid vehicles. Like rich-electrode lead-acid batteries, rich-electrode lead-carbon batteries also suffer from acid stratification. Solving the acid stratification problem or slowing its rate can further improve the cycle life of lead-carbon batteries, significantly enhancing their market competitiveness. Using a colloidal electrolyte instead of dilute sulfuric acid solution can control acid stratification. However, the introduction of a colloidal electrolyte reduces the utilization rate of electrode active materials, affecting battery capacity, and negatively impacts the battery's charge reception and high-power discharge capabilities. Summary of the Invention

[0005] The technical problem to be solved by this invention (the purpose of the invention):

[0006] A self-stirring water-circulating lead-carbon battery includes a flat plate electrode (including a positive electrode and a negative electrode) placed in a sealed battery case. The flat plate electrode is placed perpendicular to the bottom surface of the battery case. A plate of carbon material is disposed above the flat plate electrode inside the battery case. The flat plate electrode is supported by a flat plate grid with through holes. The lower part of a vertically placed grid is filled with carbon material, and the negative electrode active material is filled on the grid above the carbon material to form a negative electrode. The positive electrode active material is filled on another grid to form a positive electrode.

[0007] The carbon material used for filling is a carbon paste prepared by mixing activated carbon and binder in a mass ratio of 50-95:50-5 (preferably 75-95:25-5, more preferably 85:15).

[0008] The ratio of the area of ​​the grid region filled with carbon material in the negative electrode to the total area of ​​the grid is (0.1-10):50, preferably (0.2-4):50, and more preferably (0.5-2):50.

[0009] The carbon material has a specific surface area of ​​200-3000 m². 2 / g of activated carbon or graphitized carbon material, preferably 500-2000m 2 / g material; the carbon material for the plate is carbon felt, graphite felt, carbon paper or carbon cloth.

[0010] The carbon material used in the plate is a carbon material with hydrogen-oxygen composite function after treatment. The treatment process is as follows:

[0011] 1) Activation of plate carbon material: Take a plate carbon material and immerse it in a potassium hydroxide aqueous solution for 1-5 hours, wherein the mass ratio of the plate carbon material to the total mass of the potassium hydroxide aqueous solution is 1:(10-1000) (preferably 1:(50-200)), and the concentration of the potassium hydroxide solution is 0.1mol / L-10mol / L (preferably 0.5-5mol / L). Take out the plate carbon material after immersion and dry it at a temperature of 40-120℃ (preferably 60-80℃) for 1-24 hours (preferably 8-16 hours). Transfer the dried plate carbon material to a nitrogen atmosphere sintering furnace for activation at a temperature of 700-1200℃ for 1-10 hours (preferably 800-1000℃, 4-6 hours).

[0012] 2) Preparation of plate carbon material with hydrogen-oxygen composite function: The activated plate carbon material is immersed in chloroplatinic acid aqueous solution for 1-5 hours, wherein the mass ratio of plate carbon material to the total mass of aqueous solution is 1:(10-1000) (preferably 1:(50-200)), and the concentration of chloroplatinic acid solution is 0.1mol / L-10mol / L (preferably 0.5-5mol / L). The immersed plate carbon material is removed and dried at a temperature of 40-120℃ (preferably 60-80℃) for 1-24 hours (preferably 8-16 hours). The dried plate carbon material is then immersed in sodium borohydride solution for reduction reaction for 1-5 hours, wherein the mass ratio of activated plate carbon material to the total mass of sodium borohydride solution is 1:(10-1000) (preferably 1:(50-200)), and the concentration of sodium borohydride solution is 0.1mol / L-10mol / L (0.5-5mol / L).

[0013] The treated carbon plate material with hydrogen and oxygen functions is placed on top of the welded lead-carbon battery, avoiding contact with the electrode tabs, or the tabs are insulated. Insulation treatment refers to adding an insulating plastic sleeve or coating insulating glue to the part of the tab that is higher than the carbon plate material.

[0014] The thickness of the carbon material for the plate with hydrogen-oxygen composite function is 0.01-10mm, preferably 0.5-2mm.

[0015] In order to ensure that the amount of catalyst used in the chemical process of hydrogen-oxygen water generation is sufficient, the mass ratio of chloroplatinic acid to the mass of the carbon material being coated in the carbon material treatment process is 0.001-1000:1, preferably 50-500:1. The carbon material of the carbon material is carbon felt, carbon paper or carbon cloth.

[0016] By weight, the negative electrode of a lead-carbon battery consists of: 500-800 parts lead powder, 1-20 parts carbon material, 6-10 parts barium sulfate, and 0.1-0.5 parts short polypropylene fibers with a length of 0.1-5 mm and a diameter of 100 nm-5 μm.

[0017] The material composition of the positive electrode of the lead-carbon battery is: 500-800 parts lead powder, 6-10 parts barium sulfate, and 0.1-0.5 parts short polypropylene fibers with a length of 0.1-5 mm and a diameter of 100 nm-5 μm.

[0018] The preparation process of lead-carbon battery electrodes is as follows:

[0019] Preparation of negative electrode A: (1) By weight, 500-800 parts of lead powder, 1-20 parts of carbon material, 6-10 parts of barium sulfate, and 0.1-0.5 parts of polypropylene short fibers with a length of 0.1-5 mm and a diameter of 100 nm-5 μm are stirred and premixed. While stirring, 50-100 parts of water are added to the premixed powder and stirred for 1-60 min to obtain lead paste; (2) First, the prepared carbon paste is scraped onto the grid at the bottom of the lead-carbon battery grid, and then the prepared lead paste is scraped onto the remaining metal lead grid. After drying and curing, the negative electrode of the lead-carbon battery is obtained. The curing temperature is 30-50℃, the humidity is 70-95%, and the curing time is 10-30 hours. The drying temperature is 60-120℃ and the time is 10-30 hours.

[0020] B. Positive electrode preparation: The positive electrode of the lead-acid battery is prepared according to the same process steps as the negative electrode preparation steps (1) and (2). The difference is that no carbon material is added during the positive electrode preparation process to obtain lead paste, and only lead paste is scraped onto the grid.

[0021] In a lead-carbon battery, a flat electrode is placed in a sealed battery box with the electrode perpendicular to the bottom of the battery box. Sulfuric acid electrolyte is injected into the battery box. The mass ratio of sulfuric acid electrolyte to negative electrode lead paste active material is 60-200:50. The mass concentration of sulfuric acid electrolyte is 1.1-1.4 g / ml. The volume ratio of sulfuric acid electrolyte to battery box is (4-20):35.

[0022] Beneficial effects of this invention:

[0023] This invention provides a method to avoid electrolyte stratification in flooded lead-carbon batteries by setting up a self-stirring water-circulating flooded lead-carbon battery. Specifically, electrodes with low hydrogen evolution and oxygen evolution overpotentials are arranged at the bottom of the positive and negative plates of the lead-carbon battery. Their function is to electrolyze a certain amount of water at the end of charging to produce hydrogen and oxygen. As the hydrogen and oxygen diffuse upwards through the gaps between the plates and separators, they generate bubbles, which agitate the electrolyte, thereby eliminating acid stratification, suppressing irreversible sulfation at the bottom of the negative electrode, and improving the cycle life of the lead-carbon battery. A composite carbon felt material with catalytic activity for hydrogen-oxygen recombination is placed in the upper part of the battery cell. Hydrogen and oxygen diffused through the gaps between the plates and separators react chemically with the catalyst as they pass through the carbon felt, generating water and achieving water circulation. Using the technical solution provided by this invention, not only can acid stratification be avoided, but water consumption of the battery can also be reduced, thus further improving the cycle life of the lead-carbon battery. Detailed Implementation

[0024] The present invention will now be described in detail with reference to the embodiments.

[0025] Unless otherwise specified, the raw materials used in the examples were commercially purchased and used directly without processing; the instruments and equipment used were based on the manufacturer's recommended operating parameters.

[0026] In the embodiments, the cycle life of the lead-carbon battery was tested using a Blue Electric charge-discharge tester and a Newway charge-discharge tester.

[0027] Example 1:

[0028] 1. Activation of carbon felt: Take 4 carbon felts (70mm long, 50mm wide, and 1mm thick) and immerse them in 100ml of 3mol / L potassium hydroxide aqueous solution for 1 hour. Remove the immersed carbon felts and dry them at 80℃ for 12 hours. Transfer the dried carbon felts to a nitrogen atmosphere sintering furnace for activation at 800℃ for 5 hours.

[0029] 2. Preparation of carbon felt with hydrogen-oxygen recombination function: The activated carbon felt was immersed in 100 ml of 3 mol / L chloroplatinic acid aqueous solution for 1 hour. The immersed carbon felt was removed and dried at 80℃ for 12 hours. The dried carbon felt was then immersed in 100 ml of 3 mol / L sodium borohydride solution for a reduction reaction for 1 hour.

[0030] 3. Preparation of the negative electrode for lead-carbon batteries: Carbon material is horizontally filled into the bottom row of the grid cells to a height of 1 mm. The carbon material is a carbon paste (10% water content) prepared by mixing commercial activated carbon and PTFE binder in a mass ratio of 85:15 with water. The carbon material used has a specific surface area of ​​approximately 1300 m².2 / g of commercial activated carbon is used to fill the bottom grid with carbon paste during lead paste filling of the electrode plate. The mass of the filling is 1g, which serves as the negative electrode plate grid.

[0031] 4. The lead-carbon battery is prepared using the following steps: A. Preparation of the negative electrode: (1) 600g of lead powder, 9g of activated carbon, 8.4g of barium sulfate, and 0.3g of polypropylene short fibers with a length of 5mm and a diameter of 0.5-1.5μm are premixed using a high-speed mixer. While stirring, 84g of deionized water is added to the premixed powder, and stirring is continued for 10min to obtain lead paste; (2) The lead paste is scraped onto a metal lead grid. The grid size is 70mm long, 50mm wide (or high), and 2mm thick. The curing temperature is 40℃ and the humidity is 80℃. 0%, curing time is 20 hours; drying temperature is 80℃, time is 24 hours; B. Preparation of positive electrode: prepare lead-acid battery positive electrode according to the same process steps as negative electrode preparation steps (1) and (2), the difference is that no carbon material is added to obtain lead paste during the preparation of positive electrode, and conventional commercial grid is used, and only lead paste is scraped on the grid; C. Preparation of lead-carbon battery: three positive electrode plates and two negative electrode plates are placed alternately in parallel, and commercial AGM separator is used between positive electrode plates and negative electrode plates.

[0032] 5. Place the carbon felt with hydrogen-oxygen recombination function on top of the welded lead-carbon battery, avoiding contact with the tabs. Attach insulating plastic to the portion of the tabs above the separator. The carbon felt with hydrogen-oxygen recombination function should be 40mm wide and 65mm long. The thickness of the carbon felt with hydrogen-oxygen recombination function should be 0.01-10mm, preferably 0.5-2mm. Weld two negative plates in parallel and three positive plates in parallel. The total mass of the positive active material of the lead-acid battery (the total mass of the dried lead paste on the three positive plates) is 20.0g, referring to the total mass of the lead paste contained in the three parallel-welded positive plates. The total mass of the negative active material (the total mass of the dried lead paste on the two negative plates) is 14.3g, referring to the total mass of the lead paste contained in the two parallel-welded negative plates. The positive and negative electrode grids use conventional lead grids with dimensions of 70mm in length, 50mm in width, and 2mm in thickness. The positive and negative electrodes are placed in a tightly assembled battery box (the electrodes are perpendicular to the bottom of the battery box), which is 76mm in length, 44mm in width, and 100mm in height. 88g of sulfuric acid electrolyte with a density of 1.275g / ml is injected into the battery box.

[0033] The battery was subjected to a cycle life test under the following conditions at 25°C: constant current discharge of 4.2A for 59 seconds, discharge of 18A for 1 second, and constant current and constant voltage charging of 6.3A current and 2.3V voltage for 60 seconds. This charge and discharge condition was repeated 3600 times, followed by a 40-hour rest period. The cycle test was restarted after 40 hours. The life test was terminated when the battery voltage dropped below 1.2V.

[0034] The assembled hybrid battery has an initial voltage of 2.1824V when fully charged at room temperature, and can run 18,165 cycles in a room temperature life test. Compared with the test results of a regular lead-acid battery with the same lead content under the same test conditions (7,198 cycles), the room temperature cycle life of the hybrid lead-carbon battery can reach 2.5 times that of a traditional lead-acid battery.

[0035] Example 2:

[0036] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the amount of activated carbon added at the bottom is reduced to 0.5g. The assembled hybrid battery has an initial voltage of 2.1733V under full charge at room temperature, and can run 17726 cycles in the room temperature life test. Compared with the test results of ordinary lead-acid batteries with the same lead content under the same test conditions (7198 cycles), the room temperature cycle life of the hybrid lead-carbon battery can reach 2.5 times that of the traditional lead-acid battery.

[0037] Example 3:

[0038] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, a 2mm thick carbon felt with hydrogen-oxygen recombination function is placed on top of the battery to prepare the lead-carbon battery. The assembled internal hybrid battery has an initial voltage of 2.1824V under full charge at room temperature, and the internal hybrid battery can run 18291 cycles in the room temperature life test. Compared with the test results of ordinary lead-acid batteries with the same lead content under the same test conditions (7198 cycles), the room temperature cycle life of the internal hybrid lead-carbon battery can reach 2.5 times that of the traditional lead-acid battery.

[0039] Example 4:

[0040] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the bottom activated carbon is replaced with the same mass of activated carbon with a specific surface area of ​​1800 m². 2Lead-carbon batteries were prepared using activated carbon material at a concentration of / g. The assembled hybrid battery had an initial voltage of 2.1925V under full charge at room temperature and could run for 18076 cycles in a room temperature life test. Compared with the test results of a conventional lead-acid battery with the same lead content under the same test conditions (7198 cycles), the room temperature cycle life of the hybrid lead-carbon battery can reach 2.5 times that of the conventional lead-acid battery.

[0041] Example 5:

[0042] The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the concentration of added chloroplatinic acid is changed to 5 mol / L. The assembled hybrid battery has an initial voltage of 2.1723V under full charge at room temperature, and can run 18,132 cycles in the room temperature life test. Compared with the test results of ordinary lead-acid batteries with the same lead content under the same test conditions (7,198 cycles), the room temperature cycle life of the hybrid lead-carbon battery can reach 2.5 times that of the traditional lead-acid battery.

[0043] Example 6:

[0044] The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the carbon felt used is replaced with carbon felt of the same mass and 2mm thickness. The assembled hybrid battery has an initial voltage of 2.1834V under full charge at room temperature, and can run 18274 cycles in the room temperature life test. Compared with the test results of ordinary lead-acid batteries with the same lead content under the same test conditions (7198 cycles), the room temperature cycle life of the hybrid lead-carbon battery can reach 2.5 times that of the traditional lead-acid battery.

[0045] Example 7:

[0046] The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the concentration of the chloroplatinic acid solution used is changed to 9 mol / L. The assembled hybrid battery has an initial voltage of 2.1742V under full charge at room temperature, and can run 18372 cycles in the room temperature life test. Compared with the test results of a conventional lead-acid battery with the same lead content under the same test conditions (7198 cycles), the room temperature cycle life of the hybrid lead-carbon battery can reach 2.5 times that of a conventional lead-acid battery.

[0047] Example 8:

[0048] The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the mass of the sulfuric acid electrolyte used is changed to 190g. The assembled hybrid battery has an initial voltage of 2.1742V under full charge at room temperature, and can run 18092 cycles in the room temperature life test. Compared with the test results of ordinary lead-acid batteries with the same lead content under the same test conditions (7198 cycles), the room temperature cycle life of the hybrid lead-carbon battery can reach 2.5 times that of the traditional lead-acid battery.

[0049] Comparative Example 1

[0050] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1, no other conditions are changed, and no carbon felt with hydrogen-oxygen recombination function is added. The assembled internal hybrid battery has an initial voltage of 2.1751V under full charge at room temperature, and the battery can run for 5198 cycles under room temperature conditions.

[0051] Comparative Example 2

[0052] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1, other conditions are not changed, and the preparation of carbon felt with hydrogen-oxygen recombination function is not carried out. In the process of preparing the lead-acid battery, only the same mass and size of untreated carbon felt material are added to the surface of the negative electrode. The assembled internal hybrid battery has an initial voltage of 2.1832V under full charge at room temperature, and the battery can operate for 5425 cycles under room temperature conditions.

[0053] Comparative Example 3

[0054] The process was the same as in Example 1, except that, following the requirements of Example 1, the concentration of the chloroplatinic acid solution was changed to 0.001 mmol / L without altering other conditions. Since there was no hydrogen-oxygen composite catalyst present in the carbon felt, the hydrogen evolution in the battery was exacerbated. The initial voltage of the assembled internal hybrid battery at full charge at room temperature was 2.1824V, and the battery could operate for 3996 cycles under room temperature conditions.

[0055] Comparative Example 4

[0056] The process was the same as in Example 1, except that, following the requirements of Example 1, the concentration of the sodium borohydride solution was changed to 0.001 mmol / L without altering other conditions. Due to the lack of sodium borohydride reduction, there was no hydrogen-oxygen composite catalyst present in the carbon felt, leading to aggravated hydrogen evolution in the battery. The initial voltage of the assembled internal hybrid battery under full charge at room temperature was 2.1624V, and the battery could operate for 3678 cycles under room temperature conditions.

[0057] Comparative Example 5

[0058] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1, other conditions are not changed, and no carbon material is applied below the negative electrode. That is, during the charging and discharging process, there is no large amount of carbon material that causes gas generation and disturbance below the electrode. The assembled internal hybrid battery has an initial voltage of 2.1356V under full charge at room temperature, and the battery can operate for 2421 cycles under room temperature conditions.

[0059] Comparative Example 6

[0060] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the mass of added sulfuric acid electrolyte is changed to 40g. The assembled internal hybrid battery has an initial voltage of 2.1734V under full charge at room temperature, and the battery can run for 2654 cycles under room temperature conditions.

[0061] Comparative Example 7

[0062] Lead-carbon battery: The process is the same as in Example 1, except that, following the requirements of Example 1 without changing other conditions, the added electrolyte is replaced with 120g of sulfuric acid electrolyte with a mass density of 1.5g / ml. The assembled internal hybrid battery has an initial voltage of 2.1627V under full charge at room temperature, and the battery can run for 1342 cycles under room temperature conditions.

Claims

1. A self-stirring water-circulating lead-carbon battery, comprising a flat plate electrode with a positive and a negative electrode placed inside a sealed battery case, the flat plate electrode being placed perpendicular to the bottom surface of the battery case, characterized in that: A plate of carbon material is disposed above a plate-shaped electrode inside the battery box. The plate-shaped electrode is supported by a plate-shaped grid with through holes. Carbon material is filled in the lower part of a vertically placed grid, and negative electrode active material is filled in the grid above the carbon material to form a negative electrode. Positive electrode active material is filled in the grid to form a positive electrode. The carbon material used for filling is a carbon paste prepared by mixing activated carbon and binder in a mass ratio of 50-95:50-5. The carbon material used in the plate is a carbon material with hydrogen-oxygen composite function after treatment. The treatment process is as follows: 1) Activation of plate carbon material: Take a plate carbon material and immerse it in potassium hydroxide aqueous solution for 1-5 hours, wherein the mass ratio of plate carbon material to total mass of potassium hydroxide aqueous solution is 1:(10-1000), and the concentration of potassium hydroxide solution is 0.1mol / L-10 mol / L. Take out the plate carbon material after immersion and dry it at a temperature of 40-120℃ for 1-24 hours. Transfer the dried plate carbon material to a nitrogen atmosphere sintering furnace for activation at a temperature of 700-1200℃ for 1-10 hours. 2) Preparation of plate carbon material with hydrogen-oxygen composite function: The activated plate carbon material is immersed in chloroplatinic acid aqueous solution for 1-5 hours, wherein the mass ratio of plate carbon material to the total mass of aqueous solution is 1:(10-1000), and the concentration of chloroplatinic acid solution is 0.1 mol / L-10 mol / L. The plate carbon material after immersion is removed and dried at a temperature of 40-120℃ for 1-24 hours. The dried plate carbon material is then immersed in sodium borohydride solution for reduction reaction for 1-5 hours, wherein the mass ratio of activated plate carbon material to the total mass of sodium borohydride solution is 1:(10-1000), and the concentration of sodium borohydride solution is 0.1 mol / L-10 mol / L. The mass ratio of sulfuric acid electrolyte to negative electrode lead paste active material is 60-200:50, and the mass concentration of sulfuric acid electrolyte is 1.1-1.4 g / ml. For lead-carbon batteries, the flat electrode is placed in a sealed battery box with the electrode perpendicular to the bottom of the battery box. Sulfuric acid electrolyte is injected into the battery box, and the volume ratio of sulfuric acid electrolyte to battery box is (4-20):

35.

2. The lead-carbon battery according to claim 1, characterized in that: The ratio of the area of ​​the grid region filled with carbon material in the negative electrode to the total area of ​​the grid is (0.1-10):

50.

3. The lead-carbon battery according to claim 2, characterized in that: The ratio of the area of ​​the grid region filled with carbon material in the negative electrode to the total area of ​​the grid is (0.2-4):

50.

4. The lead-carbon battery according to claim 1, characterized in that: The carbon material has a specific surface area of ​​200-3000 m². 2 / g of activated carbon or graphitized carbon material; the carbon material for the sheet material is carbon felt, graphite felt, carbon paper or carbon cloth.

5. The lead-carbon battery according to claim 4, characterized in that: The carbon material has a specific surface area of ​​500-2000 m². 2 / g of activated carbon or graphitized carbon material.

6. The lead-carbon battery according to claim 1, characterized in that: The carbon material used in the plate is a carbon material with hydrogen-oxygen composite function after treatment. The treatment process is as follows: 1) Activation of carbon plate material: Take a carbon plate material and immerse it in a potassium hydroxide aqueous solution for 1-5 hours, wherein the mass ratio of the carbon plate material to the total mass of the potassium hydroxide aqueous solution is 1:(50-200), and the concentration of the potassium hydroxide solution is 0.5-5mol / L. Take out the immersed carbon plate material and dry it at a temperature of 60-80℃ for 8-16 hours. Transfer the dried carbon plate material to a nitrogen atmosphere sintering furnace for activation at a temperature of 800-1000℃ for 4-6 hours. 2) Preparation of plate carbon material with hydrogen-oxygen composite function: The activated plate carbon material is immersed in chloroplatinic acid aqueous solution for 1-5 hours, wherein the mass ratio of plate carbon material to the total mass of aqueous solution is 1:(50-200), and the concentration of chloroplatinic acid solution is 0.5-5 mol / L. The plate carbon material after immersion is removed and dried at a temperature of 60-80℃ for 8-16 hours. The dried plate carbon material is then immersed in sodium borohydride solution for reduction reaction for 1-5 hours, wherein the mass ratio of activated plate carbon material to the total mass of sodium borohydride solution is 1:(50-200), and the concentration of sodium borohydride solution is 0.5-5 mol / L.

7. The lead-carbon battery according to claim 1, characterized in that: The treated carbon plate material with hydrogen and oxygen functions is placed on top of the welded lead-carbon battery, avoiding contact with the electrode tabs, or the tabs are insulated. Insulation treatment refers to adding an insulating plastic sleeve or coating insulating glue to the part of the tab that is higher than the carbon plate material.

8. The lead-carbon battery according to claim 1, characterized in that: The thickness of the carbon material for the plate with hydrogen-oxygen composite function is 0.01-10 mm.

9. The lead-carbon battery according to claim 1, characterized in that: To ensure sufficient catalyst dosage in the chemical process of hydrogen-oxygen water generation, the mass ratio of chloroplatinic acid to the carbon material used in the carbon material treatment process is 0.001-1000:

1. The carbon material used in the carbon material treatment process is carbon felt, carbon paper, or carbon cloth.

10. The lead-carbon battery according to claim 1, characterized in that: By weight, the negative electrode of a lead-carbon battery consists of: 500-800 parts lead powder, 1-20 parts carbon material, 6-10 parts barium sulfate, and 0.1-0.5 parts short polypropylene fibers with a length of 0.1-5 mm and a diameter of 100 nm-5 μm. The material composition of the positive electrode of the lead-carbon battery is: 500-800 parts lead powder, 6-10 parts barium sulfate, and 0.1-0.5 parts short polypropylene fibers with a length of 0.1-5 mm and a diameter of 100 nm-5 μm.

11. The lead-carbon battery according to claim 1, characterized in that: The preparation process of lead-carbon battery electrodes is as follows: A. Preparation of negative electrode: (1) By weight, 500-800 parts of lead powder, 1-20 parts of carbon material, 6-10 parts of barium sulfate, and 0.1-0.5 parts of polypropylene short fibers with a length of 0.1-5 mm and a diameter of 100 nm-5 μm are stirred and premixed. While stirring, 50-100 parts of water are added to the premixed powder and stirred for 1-60 min to obtain lead paste; (2) First, the prepared carbon paste is scraped onto the grid at the bottom of the lead-carbon battery grid, and then the prepared lead paste is scraped onto the remaining metal lead grid. After drying and curing, the negative electrode of the lead-carbon battery is obtained; the curing temperature is 30-50℃, the humidity is 70-95%, and the curing time is 10-30 hours; the drying temperature is 60-120℃ and the time is 10-30 hours. B. Positive electrode preparation: The positive electrode of the lead-acid battery is prepared according to the same process steps as the negative electrode preparation steps (1) and (2). The difference is that no carbon material is added during the positive electrode preparation process to obtain lead paste, and only lead paste is scraped onto the grid.