A hydrogen evolution inhibitor for long-time energy storage lead-carbon battery and a manufacturing method and application thereof

Abstract

The application discloses a lead-carbon battery hydrogen evolution inhibitor for long-time energy storage and a manufacturing method and application thereof, and belongs to the technical field of energy storage batteries. The application disperses redox graphene in deionized water to form graphene slurry, then adds a lead source and an initiator to form graphene gel, uniformly stirs the graphene gel, and then vacuum dries the graphene gel, and finally calcines and cools the graphene gel to obtain the lead-carbon battery hydrogen evolution inhibitor for long-time energy storage. Lead powder, short fibers, conductive fibers, a nucleating agent, conductive carbon, the lead-carbon battery hydrogen evolution inhibitor for long-time energy storage, and water are uniformly mixed, and then sulfuric acid is added and stirred to obtain lead paste; the lead paste is coated on an alloy grid, and then the lead paste is subjected to acid spraying, drying and solidification to obtain a lead-carbon battery negative plate. The negative plate prepared by using the application has a high HRPSoC cycle life, and has a good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of energy storage battery technology, specifically relating to a hydrogen evolution inhibitor for long-term energy storage lead-carbon batteries, its manufacturing method, and its application. Background Technology

[0002] Lead-carbon batteries are high-performance super batteries developed from lead-acid batteries. Their main improvement lies in the introduction of highly conductive carbon materials into the negative electrode of traditional lead-acid batteries, successfully suppressing the negative electrode sulfation problem and significantly improving the overall performance of traditional lead-acid batteries. However, while the introduction of carbon materials successfully solved the negative electrode sulfation problem, it also resulted in a lower hydrogen evolution overpotential. This leads to severe hydrogen evolution at the negative electrode during charging, ultimately causing the lead-carbon battery to fail due to water loss, severely limiting further performance improvements. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a hydrogen evolution inhibitor for lead-carbon batteries used in long-term energy storage, its manufacturing method and application. The negative electrode plate prepared by this invention has a high HRPSoC cycle life and has good application prospects.

[0004] To achieve the above objectives, the present invention provides the following technical solution:

[0005] This invention provides a method for preparing a hydrogen evolution inhibitor for long-term energy storage lead-carbon batteries, comprising the following preparation steps: Hydrogen evolution inhibitors were synthesized by citric acid bridging method. First, graphene oxide was dispersed in deionized water to form a graphene slurry. Then, a lead source and an initiator were added to form a graphene gel. After stirring evenly, the gel was vacuum dried, calcined and cooled to obtain a hydrogen evolution inhibitor for long-term energy storage lead-carbon batteries.

[0006] Preferably, the mass ratio of the redox graphene, lead source, and initiator is 1:(0.02-0.2):(0.5-1.5).

[0007] Preferably, the redox graphene is SnO2@nitrogen-doped graphene; The preparation method of SnO2@nitrogen-doped graphene is as follows: stannous sulfate and nitrogen-doped graphene are dispersed in deionized water at a mass ratio of 1:3, and the pH of the reaction system is adjusted to 3 with dilute sulfuric acid. Then, the mixed solution is transferred to a high-pressure reactor and reacted at 180°C for 12 hours. The product is centrifuged and repeatedly washed with deionized water and ethanol until the washing liquid is neutral. It is then vacuum dried for 6 hours.

[0008] Preferably, the lead source is lead acetate and / or lead nitrate.

[0009] Preferably, the initiator is one or a combination of citric acid, oxalic acid, dihydroxysuccinic acid, and 2-hydroxysuccinic acid.

[0010] Preferably, the calcination temperature is 400-600 ℃ and the time is 0.5-3 h.

[0011] The present invention also provides the application of the hydrogen evolution inhibitor for long-term energy storage lead-carbon batteries prepared by the above-mentioned preparation method in the preparation of negative plates for long-term energy storage lead-carbon batteries.

[0012] As a preferred embodiment, the preparation method of the negative electrode plate of the lead-carbon battery is as follows: lead powder, short fiber, conductive fiber, nucleating agent, conductive carbon, hydrogen evolution inhibitor for long-term energy storage lead-carbon battery, and water are mixed evenly and then sulfuric acid is added and stirred to obtain lead paste. The lead paste is applied to the alloy grid, and then cured by acid treatment and drying.

[0013] As a preferred embodiment, the mass fractions of each raw material are as follows: 100 parts lead powder, 8-15 parts water, 6-10 parts sulfuric acid, 0.1-0.2 parts short fiber, 0.1-0.2 parts conductive fiber, 0.5-1.5 parts nucleating agent, 0.5-1 part conductive carbon, and 0.5-1 part hydrogen evolution inhibitor for lead-carbon batteries for long-term energy storage.

[0014] Preferably, the sulfuric acid has a density of 1.0-1.4 g / mL.

[0015] Preferably, the short fibers are any one or more combinations of polypropylene fibers, polyacrylonitrile fibers, carbon fibers, polyacetylene fibers, polypyrrole fibers, and polyester fibers.

[0016] Preferably, the conductive fiber is carbon fiber.

[0017] Preferably, the nucleating agent is barium sulfate.

[0018] It contains at least the following beneficial technical effects: This invention provides a hydrogen evolution inhibitor negative electrode plate for lead-carbon batteries used in long-term energy storage. Hydrophilic groups are introduced during the synthesis of the hydrogen evolution inhibitor. The hydrophilicity in the negative electrode plate increases the contact area between the composite material and the electrolyte, facilitating the transport of the electrolyte into the active material. Furthermore, the presence of Pb and PbO nanoparticles not only increases the hydrogen evolution overpotential of the composite material but also acts as a "nucleus" to promote lead deposition, thereby improving the conversion efficiency of the active material and significantly increasing the battery's capacity and lifespan. The graphene coating not only provides a high-speed electron pathway for the PbO and carbon interface, but also helps to build a conductive network inside the active material, improves the utilization rate of the active material, facilitates the decomposition of lead sulfate crystals, inhibits the growth of lead sulfate crystals, and thus prevents sulfation of the negative electrode plate. After testing, the negative electrode plate prepared using this invention has a high HRPSoC cycle life and has good application prospects. Attached Figure Description

[0019] Figure 1 The image shows the SEM image of the negative electrode plate prepared in Example 1 after cycling. Detailed Implementation

[0020] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0021] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0022] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0023] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This application specification and embodiments are merely exemplary.

[0024] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0025] Unless otherwise specified, "room temperature" and "normal temperature" in this invention refer to 25±2℃.

[0026] Unless otherwise specified, all raw materials or instruments used in the following embodiments of the present invention are commercially available.

[0027] Preparation of SnO2@nitrogen-doped graphene: Stannous sulfate and nitrogen-doped graphene were dispersed in deionized water at a mass ratio of 1:3, and the pH of the reaction system was adjusted to 3 with dilute sulfuric acid. The mixed solution was then transferred to a high-pressure reactor and reacted at 180°C for 12 hours. The product was centrifuged and repeatedly washed with deionized water and ethanol until the washings were neutral. The product was then vacuum dried for 6 hours.

[0028] Example 1: A negative electrode plate for hydrogen evolution inhibitors in lead-carbon batteries for long-term energy storage includes a Pb-Ca alloy grid (72mm×39mm×1.8mm) coated with lead paste. By weight, lead paste comprises the following components: 100 parts lead powder, 0.15 parts polyacrylonitrile short fiber, 0.15 parts carbon conductive fiber, 1.0 part barium sulfate, 0.75 parts conductive carbon, 1 part SnO2@nitrogen-doped graphene, 0.75 parts carbon-coated lead nanoparticle hydrogen evolution inhibitor, 10 parts water, and 8 parts sulfuric acid (sulfuric acid density is 1.2 g / ml).

[0029] The preparation method of the hydrogen evolution inhibitor using carbon-coated lead nanoparticles is as follows: 50g of reduced graphene produced by Guangdong Yina was dispersed in deionized water to form a graphene slurry. Then, 1g of lead acetate and 25g of citric acid were added to the slurry. The prepared initiator solution was then pumped into the slurry using a peristaltic pump to form a graphene gel, which was stirred for 2 hours. The graphene gel was then placed in a vacuum environment for vacuum drying at 100℃ to remove moisture. After drying, the sample was placed in a tube furnace under a nitrogen atmosphere and heated to 500℃ for 2 hours. After cooling to room temperature, the carbon-coated lead nanoparticle hydrogen evolution inhibitor was obtained.

[0030] The above-mentioned method for preparing the negative electrode plate of the hydrogen evolution inhibitor for lead-carbon batteries used in long-term energy storage: Lead powder, polyacrylonitrile short fibers, carbon conductive fibers, nucleating agent, conductive carbon, carbon-coated lead nanoparticle hydrogen evolution inhibitor, and water are mixed and stirred for 30 minutes to form a paste. Then, sulfuric acid is added and stirring is continued for 30 minutes to obtain lead paste. The lead paste is coated on an alloy grid with a coating thickness of 2 mm. After acid leaching with sulfuric acid with a density of 1.4 g / mL (25℃), it is placed in a constant temperature and humidity oven for drying and curing.

[0031] Example 2: A negative electrode plate for hydrogen evolution inhibitors in lead-carbon batteries for long-term energy storage includes a Pb-Ca alloy grid (72mm×39mm×1.8mm) coated with lead paste. By weight, lead paste comprises the following components: 100 parts lead powder, 0.1 parts polyacrylonitrile short fiber, 0.1 parts carbon conductive fiber, 0.5 parts barium sulfate, 0.5 parts conductive carbon, 3 parts SnO2@nitrogen-doped graphene, 0.5 parts carbon-coated lead nanoparticle hydrogen evolution inhibitor, 8 parts water, and 6 parts sulfuric acid (sulfuric acid density is 1.0 g / ml).

[0032] The preparation method of the hydrogen evolution inhibitor using carbon-coated lead nanoparticles is as follows: 50g of reduced graphene produced by Guangdong Yina was dispersed in deionized water to form a graphene slurry. Then, 5g of lead nitrate and 50g of oxalic acid were added to the slurry. The prepared initiator solution was then pumped into the slurry using a peristaltic pump to form a graphene gel, which was stirred for 0.5 h. The graphene gel was then placed in a vacuum environment for vacuum drying at a temperature of 80 ℃ to remove moisture. After drying, the sample was placed in a tube furnace under a nitrogen atmosphere and heated to 400 ℃ for 0.5 h. After cooling to room temperature, the carbon-coated lead nanoparticle hydrogen evolution inhibitor was obtained.

[0033] The above-mentioned method for preparing the negative electrode plate of the hydrogen evolution inhibitor for lead-carbon batteries used in long-term energy storage: Lead powder, short fibers, conductive fibers, nucleating agent, conductive carbon, carbon-coated lead nanoparticle hydrogen evolution inhibitor, and water are mixed and stirred for 30 minutes to form a paste. Sulfuric acid is then added, and stirring is continued for 30 minutes to obtain lead paste. The lead paste is then coated onto an alloy grid to a thickness of 2 mm. After acid leaching with sulfuric acid with a density of 1.4 g / mL (25℃), the mixture is placed in a constant temperature and humidity oven for drying and curing.

[0034] Example 3: A negative electrode plate for hydrogen evolution inhibitors in lead-carbon batteries for long-term energy storage includes a Pb-Ca alloy grid (72mm×39mm×1.8mm) coated with lead paste. By weight, lead paste comprises the following components: 100 parts lead powder, 0.2 parts polyacrylonitrile short fiber, 0.2 parts carbon conductive fiber, 1.5 parts barium sulfate, 1 part conductive carbon, 5 parts SnO2@nitrogen-doped graphene, 1 part carbon-coated lead nanoparticle hydrogen evolution inhibitor, 12 parts water, and 10 parts sulfuric acid (sulfuric acid density is 1.4 g / ml).

[0035] The preparation method of the hydrogen evolution inhibitor using carbon-coated lead nanoparticles is as follows: 50g of reduced graphene produced by Guangdong Yina was dispersed in deionized water to form a graphene slurry. Then, 10g of lead nitrate and 30g of dihydroxysuccinic acid were added to the slurry. The prepared initiator solution was then pumped into the slurry using a peristaltic pump to form a graphene gel, which was stirred for 3 hours. The graphene gel was then placed in a vacuum environment for vacuum drying at 120 °C to remove moisture. After drying, the sample was placed in a tube furnace under a nitrogen atmosphere and heated to 600 °C for 3 hours. After cooling to room temperature, the carbon-coated lead nanoparticle hydrogen evolution inhibitor was obtained.

[0036] The above-mentioned method for preparing the negative electrode plate of the hydrogen evolution inhibitor for lead-carbon batteries used in long-term energy storage: Lead powder, short fibers, conductive fibers, nucleating agent, conductive carbon, carbon-coated lead nanoparticle hydrogen evolution inhibitor, and water are mixed and stirred for 30 minutes to form a paste. Sulfuric acid is then added, and stirring is continued for 30 minutes to obtain lead paste. The lead paste is then coated onto an alloy grid to a thickness of 2 mm. After acid leaching with sulfuric acid with a density of 1.4 g / mL (25℃), the mixture is placed in a constant temperature and humidity oven for drying and curing.

[0037] Comparative Example 1: It is basically the same as Example 1, except that no hydrogen evolution inhibitor for carbon-coated lead nanoparticles is added.

[0038] Comparative Example 2: The method is basically the same as in Example 1, except that graphene is used to replace the hydrogen evolution inhibitor of carbon-coated lead nanoparticles in an equal amount.

[0039] Comparative Example 3: This is basically the same as Example 1, except that activated carbon is used to replace the carbon-coated lead nanoparticle hydrogen evolution inhibitor in an equal amount.

[0040] Performance testing: The negative electrode plates prepared in Examples 1-3 and Comparative Examples 1-3 of this invention were subjected to performance testing. The specific testing methods are as follows: The self-made negative electrode plate was sandwiched between two negative electrode plates and three commercially available positive electrode plates. Each electrode plate was then wrapped with a 2mm thick AGM separator, inserted into a battery case, and filled with 1.28 g / mL dilute sulfuric acid. The case was then sealed, completing the assembly. The lead-carbon battery was formed and subjected to HRPSoC cycle performance testing using a Xinwei BTS-5V6A testing system. Before testing, the battery was fully charged, then discharged at 1C for 60 minutes (50% SoC), followed by high-rate charge-discharge cycles. Each micro-cycle test consisted of: charging at 2C for 60 seconds, resting for 10 seconds; then discharging at 2C for 60 seconds, resting for 10 seconds. 1000 micro-cycles constituted one large cycle. A capacity test was performed after each large cycle, and the cycle test was stopped when the capacity fell below 75% of the rated capacity.

[0041] The test results are shown in Table 1.

[0042] Table 1:

[0043] As shown in Table 1 above, the negative electrode plate prepared using the present invention has a high HRPSo C cycle life and has good application prospects.

[0044] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a hydrogen evolution inhibitor for long-term energy storage lead-carbon batteries, characterized in that, The preparation steps include the following: Redox graphene is dispersed in deionized water to form a graphene slurry. Then, a lead source and an initiator are added to form a graphene gel. After stirring evenly, the gel is vacuum dried, calcined, and cooled to obtain a hydrogen evolution inhibitor for long-term energy storage lead-carbon batteries.

2. The preparation method according to claim 1, characterized in that, The mass ratio of the redox graphene, lead source, and initiator is 1:(0.02-0.2):(0.5-1.5).

3. The preparation method according to claim 1, characterized in that, The redox graphene is SnO2@nitrogen-doped graphene; The preparation method of SnO2@nitrogen-doped graphene is as follows: stannous sulfate and nitrogen-doped graphene are dispersed in deionized water at a mass ratio of 1:3, and the pH of the reaction system is adjusted to 3 with dilute sulfuric acid. Then, the mixed solution is transferred to a high-pressure reactor and reacted at 180°C for 12 hours. The product is centrifuged and repeatedly washed with deionized water and ethanol until the washing liquid is neutral. It is then vacuum dried for 6 hours.

4. The preparation method according to claim 1, characterized in that, The lead source is lead acetate and / or lead nitrate.

5. The preparation method according to claim 1, characterized in that, The initiator is one or more of citric acid, oxalic acid, dihydroxysuccinic acid, and 2-hydroxysuccinic acid.

6. The preparation method according to claim 1, characterized in that, The calcination temperature is 400-600 ℃, and the time is 0.5-3 h.

7. The application of the hydrogen evolution inhibitor for long-term energy storage lead-carbon batteries prepared by the preparation method according to any one of claims 1-6 in the preparation of negative plates for long-term energy storage lead-carbon batteries.

8. The application according to claim 7, characterized in that, The preparation method of the negative electrode plate of the lead-carbon battery is as follows: lead powder, short fiber, conductive fiber, nucleating agent, conductive carbon, hydrogen evolution inhibitor for long-term energy storage lead-carbon battery, and water are mixed evenly and then sulfuric acid is added and stirred to obtain lead paste. The lead paste is applied to the alloy grid, and then cured by acid treatment and drying.

9. The application according to claim 8, characterized in that, The mass fractions of each raw material are as follows: 100 parts lead powder, 8-15 parts water, 6-10 parts sulfuric acid, 0.1-0.2 parts short fiber, 0.1-0.2 parts conductive fiber, 0.5-1.5 parts nucleating agent, 0.5-1 part conductive carbon, and 0.5-1 part hydrogen evolution inhibitor for lead-carbon batteries for long-term energy storage.

10. The application according to claim 9, characterized in that, The sulfuric acid has a density of 1.0-1.4 g / mL.

Images