A green sheet gelled cell and a manufacturing process thereof

Abstract

The present application relates to the technical field of lead-acid battery preparation, and particularly relates to a green plate gel battery and a preparation process thereof, which comprises positive plate lead paste and negative plate lead paste, the positive plate lead paste comprises the following components: lead powder 100 parts, short fiber 0.08-0.12 parts, sulfuric acid 6.5-8.0 parts, and water 11-14 parts; the negative plate lead paste comprises the following components: lead powder 100 parts, sulfuric acid 5-6 parts, short fiber 0.05-0.1 parts, composite activated carbon 0.5-3 parts, sodium lignosulfonate 0.6-0.8 parts, barium sulfate 0.2-0.4 parts, humic acid 0.1-0.3 parts, and water 11-14 parts. The gel battery prepared by introducing the composite activated carbon into the negative plate lead paste and synergizing with the composite expansion agent system has a significant improvement in initial capacity and deep cycle life.

Description

Technical Field

[0001] This invention relates to the technical field of lead-acid battery manufacturing, and more particularly to a raw plate gel battery and its manufacturing process. Background Technology

[0002] Gel batteries, an important branch of valve-regulated lead-acid batteries, are characterized by immobilizing sulfuric acid electrolyte within a silica gel network formed by gelling agents such as fumed silica. Compared to lead-acid batteries using adsorbed glass fiber separators (AGM), gel batteries typically exhibit superior deep discharge cycle performance, lower water loss, and better thermal stability, leading to their widespread application in energy storage, communication backup power, and electric vehicles. A key process in gel battery manufacturing is the filling and gelation of the gel. Ideally, the filled acid-gel mixture should have a sufficiently long gelation time to ensure complete and uniform penetration into the microporous structure of the electrodes and separators, forming a monolithic gel with no dead zones in the ion-conducting pathway. This is fundamental to achieving excellent electrochemical performance in the battery.

[0003] To further improve the performance of gel batteries, existing technologies have explored various approaches at the lead paste formulation level. For example, Chinese patent CN106169565A discloses a lead-carbon gel battery electrode lead paste formulation, which adds a specific "Cypbrid carbon" material to the negative electrode lead paste and simultaneously premixes components with gelling properties, such as nano-sized silica and polyanionic cellulose, into both the positive and negative electrode lead pastes, aiming to improve the battery's power characteristics and cycle life. However, such solutions fail to fundamentally solve the core technical challenges faced when using the one-step "internal formation of green electrode plates" process. When the acid-gel mixture comes into contact with the highly active unformed electrode plates, the intense exothermic reaction causes a rapid increase in the battery's internal temperature, accelerating the electrolyte gelation process. Simply adding carbon materials and gelling agents to the lead paste cannot effectively suppress this uneven and rapid gelation. The ultimate problem is that the formed gel structure is uneven, and some active materials cannot be effectively wetted by the electrolyte, resulting in a significant reduction in lead paste utilization, causing the battery's initial capacity and long-term cycle life to fall short of ideal results. Summary of the Invention

[0004] In view of this, the present invention proposes a raw plate gel battery and its preparation method to solve the technical problem in the prior art of uneven gelation caused by the violent reaction of lead paste and acid glue mixture, which in turn leads to reduced battery capacity and shortened cycle life.

[0005] The technical solution of this invention is implemented as follows: This invention provides a raw electrode plate gel battery, including positive electrode plate lead paste and negative electrode plate lead paste.

[0006] The positive electrode plate lead paste comprises the following components: 100 parts lead powder, 0.08~0.12 parts short fiber, 6.5~8.0 parts sulfuric acid, 0.2~0.5 parts red lead, 0.1~0.3 parts graphene, and 11~14 parts water;

[0007] The negative electrode plate lead paste includes the following components: 100 parts lead powder, 5-6 parts sulfuric acid, 0.05-0.1 parts short fiber, 0.5-3 parts composite activated carbon, 0.6-0.8 parts sodium lignosulfonate, 0.2-0.4 parts barium sulfate, 0.1-0.3 parts humic acid, and 11-14 parts water.

[0008] Specifically, this invention fundamentally optimizes the reaction uniformity of the green electrode plate in the one-step internal formation process by constructing a microscopic electrochemical network within the negative electrode plate lead paste, consisting of composite activated carbon, composite expanding agents (sodium lignosulfonate, barium sulfate, and humic acid), and lead powder working synergistically. The composite activated carbon forms numerous tiny electrochemical capacitors within the lead paste, effectively buffering and dispersing the strong current surges during the initial formation stage and suppressing the polarization of the active materials in the lead paste. Simultaneously, the composite expanding agent system ensures that the lead paste forms and maintains a highly porous and open physical structure during curing and formation. This synergistic effect of physical and electrochemical processes allows the formation reaction to proceed more uniformly and gently throughout the entire electrode plate volume after the acid-gel mixture is poured in, avoiding rapid and uneven gelation of the electrolyte caused by localized overheating. This improves the utilization rate of the active materials in the electrode plate, thereby enhancing the initial capacity and deep cycle life of the battery.

[0009] Based on the above technical solutions, a preferred method for preparing composite activated carbon includes:

[0010] S1. Disperse activated carbon in deionized water, add stannous chloride and urea, stir and mix, and perform hydrothermal reaction at 150~200℃ for 10~14h to obtain modified activated carbon;

[0011] S2. Disperse the modified activated carbon in anhydrous toluene, add γ-glycidoxypropyltrimethoxysilane, heat to 100~120℃ and reflux for 22~24h to obtain silanized activated carbon;

[0012] S3. Disperse silanized activated carbon in anhydrous DMF, add [1,2,4]triazolopyrimidine-7-amine and triethylamine, and stir the mixture at 60~80℃ for 2~4h under nitrogen protection to obtain composite activated carbon.

[0013] Specifically, in step S1, a layer of nano-sized tin dioxide particles is deposited in situ on the surface of activated carbon via a hydrothermal reaction. This tin dioxide conductive network not only increases the specific surface area and electrochemical activity of the material, but more importantly, it significantly improves the affinity (i.e., wettability) between the carbon material and the sulfuric acid electrolyte, providing an excellent interface for subsequent electrochemical reactions. In step S2, γ-glycidoxypropyltrimethoxysilane is used as a "molecular bridge." The siloxane group at one end is firmly bonded to the hydroxyl groups on the tin dioxide surface, while a highly active epoxy group is introduced at the other end, providing a stable reaction site for subsequent grafting of functional molecules. In step S3, the epoxy group undergoes a ring-opening reaction with the [1,2,4]triazolo[1,5~a]pyrimidine~7~amine molecule, grafting this functional molecule onto the material surface. On the one hand, the molecular structure of [1,2,4]triazolo[1,5~a]pyrimidine~7~amine can efficiently capture Pb on the negative electrode surface. 2+ The nitrogen-containing heterocyclic molecule effectively inhibits the crystallization of lead dioxide into irreversible large-particle lead sulfate, thus significantly slowing down the sulfation process of the negative electrode. On the other hand, the nitrogen-containing heterocyclic molecule can effectively increase the hydrogen evolution overpotential of the negative electrode, thereby significantly suppressing the hydrogen evolution side reaction and water loss during battery charging. Through the synergistic effect of tin dioxide and the nitrogen-containing heterocyclic molecule, tin dioxide ensures sufficient contact between activated carbon and electrolyte, while the functionalized nitrogen-containing heterocyclic molecule actively intervenes at the molecular level, inhibiting the main cause of capacity decay (sulfation) and solving the problems of energy loss and water loss during charging, thereby improving the initial capacity and deep cycle life of the battery.

[0014] Based on the above technical solution, preferably, in step S1, the mass ratio of activated carbon, stannous chloride and urea is 2 : (3.5~4.5) : (2.5~3.5).

[0015] Based on the above technical solutions, preferably, in step S2, the mass ratio of modified activated carbon to γ-glycidoxypropyltrimethoxysilane is 1:(0.1~0.3).

[0016] Based on the above technical solution, preferably, in step S3, the mass ratio of silanized activated carbon, [1,2,4]triazolopyrimidine-7-amine and triethylamine is 10 : (3.5~4.5) : (2.5~3.5).

[0017] Based on the above technical solutions, preferably, the dry paste amount of the negative electrode plate is 8-10 g / Ah; and the dry paste amount of the positive electrode plate is 14-16 g / Ah.

[0018] Based on the above technical solutions, the preferred method for preparing positive electrode plate lead paste includes: adding lead powder, short fiber and water in sequence to a paste mixer, stirring evenly, slowly adding sulfuric acid, controlling the paste mixing temperature and final density, and obtaining positive electrode plate lead paste.

[0019] The preparation method of negative electrode plate lead paste includes: adding lead powder, composite activated carbon, sodium lignosulfonate, barium sulfate, humic acid, short fiber and water in sequence in a paste mixer, stirring evenly, and then slowly adding sulfuric acid, controlling the paste mixing temperature and the final density to obtain negative electrode plate lead paste.

[0020] This invention provides a process for preparing a bio-electrode gel battery, comprising the following steps:

[0021] (1) Electrode plate manufacturing and battery assembly: positive and negative lead paste are applied to the positive and negative electrode grids respectively, and positive and negative live plates are obtained after curing and drying. The positive and negative live plates are arranged alternately and separated by PVC separators and then placed into the battery case. Welding and sealing are completed to obtain the battery to be formed.

[0022] (2) Filling and formation: Fill the battery to be formed with pre-cooled gel electrolyte, then place the battery in a cold water bath for 2-6 hours, and finally perform multi-stage constant current charging to complete the formation and obtain a gel battery.

[0023] Based on the above technical solutions, preferably, the electrolyte is an electrolyte containing fumed silica gel and has an acid content of 21-33%.

[0024] Based on the above technical solutions, the preferred spacing between the positive and negative electrode plates is 1.8 to 2.6 mm.

[0025] The bio-plate gel battery and its preparation process of the present invention have the following advantages over the prior art:

[0026] (1) The present invention provides a gel battery with a live plate and its preparation method. By introducing composite activated carbon into the negative electrode lead paste and working in synergy with the composite expansion agent system, the reaction rate in the early stage of formation is effectively slowed down, local high temperature inside the battery is avoided, and the gel electrolyte can slowly and uniformly penetrate into all the pores of the plate and the separator, forming a uniform and complete gel network, thereby improving the utilization rate of the active material of the plate. The initial capacity and deep cycle life of the gel battery prepared by the present invention are significantly improved.

[0027] (2) The composite activated carbon used in this invention firstly improves the hydrophilicity of the carbon material through the in-situ deposited nano-tin dioxide intermediate layer, ensuring its excellent wetting with sulfuric acid electrolyte and providing a sufficient interface for electrochemical reaction; secondly, by chemically grafting the [1,2,4]triazolo[1,5~a]pyrimidine~7~amine functional molecule on the outermost layer, it can efficiently capture Pb. 2+ The ions inhibit irreversible sulfation, a key factor leading to battery capacity decay, at its source. Furthermore, as a hydrogen evolution inhibitor, they effectively increase the hydrogen evolution overpotential of the negative electrode. The introduction of this composite activated carbon gives the negative electrode plate stronger resistance to sulfation and a lower charging gas evolution rate, significantly reducing water loss in the gel battery throughout its lifespan and extending its service life. Detailed Implementation

[0028] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0029] It should be noted that the short fiber in this invention is polyester short fiber.

[0030] Example 1

[0031] This embodiment provides a bio-plate gel battery and its preparation process, wherein the positive electrode plate lead paste includes the following components: 100 parts lead powder, 0.1 parts short fiber, 7.5 parts sulfuric acid, 0.4 parts red lead, 0.2 parts graphene, and 12.5 parts water; the negative electrode plate lead paste includes the following components: 100 parts lead powder, 5.5 parts sulfuric acid, 0.08 parts short fiber, 2.2 parts composite activated carbon, 0.7 parts sodium lignosulfonate, 0.3 parts barium sulfate, 0.2 parts humic acid, and 12.5 parts water.

[0032] The preparation methods for composite activated carbon include:

[0033] S1. Soak 200g of activated carbon in HNO3 (10%) solution, wash until neutral, dry, then disperse in 1500ml of deionized water, add 40g of stannous chloride and 30g of urea, stir and mix, and hydrothermally react at 180℃ for 12h. After the reaction is completed, cool naturally to room temperature, centrifuge the product, wash several times with deionized water and anhydrous ethanol alternately until the washing solution is neutral, and vacuum dry to obtain modified activated carbon.

[0034] S2. Disperse 100g of modified activated carbon in 1000ml of anhydrous toluene, add 20g of γ-glycidyl etheroxypropyltrimethoxysilane, heat to 110℃ and reflux for 23h. After the reaction is completed, cool the mixture, filter, wash and vacuum dry to obtain silanized activated carbon.

[0035] S3. Disperse 100g of silanized activated carbon in 1000ml of anhydrous DMF, add 40g of [1,2,4]triazolopyrimidine-7-amine and 30g of triethylamine, and stir the reaction at 70℃ for 3h under nitrogen protection. After the reaction is completed, filter and collect the product, wash thoroughly with anhydrous DMF and hot deionized water in sequence, and vacuum dry to obtain composite activated carbon.

[0036] The preparation process includes the following steps:

[0037] (1) Add lead powder, short fiber and water to the paste mixer in sequence, stir evenly, and then slowly add a specific gravity of 1.40 g / cm³. 3 Sulfuric acid was used to prepare positive electrode plate lead paste; lead powder, composite activated carbon, sodium lignosulfonate, barium sulfate, humic acid, short fibers, and water were added sequentially to a paste mixer, and after stirring evenly, a specific gravity of 1.40 g / cm³ was slowly added. 3 Sulfuric acid was used to prepare negative electrode plate lead paste. The positive and negative electrode lead pastes were coated onto the positive and negative electrode plate grids respectively. The coated plates were cured in an environment of 50℃ and 95% humidity for 24 hours, and then dried at 60℃ for 16 hours to obtain positive and negative live plates. The positive and negative live plates were arranged alternately and separated by PVC separators and then placed into the battery case. The plate spacing between the positive and negative live plates was 2.2 mm. Welding and sealing were completed to obtain the battery to be formed.

[0038] (2) Pour a pre-cooled colloidal electrolyte to the battery to be formed into the colloidal electrolyte containing fumed silica and an acid content of 28%. Then place the battery in a cold water bath at 15°C for 4 hours. Finally, charge the battery with a multi-stage constant current, with the charging current controlled at the maximum constant current of 0.2CA, and the charging time is 100 hours to complete the formation and obtain the colloidal battery.

[0039] Example 2

[0040] This embodiment provides a bio-plate gel battery and its preparation process, wherein the positive electrode lead paste includes the following components: 100 parts lead powder, 0.08 parts short fiber, 6.5 parts sulfuric acid, 0.2 parts red lead, 0.1 parts graphene, and 11 parts water; the negative electrode lead paste includes the following components: 100 parts lead powder, 5 parts sulfuric acid, 0.05 parts short fiber, 0.5 parts composite activated carbon, 0.6 parts sodium lignosulfonate, 0.2 parts barium sulfate, 0.1 parts humic acid, and 11 parts water.

[0041] The preparation methods for composite activated carbon include:

[0042] S1. Soak 200g of activated carbon in HNO3 (10%) solution, wash until neutral, dry, then disperse in 1500ml of deionized water, add 35g of stannous chloride and 25g of urea, stir and mix, and hydrothermally react at 150℃ for 14h. After the reaction is completed, cool naturally to room temperature, centrifuge the product, wash several times with deionized water and anhydrous ethanol alternately until the washing solution is neutral, and vacuum dry to obtain modified activated carbon.

[0043] S2. Disperse 100g of modified activated carbon in 1000ml of anhydrous toluene, add 20g of γ-glycidyl etheroxypropyltrimethoxysilane, heat to 100℃ and reflux for 24h. After the reaction is completed, cool the mixture, filter, wash, and vacuum dry to obtain silanized activated carbon.

[0044] S3. Disperse 100g of silanized activated carbon in 1000ml of anhydrous DMF, add 35g of [1,2,4]triazolopyrimidine-7-amine and 25g of triethylamine, and stir the reaction at 60℃ for 4h under nitrogen protection. After the reaction is completed, filter and collect the product, wash thoroughly with anhydrous DMF and hot deionized water in sequence, and dry under vacuum to obtain composite activated carbon.

[0045] The preparation process includes the following steps:

[0046] (1) Add lead powder, short fiber and water to the paste mixer in sequence, stir evenly, and then slowly add a specific gravity of 1.40 g / cm³. 3 Sulfuric acid was used to prepare positive electrode plate lead paste; lead powder, composite activated carbon, sodium lignosulfonate, barium sulfate, humic acid, short fibers, and water were added sequentially to a paste mixer, and after stirring evenly, a specific gravity of 1.40 g / cm³ was slowly added. 3 Sulfuric acid was used to prepare negative electrode plate lead paste. The positive and negative electrode lead pastes were coated onto the positive and negative electrode plate grids respectively. The coated plates were cured in an environment of 50°C and 95% humidity for 24 hours, and then dried at 60°C for 16 hours to obtain positive and negative live plates. The positive and negative live plates were arranged alternately and separated by PVC separators and then placed into the battery case. The plate spacing between the positive and negative live plates was 1.8 mm. Welding and sealing were completed to obtain the battery to be formed.

[0047] (2) Pour a pre-cooled gel electrolyte to 5°C into the battery to be formed. The electrolyte is a gel electrolyte containing fumed silica with an acid content of 21%. Then place the battery in a cold water bath at 15°C for 4 hours. Finally, charge the battery with a multi-stage constant current, with the charging current controlled at the maximum constant current of 0.03CA, and the charging time is 150 hours to complete the formation and obtain a gel battery.

[0048] Example 3

[0049] This embodiment provides a bio-plate gel battery and its preparation process, wherein the positive electrode plate lead paste includes the following components: 100 parts lead powder, 0.12 parts short fiber, 8.0 parts sulfuric acid, 0.5 parts red lead, 0.3 parts graphene, and 14 parts water; the negative electrode plate lead paste includes the following components: 100 parts lead powder, 6 parts sulfuric acid, 0.1 parts short fiber, 3 parts composite activated carbon, 0.8 parts sodium lignosulfonate, 0.4 parts barium sulfate, 0.3 parts humic acid, and 14 parts water.

[0050] The preparation methods for composite activated carbon include:

[0051] S1. Soak 200g of activated carbon in HNO3 (10%) solution, wash until neutral, dry, then disperse in 1500ml of deionized water, add 45g of stannous chloride and 35g of urea, stir and mix, and hydrothermally react at 200℃ for 10h. After the reaction is completed, cool naturally to room temperature, centrifuge the product, wash several times with deionized water and anhydrous ethanol alternately until the washing solution is neutral, and vacuum dry to obtain modified activated carbon.

[0052] S2. Disperse 100g of modified activated carbon in 1000ml of anhydrous toluene, add 30g of γ-glycidyl etheroxypropyltrimethoxysilane, heat to 120℃ and reflux for 22h. After the reaction is completed, cool the mixture, filter, wash and vacuum dry to obtain silanized activated carbon.

[0053] S3. Disperse 100g of silanized activated carbon in 1000ml of anhydrous DMF, add 45g of [1,2,4]triazolopyrimidine-7-amine and 35g of triethylamine, and stir the reaction at 80℃ for 2h under nitrogen protection. After the reaction is completed, filter and collect the product, wash thoroughly with anhydrous DMF and hot deionized water in sequence, and vacuum dry to obtain composite activated carbon.

[0054] The preparation process includes the following steps:

[0055] (1) Add lead powder, short fiber and water to the paste mixer in sequence, stir evenly, and then slowly add a specific gravity of 1.40 g / cm³. 3 Sulfuric acid was used to prepare positive electrode plate lead paste; lead powder, composite activated carbon, sodium lignosulfonate, barium sulfate, humic acid, short fibers, and water were added sequentially to a paste mixer, and after stirring evenly, a specific gravity of 1.40 g / cm³ was slowly added. 3Sulfuric acid was used to prepare negative electrode plate lead paste. The positive and negative electrode lead pastes were coated onto the positive and negative electrode plate grids, respectively. The coated plates were cured in an environment of 50°C and 95% humidity for 24 hours, and then dried at 60°C for 16 hours to obtain positive and negative live plates. The positive and negative live plates were arranged alternately and separated by PVC separators and then placed into the battery case. The plate spacing between the positive and negative live plates was 2.6 mm. Welding and sealing were completed to obtain the battery to be formed.

[0056] (2) Pour a pre-cooled gel electrolyte to 20°C into the battery to be formed. The electrolyte is a gel electrolyte containing fumed silica with an acid content of 33%. Then place the battery in a cold water bath at 15°C for 4 hours. Finally, charge the battery with a multi-stage constant current, with the charging current controlled at the maximum constant current of 0.15CA, and the charging time is 90 hours to complete the formation and obtain a gel battery.

[0057] Comparative Example 1

[0058] This comparative example provides a live plate gel battery and its preparation process. The preparation process is the same as in Example 1, except that the negative plate lead paste includes the following components: 100 parts lead powder, 5.5 parts sulfuric acid, 0.08 parts short fiber, 2.2 parts Cypbrid carbon, 0.7 parts sodium lignosulfonate, 0.3 parts barium sulfate, 0.2 parts humic acid, and 12.5 parts water.

[0059] Comparative Example 2

[0060] This comparative example provides a bio-plate gel battery and its preparation process. The preparation process is the same as in Example 1, except that the method for preparing the composite activated carbon includes:

[0061] 200g of activated carbon was soaked in HNO3 (10%) solution, washed until neutral, dried, and then dispersed in 1500ml of deionized water. 40g of stannous chloride and 30g of urea were added, stirred and mixed, and hydrothermally reacted at 180℃ for 12h. After the reaction was completed, the mixture was naturally cooled to room temperature. The product was centrifuged and washed several times with deionized water and anhydrous ethanol alternately until the washing solution was neutral. The product was then vacuum dried to obtain modified activated carbon, which is the composite activated carbon.

[0062] Comparative Example 3

[0063] This comparative example provides a bio-plate gel battery and its preparation process. The preparation process is the same as in Example 1, except that the method for preparing the composite activated carbon includes:

[0064] S1. Soak 100g of activated carbon in HNO3 (5~10%) solution, wash until neutral, dry, and then disperse in 1000ml of anhydrous toluene. Add 20g of γ-glycidyl etheroxypropyltrimethoxysilane, heat to 110℃ and reflux for 23h. After the reaction is completed, cool the mixture, filter, wash, and vacuum dry to obtain silanized activated carbon.

[0065] S2. Disperse 100g of silanized activated carbon in 1000ml of anhydrous DMF, add 40g of [1,2,4]triazolopyrimidine-7-amine and 30g of triethylamine, and stir the reaction at 70℃ for 3h under nitrogen protection. After the reaction is completed, filter and collect the product, wash thoroughly with anhydrous DMF and hot deionized water in sequence, and vacuum dry to obtain composite activated carbon.

[0066] Comparative Example 4

[0067] This comparative example provides a bio-plate gel battery and its preparation process. The preparation process is the same as in Example 1, except that the method for preparing the composite activated carbon includes:

[0068] S1. Soak 200g of activated carbon in HNO3 (5~10%) solution, wash until neutral, dry, then disperse in 1500ml of deionized water, add 40g of stannous chloride and 30g of urea, stir and mix, and hydrothermally react at 180℃ for 12h. After the reaction is completed, cool naturally to room temperature, centrifuge the product, wash several times with deionized water and anhydrous ethanol alternately until the washing solution is neutral, and vacuum dry to obtain modified activated carbon.

[0069] S2. Add 100g of modified activated carbon and 40g of [1,2,4]triazolopyrimidine-7-amine to the ball mill jar of a planetary ball mill. Under an argon atmosphere, the mixture is ball-milled at a speed of 400 rpm for 6 hours to ensure uniform blending and obtain composite activated carbon.

[0070] Performance testing

[0071] The electrical performance of the gel batteries prepared in the examples and comparative examples was tested according to the YD / T 1360-2005 standard. Capacity test: 0.1C. 10 A. Constant current discharge to 10.8V, 10-hour rate capacity test; Cycle life test: 0.1C 10 A. Charge and discharge cycle, 100% DOD deep discharge, 500 cycles, then capacity retention was tested. The test results are shown in Table 1.

[0072] Table 1 Electrical Performance Testing

[0073]

[0074] As shown in Table 1, the gel batteries prepared in the embodiments of the present invention exhibit significantly improved specific capacity and cycle stability. Comparative Example 1 used commercially available Cypbrid carbon material, but it mainly addresses the negative electrode sulfation problem during cycling. However, the battery experienced severe gas evolution and water loss at the end of charging, leading to accelerated capacity decay in the later stages of cycling. In Comparative Example 2, although tin dioxide improved the hydrophilicity of activated carbon and provided certain active sites for electrochemical reactions, it itself does not possess the ability to inhibit hydrogen evolution and capture Pb. 2+ Therefore, during charging, the hydrogen evolution side reaction at the negative electrode remains severe, and irreversible sulfation cannot be fundamentally suppressed. In Comparative Example 3, the reaction is directly carried out on the hydrophobic original activated carbon, resulting in difficulty in electrolyte wetting, increased electrochemical polarization, and low utilization of active materials, thus significantly reducing its initial capacity. In Comparative Example 4, physical blending merely mixes [1,2,4]triazolopyrimidine-7-amine molecules with modified activated carbon through weak van der Waals forces. Therefore, although its initial capacity is acceptable, its function is rapidly lost with cycling, leading to intensified hydrogen evolution and sulfation, and a significant decrease in capacity retention.

[0075] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A gel battery with a live plate, comprising positive electrode lead paste and negative electrode lead paste, characterized in that: The positive electrode plate lead paste comprises the following components: 100 parts lead powder, 0.08~0.12 parts short fiber, 6.5~8.0 parts sulfuric acid, 0.2~0.5 parts red lead, 0.1~0.3 parts graphene, and 11~14 parts water; The negative electrode plate lead paste comprises the following components: 100 parts lead powder, 5-6 parts sulfuric acid, 0.05-0.1 parts short fiber, 0.5-3 parts composite activated carbon, 0.6-0.8 parts sodium lignosulfonate, 0.2-0.4 parts barium sulfate, 0.1-0.3 parts humic acid, and 11-14 parts water; Methods for preparing composite activated carbon include: S1. Disperse activated carbon in deionized water, add stannous chloride and urea, stir and mix, and perform hydrothermal reaction at 150~200℃ for 10~14h to obtain modified activated carbon; S2. Disperse the modified activated carbon in anhydrous toluene, add γ-glycidoxypropyltrimethoxysilane, heat to 100~120℃ and reflux for 22~24h to obtain silanized activated carbon; S3. Disperse silanized activated carbon in anhydrous DMF, add [1,2,4]triazolopyrimidine-7-amine and triethylamine, and stir the mixture at 60~80℃ for 2~4h under nitrogen protection to obtain composite activated carbon.

2. The raw electrode plate gel battery as described in claim 1, characterized in that: In step S1, the mass ratio of activated carbon, stannous chloride, and urea is 2:(3.5~4.5):(2.5~3.5).

3. The raw electrode plate gel battery as described in claim 1, characterized in that: In step S2, the mass ratio of modified activated carbon to γ-glycidoxypropyltrimethoxysilane is 1:(0.1-0.3).

4. A gel battery with a raw electrode plate as described in claim 1, characterized in that: In step S3, the mass ratio of silanized activated carbon, [1,2,4]triazolopyrimidine-7-amine, and triethylamine is 10 : (3.5~4.5) : (2.5~3.5).

5. A gel battery with a raw electrode plate as described in claim 1, characterized in that: The dry paste amount for the negative electrode plate is 8-10 g / Ah; the dry paste amount for the positive electrode plate is 14-16 g / Ah.

6. A gel battery with a raw electrode plate as described in claim 1, characterized in that: The preparation method of positive electrode plate lead paste includes: adding lead powder, short fiber, red lead, graphene and water in sequence, stirring evenly, and then adding sulfuric acid to obtain positive electrode plate lead paste; The preparation method of negative electrode plate lead paste includes: adding lead powder, composite activated carbon, sodium lignosulfonate, barium sulfate, humic acid, short fiber and water in sequence, stirring evenly, and then adding sulfuric acid to obtain negative electrode plate lead paste.

7. The manufacturing process of a bio-plate gel battery according to any one of claims 1 to 6, characterized in that: Includes the following steps: (1) Electrode plate manufacturing and battery assembly: positive and negative lead paste are applied to the positive and negative electrode grids respectively, and positive and negative live plates are obtained after curing and drying. The positive and negative live plates are arranged alternately and separated by PVC separators and then placed into the battery case. Welding and sealing are completed to obtain the battery to be formed. (2) Filling and formation: Fill the battery to be formed with pre-cooled gel electrolyte, then place the battery in a cold water bath for 2-6 hours, and finally charge the battery with constant current to complete the formation, thus obtaining a gel battery.

8. The preparation process of a bio-plate gel battery as described in claim 7, characterized in that: The colloidal electrolyte is an electrolyte containing fumed silica gel and has an acid content of 21-33%.

9. The manufacturing process of a bio-plate gel battery as described in claim 7, characterized in that: The spacing between the positive and negative electrode plates is 1.8–2.6 mm.

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