Porous carbon loaded hybrid capacitor battery and preparation method thereof

Abstract

The invention relates to the technical field of capacitor batteries, in particular to a porous carbon-loaded hybrid capacitor battery and a preparation method thereof. The porous carbon-loaded hybrid capacitor battery is composed of a porous carbon-loaded bromine-manganese dioxide composite material positive electrode, an electro-deposition zinc carbon cloth negative electrode, a glass fiber filter paper composite diaphragm and an aqueous electrolyte, physical confinement of bromine species is realized through hierarchical porous biomass carbon, a halogen polymer is dynamically captured through a manganese dioxide nanosheet grown through biomimetic mineralization to form a self-repairing interface, and a shuttle effect is inhibited by anchoring bromine species through ionic liquid low-pressure impregnation, so that the key problem of short cycle life caused by manganese dissolution and halogen shuttle is solved; and a brand new strategy with exquisite structure, excellent performance and ultra-long cycle life is provided for the aqueous zinc ion hybrid capacitor battery by matching with a multi-dimensional collaborative design of negative electrode coating dendritic crystal inhibition, modified diaphragm ion selection and electrolyte bromine source supplementation.

Description

Technical Field

[0001] This invention relates to the field of capacitor battery technology, specifically to a porous carbon-supported hybrid capacitor battery and its preparation method. Background Technology

[0002] In the field of aqueous zinc-ion capacitor batteries, manganese dissolution and halogen shuttle effect of cathode materials are the two major challenges restricting their development. During the charging and discharging process, manganese dioxide cathodes are prone to the Jahn-Teller effect, which leads to the dissolution of manganese ions, resulting in rapid capacity decay and poor cycle stability. When halogen conversion reactions are introduced to increase energy density, the generated halogen polymers can easily diffuse through the separator to the negative electrode, causing a severe shuttle effect, which leads to a decrease in coulombic efficiency and an increase in self-discharge. This makes it difficult for traditional single modification strategies to meet the dual requirements of high energy density and long cycle life.

[0003] Research has found that synergistically designing physical confinement, chemical anchoring, and electrochemical trapping on electrode materials can effectively overcome the limitations of traditional modification techniques. However, existing technical solutions employ simple blending and layered coating methods, failing to achieve precise integration and orderly synergy of various mechanisms. Specifically, there is a lack of a multi-level porous carrier that can integrate halogen anchoring sites, manganese-based active materials, and self-healing interfaces. This leads to mutual interference and synergistic failure of various functional modules during cycling, preventing them from being synchronously and orderly activated and exerting synergistic effects in the electrochemical environment. This severely restricts the practical application of aqueous zinc-ion capacitor batteries.

[0004] To address the above problems, the present invention provides a solution. Summary of the Invention

[0005] The purpose of this invention is to provide a porous carbon-loaded hybrid capacitor battery and its preparation method, which has significant advantages such as excellent performance and ultra-long cycle life.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a porous carbon-loaded hybrid capacitor battery is composed of a porous carbon-loaded bromine-manganese dioxide composite positive electrode, an electrodeposited zinc carbon cloth negative electrode, a glass fiber composite separator, and an aqueous electrolyte; Furthermore, the preparation method of the porous carbon-supported bromine-manganese dioxide composite cathode includes the following steps: A1: Place durian shells and coconut shells in a vacuum drying oven, set the temperature to 80℃ and the vacuum degree to -0.08MPa, and dry for 12 hours. The mass ratio of durian shells to coconut shells is 1:1. After drying, transfer them to a pulverizer for crushing and pass them through a 60-mesh sieve to obtain biomass powder. Mix choline chloride and urea and add them to a reaction vessel, heat to 80℃ and stir to dissolve to obtain a eutectic solvent. The molar ratio of choline chloride to urea is 1:2. Add the biomass powder to the eutectic solvent. The mass ratio of biomass powder to eutectic solvent is 1:10. Set the stirrer speed to 200rpm and stir for 3 hours under a 90℃ water bath. After treatment, filter and wash three times with deionized water to obtain a pretreated biomass filter cake. A2: Transfer the pretreated biomass filter cake to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12h to obtain pretreated biomass. Transfer the pretreated biomass to a hydrothermal reactor, add deionized water, wherein the mass ratio of pretreated biomass to deionized water is 1:8, set the reaction temperature to 200℃, and the reaction time to 8h. After the reaction is completed, allow it to cool naturally to room temperature, filter and collect the solid product, wash it 3 times with deionized water to obtain hydrothermal coke. A3: Transfer the hydrothermal coke to a vacuum drying oven, set the temperature to 80℃ and the vacuum degree to -0.08MPa, and dry for 12h. After drying, transfer it to a tube furnace and heat it to 850℃ at a heating rate of 5℃ / min under nitrogen protection. Then switch to CO2 atmosphere, gas flow rate of 150ml / min, and activate at a constant temperature for 1.5h. After activation, allow it to cool naturally to room temperature to obtain hierarchical porous biomass carbon powder. Add the hierarchical porous biomass carbon powder to 0.05mol / L Tris-HCl buffer solution with a pH of 8.5, where the mass ratio of hierarchical porous biomass carbon powder to Tris-HCl buffer solution is 1:50. Disperse the solution by sonication for 15min to obtain a carbon dispersion. A4: Add dopamine hydrochloride to the carbon dispersion, wherein the mass ratio of multi-porous biomass carbon powder to dopamine hydrochloride is 5:1. Set the stirrer speed to 300 rpm and stir the reaction at room temperature for 8 hours. After the reaction is completed, centrifuge and wash three times with deionized water to obtain polydopamine-modified carbon material. Add the polydopamine-modified carbon material to 0.02 mol / L potassium permanganate solution, wherein the mass ratio of polydopamine-modified carbon material to potassium permanganate solution is 1:80. Set the stirrer speed to 200 rpm and stir the reaction at 60℃ water bath for 3 hours. After the reaction is completed, centrifuge and wash three times with deionized water to obtain manganese dioxide-carbon composite material. A5: Transfer the manganese dioxide-carbon composite material to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12h to obtain the primary composite material. Dissolve 1-ethyl-3-methylimidazolium bromide in anhydrous ethanol to prepare an ionic liquid ethanol solution with a concentration of 0.2mol / L. Transfer the primary composite material to a vacuum dryer, set the vacuum degree to -0.09MPa, and vacuum for 30min. Under vacuum, slowly drip the ionic liquid ethanol solution into the vacuum dryer through a constant pressure dropping funnel to completely wet the primary composite material. The mass ratio of the primary composite material to the ionic liquid ethanol solution is 1:10. A6: Maintain vacuum for 3 hours of soaking. After soaking, slowly restore normal pressure and continue soaking for 8 hours. After soaking, filter and wash 3 times with anhydrous ethanol. Then transfer the filter cake to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12 hours to obtain the intermediate composite material. A7: Weigh the intermediate composite material, conductive carbon black, and polyvinylidene fluoride, add them to the reactor, set the reactor stirrer speed to 300 rpm, and stir for 15 min to obtain a solid mixture, wherein the mass ratio of intermediate composite material, conductive carbon black, and polyvinylidene fluoride is 80:10:10. Then add N-methylpyrrolidone, wherein the mass ratio of solid mixture to N-methylpyrrolidone is 1:5, set the stirrer speed to 800 rpm, and stir for 2 h to obtain the positive electrode slurry; A8: Transfer the positive electrode slurry to a vacuum degassing machine, set the vacuum level to -0.09 MPa, and degas for 30 minutes. After degassing, use a coating machine to evenly coat the slurry onto the titanium foil current collector, controlling the coating thickness to 150 μm. Transfer the coated electrode to a vacuum drying oven, set the temperature to 80℃, the vacuum level to -0.08 MPa, and dry for 12 hours. After drying, use a roller press to compact the material, controlling the compaction density to 1.2 g / cm³. 3 A porous carbon-supported bromine-manganese dioxide composite positive electrode sheet was obtained; Furthermore, the method for preparing the electrodeposited zinc-carbon cloth negative electrode includes the following steps: B1: After the carbon cloth is cut, it is immersed in acetone and ultrasonically cleaned for 15 minutes. After ultrasonic cleaning in acetone, it is transferred to anhydrous ethanol and ultrasonically cleaned for 15 minutes. After ultrasonic cleaning in anhydrous ethanol, it is transferred to deionized water and ultrasonically cleaned for 15 minutes again. After cleaning, it is transferred to a vacuum drying oven, the temperature is set to 60℃, and it is dried for 6 hours to obtain the pretreated carbon cloth. B2: An electrodeposition electrolyte was prepared by mixing 1 mol / L zinc sulfate solution and 1 mol / L sodium sulfate solution, with a volume ratio of 1:1. Pretreated carbon cloth was used as the working electrode, and zinc foil as both the counter and reference electrodes. Constant current electrodeposition was employed, with a current density of 10 mA / cm². 2 The electrodeposition time was 30 min, and the electrolyte was continuously stirred slowly at a stirring rate of 50 rpm during the electrodeposition process. B3: After electrodeposition, the carbon cloth is removed, washed three times with deionized water, and then transferred to a vacuum drying oven at 40℃ for 4 hours to obtain electrodeposited zinc carbon cloth. Pyrrole is added to deionized water to prepare a 0.1 mol / L pyrrole solution, and ammonium persulfate is added to deionized water to prepare a 0.05 mol / L ammonium persulfate solution. The pyrrole solution and ammonium persulfate solution are mixed and stirred for 10 minutes to obtain the polymerization reaction solution, wherein the volume ratio of pyrrole solution to ammonium persulfate solution is 1:1. B4: Immerse the electrodeposited zinc carbon cloth in the polymerization reaction solution, set the ice-water bath to control the reaction temperature at 4℃, and polymerize for 2 hours. After the reaction is completed, take out the carbon cloth, wash it 3 times with deionized water, and then transfer it to a vacuum drying oven, set the temperature at 40℃, and dry for 4 hours to obtain the electrodeposited zinc carbon cloth negative electrode. Furthermore, the preparation method of the glass fiber composite diaphragm includes the following steps: C1: Glass fiber filter paper with a thickness of 0.3 mm and a pore size of 1 μm is selected as the substrate. After cutting, it is transferred to a vacuum drying oven, the temperature is set to 60℃, and it is dried for 4 hours to obtain a pretreated glass fiber membrane. C2: Weigh nano-silica, polyvinylidene fluoride and sodium carboxymethyl cellulose, add them to the reaction vessel, set the stirring speed of the reaction vessel to 300 rpm, and stir for 15 min to obtain a mixture, wherein the mass ratio of nano-silica, polyvinylidene fluoride and sodium carboxymethyl cellulose is 80:15:5. Then add N-methylpyrrolidone, wherein the mass ratio of the mixture to N-methylpyrrolidone is 1:10, set the stirring speed to 800 rpm, and stir for 2 h to obtain the coating slurry; C3: Transfer the coating slurry to a vacuum degassing machine, set the vacuum degree to -0.09MPa, and degas for 30 minutes. After degassing, use a coating machine to evenly coat the slurry on one side of the pretreated glass fiber membrane. The coating thickness is controlled at 10µm. Transfer the coated membrane to a vacuum drying oven, set the temperature to 60℃, the vacuum degree to -0.08MPa, and dry for 12 hours. After drying, the primary glass fiber composite membrane is obtained. C4: Sulfonated polyether ether ketone was dissolved in dimethylacetamide to prepare a 5% casting solution. The stirrer was set to 400 rpm and stirred and dissolved in a 60°C water bath for 4 hours to obtain a homogeneous casting solution. Then, it was transferred to a vacuum degassing machine and degassed for 1 hour with a vacuum of -0.09 MPa. C5: After degassing, pour the casting solution into the coating tank and use a scraper to evenly coat the uncoated surface of the glass fiber filter paper composite membrane with the casting solution. The coating thickness is controlled at 20 μm. After coating, let it stand in the air for 30 seconds, and then immerse it in a deionized water coagulation bath. The coagulation bath temperature is 25°C and the film formation time in the coagulation bath is 10 min. C6: After the film is formed in the coagulation bath, it is washed three times with deionized water and then transferred to a vacuum drying oven. The temperature is set at 60℃ and the vacuum degree is -0.08MPa. After drying for 12 hours, a glass fiber composite membrane is obtained. Furthermore, the aqueous electrolyte is composed of the following components by mass percentage: 80% deionized water, 13.5% zinc sulfate, 5% zinc bromide, 1% manganese sulfate, 0.3% polyvinylpyrrolidone, and 0.2% sodium dodecyl sulfate. The method for preparing the aqueous electrolyte includes the following steps: D1: Weigh zinc sulfate, zinc bromide and manganese sulfate and add them to the reaction vessel. Add 90% of the total amount of deionized water according to the formula. Set the stirrer speed to 400 rpm and stir to dissolve for 30 minutes at room temperature to obtain the basic electrolyte. D2: Weigh sodium dodecyl sulfate and add it to 5% of the total amount of deionized water in the formula. Heat to 40°C and stir to dissolve to obtain a surfactant solution. Slowly add the surfactant solution to the basic electrolyte and continue stirring for 15 minutes to obtain the secondary electrolyte. D3: Add polyvinylpyrrolidone to 5% of the total amount of the formula in deionized water, stir and dissolve for 5 minutes to obtain a polyvinylpyrrolidone solution, add the polyvinylpyrrolidone solution to the secondary electrolyte and continue stirring for 10 minutes, and after stirring is completed, filter through a 0.45um filter membrane to obtain an aqueous electrolyte. Furthermore, a method for preparing a porous carbon-supported hybrid capacitor battery includes the following steps: S1: Cut the porous carbon-supported bromine-manganese dioxide composite positive electrode sheet, the electrodeposited zinc carbon cloth negative electrode sheet and the glass fiber composite separator into the required sizes respectively. The positive electrode size is 50mm×50mm, the negative electrode size is 52mm×52mm, and the glass fiber composite separator is cut into 60mm×60mm. S2: Stack the positive electrode, glass fiber filter paper composite diaphragm and negative electrode in sequence, with the functional coating of the diaphragm facing the positive electrode. Weld nickel tabs to the positive and negative electrode respectively, and encapsulate them with aluminum-plastic film, leaving a liquid injection port. S3: Transfer the packaged battery to a vacuum oven, set the temperature to 60℃ and the vacuum degree to -0.09MPa, and dry for 12 hours. After drying, transfer it to a glove box. S4: In the glove box, inject 2ml of aqueous electrolyte through the injection port. After the injection is completed, seal the glove box with a vacuum sealer and let it stand for 12 hours to obtain a porous carbon-loaded hybrid capacitor battery.

[0007] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are as follows: 1. This invention establishes a novel three-tiered synergistic energy storage model based on carbon confinement, biomimetic mineralization, and dynamic capture. It utilizes hierarchical porous biomass carbon as a carrier to achieve physical confinement of bromine species in micropores and uniform loading of manganese dioxide nanosheets in mesopores. Through a dopamine-inspired biomimetic mineralization strategy, ultrathin manganese dioxide nanosheets are grown in situ within the carbon channels. The zinc ion intercalation reaction in the low-potential region of these nanosheets is used to capture halogen polymers dissolved from the positive electrode in situ. The synergistic cementing effect of the modified nano-gypsum core and the mineralized shell forms a dynamic self-healing interface layer. This systematically solves the key problems in traditional aqueous zinc-ion mixed capacitors, such as short cycle life due to manganese dioxide dissolution, low coulombic efficiency caused by halogen shuttle effect, and poor positive-negative electrode matching. 2: This invention constructs a multi-component functionally integrated composite cathode material with hierarchical porous biomass carbon support, ultrathin manganese dioxide nanosheets, and halogen ionic liquid as its core components. The components work in precise coordination in terms of spatial structure and action sequence. The hierarchical porous carbon is responsible for providing fast ion transport channels and anchoring sites for bromine species, the manganese dioxide nanosheets are responsible for contributing intercalation pseudocapacitance and dynamically capturing dissolved bromine species, and the ionic liquid is responsible for providing high-potential halogen redox capacitance. In terms of action mechanism, it achieves comprehensive and multi-level bromine shuttle suppression from physical confinement, chemical anchoring to electrochemical capture, showing excellent results, especially for high-rate cycling and long-life energy storage scenarios. 3. This invention successfully anchors halogen ionic liquids in the micropores of carbon materials in the form of ion pairs through a vacuum-assisted low-pressure impregnation process, avoiding the shuttle effect of free halogens. Through biomimetic mineralization technology, manganese dioxide nanosheets are formed with carbon carriers to form a strong chemical bond interface, which greatly improves structural stability. Through a multi-dimensional synergistic design of polypyrrole-coated negative electrode, sulfonated polyether ether ketone modified separator, and bromine source supplementation in electrolyte, an optimized scheme for the entire battery system from positive electrode, negative electrode, separator to electrolyte is constructed. This provides a new strategy for high-performance aqueous zinc-ion hybrid capacitors with green material sources, controllable preparation process, excellent electrochemical performance, and ultra-long cycle life. Detailed Implementation

[0008] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments.

[0009] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0010] Example 1 1. Place 255g of durian shell and 255g of coconut shell in a vacuum drying oven, set the temperature to 80℃ and the vacuum degree to -0.08MPa, and dry for 12h. After drying, transfer to a pulverizer to pulverize and pass through a 60-mesh sieve to obtain 500g of biomass powder. Mix 20mol of choline chloride and 40mol of urea and add to a reaction vessel, heat to 80℃ and stir to dissolve to obtain a eutectic solvent. Add 500g of biomass powder to 5kg of eutectic solvent, set the stirrer speed to 200rpm, and stir for 3h under a 90℃ water bath. After treatment, filter and wash with deionized water 3 times to obtain 765g of pretreated biomass filter cake. 2: Transfer the pretreated biomass filter cake to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12h to obtain 326g of pretreated biomass. Transfer the pretreated biomass to a hydrothermal reactor, add 2608g of deionized water, set the reaction temperature to 200℃ and the reaction time to 8h. After the reaction is completed, allow it to cool naturally to room temperature, filter and collect the solid product, wash it 3 times with deionized water to obtain 245g of hydrothermal coke. 3. Transfer the hydrothermal coke to a vacuum drying oven, set the temperature to 80℃ and the vacuum degree to -0.08MPa, and dry for 12h. After drying, transfer it to a tube furnace and heat it to 850℃ at a heating rate of 5℃ / min under nitrogen protection. Then switch to CO2 atmosphere, gas flow rate of 150ml / min, and activate at a constant temperature for 1.5h. After activation, allow it to cool naturally to room temperature to obtain 185g of hierarchical porous biomass carbon powder. Add the hierarchical porous biomass carbon powder to 9.25kg of 0.05mol / L Tris-HCl buffer solution with pH 8.5 and sonicate for 15min to obtain a carbon dispersion. 4: Add 37g of dopamine hydrochloride to the carbon dispersion, set the stirrer speed to 300rpm, and stir for 8h at room temperature. After the reaction is complete, centrifuge and wash three times with deionized water to obtain 208g of polydopamine-modified carbon material. Add the polydopamine-modified carbon material to 16.64kg of 0.02mol / L potassium permanganate solution, set the stirrer speed to 200rpm, and stir for 3h in a 60℃ water bath. After the reaction is complete, centrifuge and wash three times with deionized water to obtain 236g of manganese dioxide-carbon composite material. 5: Transfer the manganese dioxide-carbon composite material to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12h to obtain 224g of primary composite material. Dissolve 1-ethyl-3-methylimidazolium bromide in anhydrous ethanol to prepare an ionic liquid ethanol solution with a concentration of 0.2mol / L. Transfer the primary composite material to a vacuum dryer, set the vacuum degree to -0.09MPa, and vacuum for 30min. Under vacuum, slowly drip 2.24kg of ionic liquid ethanol solution into the vacuum dryer through a constant pressure dropping funnel to completely wet the primary composite material with the ionic liquid solution. 6: Maintain vacuum for 3 hours of soaking. After soaking, slowly restore normal pressure and continue soaking for 8 hours. After soaking, filter and wash three times with anhydrous ethanol. Then transfer the filter cake to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12 hours to obtain 256g of medium-grade composite material. 7: Weigh 204.8g of intermediate composite material, 25.6g of conductive carbon black and 25.6g of polyvinylidene fluoride, add them to the reactor, set the reactor stirrer speed to 300rpm, stir for 15min to obtain 256g of solid mixture, then add 1.28kg of N-methylpyrrolidone, set the stirrer speed to 800rpm, stir and mix for 2h to obtain positive electrode slurry; 8. Transfer the positive electrode slurry to a vacuum degassing machine, set the vacuum level to -0.09 MPa, and degas for 30 minutes. After degassing, use a coating machine to evenly coat the slurry onto the titanium foil current collector, controlling the coating thickness to 150 μm. Transfer the coated electrode to a vacuum drying oven, set the temperature to 80℃, the vacuum level to -0.08 MPa, and dry for 12 hours. After drying, use a roller press to compact the material, controlling the compaction density to 1.2 g / cm³. 3 The porous carbon-supported bromine-manganese dioxide composite positive electrode sheet prepared in Example 1 was obtained. Example 2 1. Cut the carbon cloth into 52mm×52mm pieces, immerse it in acetone and ultrasonically clean it for 15 minutes. After ultrasonic cleaning in acetone, transfer it to anhydrous ethanol and repeat ultrasonic cleaning for 15 minutes. After ultrasonic cleaning in anhydrous ethanol, transfer it to deionized water and ultrasonically clean it again for 15 minutes. After cleaning, transfer it to a vacuum drying oven, set the temperature to 60℃, and dry it for 6 hours to obtain the pretreated carbon cloth. 2. Prepare the electrodeposition electrolyte by mixing 200 ml of 1 mol / L zinc sulfate solution and 200 ml of 1 mol / L sodium sulfate solution. Use pretreated carbon cloth as the working electrode, and zinc foil as the counter and reference electrodes. Perform constant current electrodeposition with a current density of 10 mA / cm². 2The electrodeposition time was 30 min, and the electrolyte was continuously stirred slowly at a stirring rate of 50 rpm during the electrodeposition process. 3: After electrodeposition, remove the carbon cloth, wash it three times with deionized water, and then transfer it to a vacuum drying oven. Set the temperature to 40℃ and dry for 4 hours to obtain electrodeposited zinc carbon cloth. Add pyrrole to deionized water to prepare a 0.1 mol / L pyrrole solution, and add ammonium persulfate to deionized water to prepare a 0.05 mol / L ammonium persulfate solution. Mix 200 ml of pyrrole solution and 200 ml of ammonium persulfate solution and stir for 10 min to obtain the polymerization reaction solution. 4: Immerse the electrodeposited zinc carbon cloth in the polymerization reaction solution, set the ice-water bath to control the reaction temperature at 4°C, and polymerize for 2 hours. After the reaction is complete, take out the carbon cloth, wash it 3 times with deionized water, and then transfer it to a vacuum drying oven. Set the temperature to 40°C and dry for 4 hours to obtain the electrodeposited zinc carbon cloth negative electrode prepared in Example 2. Example 3 1: Select glass fiber filter paper with a thickness of 0.3mm and a pore size of 1um as the substrate, cut it into 60mm×60mm pieces, transfer it to a vacuum drying oven, set the temperature to 60℃, and dry for 4 hours to obtain a pretreated glass fiber membrane. 2: Weigh 160g of nano silica, 30g of polyvinylidene fluoride and 10g of sodium carboxymethyl cellulose, add them to the reaction vessel, set the stirring speed of the reaction vessel to 300 rpm, stir for 15 minutes to obtain 200g of mixture, then add 2kg of N-methylpyrrolidone, set the stirring speed of the stirring vessel to 800 rpm, stir and mix for 2 hours to obtain coating slurry; 3: Transfer the coating slurry to a vacuum degassing machine, set the vacuum degree to -0.09MPa, and degas for 30 minutes. After degassing, use a coating machine to evenly coat the slurry on one side of the pretreated glass fiber membrane. The coating thickness is controlled at 10µm. Transfer the coated membrane to a vacuum drying oven, set the temperature to 60℃, the vacuum degree to -0.08MPa, and dry for 12 hours. After drying, the primary glass fiber composite membrane is obtained. 4: Dissolve sulfonated polyether ether ketone in dimethylacetamide to prepare a 5% casting solution. Set the stirrer speed to 400 rpm and stir and dissolve in a 60℃ water bath for 4 hours to obtain a homogeneous casting solution. Then transfer it to a vacuum degassing machine, set the vacuum degree to -0.09 MPa, and degas for 1 hour. 5: After degassing, pour the casting solution into the coating tank and use a scraper to evenly coat the uncoated surface of the glass fiber filter paper composite membrane with the casting solution. The coating thickness is controlled at 20 μm. After coating, let it stand in the air for 30 seconds, and then immerse it in a deionized water coagulation bath. The coagulation bath temperature is 25°C and the film formation time is 10 min. 6: After the film is formed in the coagulation bath, it is washed three times with deionized water and then transferred to a vacuum drying oven. The temperature is set at 60°C and the vacuum degree is -0.08MPa. After drying for 12 hours, the glass fiber composite membrane prepared in Example 3 is obtained. Example 4 1: Weigh 27g zinc sulfate, 10g zinc bromide and 2g manganese sulfate and add them to the reaction vessel. Add 144g deionized water, set the stirrer speed to 400rpm, and stir to dissolve for 30min at room temperature to obtain the basic electrolyte. 2: Weigh 2g of sodium dodecyl sulfate and add it to 8g of deionized water. Heat to 40℃ and stir to dissolve to obtain a surfactant solution. Slowly add the surfactant solution to the basic electrolyte and continue stirring for 15 minutes to obtain the secondary electrolyte. 3: Add 3g of polyvinylpyrrolidone to 8g of deionized water and stir to dissolve for 5min to obtain a polyvinylpyrrolidone solution. Add the polyvinylpyrrolidone solution to the secondary electrolyte and continue stirring for 10min. After stirring, filter through a 0.45um filter membrane to obtain the aqueous electrolyte prepared in Example 4. Example 5 1: The porous carbon-supported bromine-manganese dioxide composite positive electrode prepared in Example 1, the electrodeposited zinc carbon cloth negative electrode prepared in Example 2, and the glass fiber composite separator prepared in Example 3 were cut into the required sizes respectively. The positive electrode size was 50mm×50mm, the negative electrode size was 52mm×52mm, and the glass fiber composite separator was cut into 60mm×60mm. 2: Stack the positive electrode, glass fiber filter paper composite diaphragm and negative electrode in sequence, with the functional coating of the diaphragm facing the positive electrode. Weld nickel tabs to the positive and negative electrode respectively, and encapsulate with aluminum-plastic film, leaving a liquid injection port. 3: Transfer the packaged battery to a vacuum oven, set the temperature to 60℃ and the vacuum degree to -0.09MPa, and dry for 12 hours. After drying, transfer it to a glove box. 4: In the glove box, inject aqueous electrolyte through the injection port. The injection volume is 2 ml. After the injection is completed, seal the glove box with a vacuum sealer and let it stand for 12 hours to obtain the porous carbon-loaded hybrid capacitor battery prepared in Example 5.

[0011] Comparative Example 1 The difference between this comparative example and Example 5 is that the positive electrode material is a physical mixture of commercially available manganese dioxide powder and activated carbon. The preparation method of the positive electrode in this comparative example is as follows: 1: Weigh out 80g of manganese dioxide powder with a particle size of 10µm and 80g of powder with a specific surface area of ​​1500m². 2 / g of activated carbon with a pore size distribution of 5nm was added to the reaction vessel, and the stirrer speed was set to 300rpm. The mixture was dry-mixed for 15min to obtain the positive electrode active mixture. 2: Weigh 160g of positive electrode active mixture, 20g of conductive carbon black and 20g of polyvinylidene fluoride, add them to the reaction vessel, set the stirrer speed to 300rpm, stir for 15min to obtain a solid mixture, then add 1kg of N-methylpyrrolidone, set the stirrer speed to 800rpm, stir and mix for 2h to obtain positive electrode slurry; 3: Transfer the positive electrode slurry to a vacuum degassing machine, set the vacuum degree to -0.09MPa, degas for 30 minutes, and after degassing, use a coating machine to evenly coat the slurry onto the titanium foil current collector, with the coating thickness controlled at 150um; 4. Transfer the coated electrode sheets to a vacuum drying oven, set the temperature to 80℃ and the vacuum degree to -0.08MPa, and dry for 12 hours. After drying, compact the sheets using a roller press, controlling the compaction density to 1.2g / cm³. 3 Thus, the positive electrode of Comparative Example 1 was obtained; The rest are the same as in Example 5.

[0012] Comparative Example 2 The difference between this comparative example and Example 5 is that the negative electrode uses conventional zinc foil with a thickness of 0.1 mm and a purity of 99.9%. The preparation method of the comparative example negative electrode is as follows: zinc foil is cut into 52mm×52mm pieces, immersed in acetone and ultrasonically cleaned for 15min. After ultrasonic cleaning in acetone, it is transferred to anhydrous ethanol and ultrasonically cleaned for 15min. After ultrasonic cleaning in anhydrous ethanol, it is transferred to deionized water and ultrasonically cleaned again for 15min. After cleaning, it is transferred to a vacuum drying oven, the temperature is set at 40℃, and it is dried for 4h to obtain the comparative example 2 negative electrode. The rest are the same as in Example 5.

[0013] Comparative Example 3 The difference between this comparative example and Example 5 is that the diaphragm is made of ordinary glass fiber filter paper with a thickness of 0.3 mm and a pore size of 1 μm. The comparative example diaphragm preparation method is as follows: glass fiber filter paper is cut into 60mm×60mm pieces, transferred to a vacuum drying oven, and dried at 60℃ for 4 hours to obtain the comparative example 3 diaphragm; The rest are the same as in Example 5.

[0014] Comparative Example 4 The difference between this comparative example and Example 5 is that the electrolyte used is a 2 mol / L zinc sulfate aqueous solution; The preparation method of the comparative electrolyte is as follows: zinc sulfate is weighed and added to deionized water to prepare a 2 mol / L zinc sulfate solution. The stirrer speed is set to 400 rpm and the solution is stirred and dissolved at room temperature for 30 min. After stirring, the solution is filtered through a 0.45 μm filter membrane to obtain the electrolyte of comparative example 4. The rest are the same as in Example 5.

[0015] Cyclic stability test The capacitor batteries prepared in Example 5 and Comparative Examples 1-4 were subjected to constant current charge-discharge tests using a battery testing system. The test voltage range was 0.8-1.8V, the current density was 2C, and the cycle time was 10,000 times. The capacity retention rate was recorded. Table 1. Cyclic stability test results

[0016] Analysis of Table 1 shows that the initial specific capacity of the capacitor battery prepared in Example 5 reached 285 mAh / g, and the capacity retention rate after 10,000 cycles was as high as 86.3%, which was significantly better than the comparative examples. Comparative Example 1 used a conventional positive electrode, with an initial capacity of only 168 mAh / g and a capacity retention rate of only 31.7% after 10,000 cycles, indicating that the positive electrode material of the present invention made a significant contribution to the capacity and cycle stability. After replacing the conventional negative electrode, separator and electrolyte in Comparative Examples 2-4, the cycle stability decreased to varying degrees.

[0017] Ratio Performance Test The rate performance of the capacitor batteries prepared in Example 5 and Comparative Examples 1-4 was tested using a battery testing system. The test voltage range was 0.8-1.8V. The batteries were charged and discharged at current densities of 0.2C, 0.5C, 1C, 2C, 5C and 10C, respectively, and the capacity retention rate at each rate was recorded (based on the 0.2C capacity). Table 2, Results of Ratio Performance Test

[0018] Analysis of Table 2 shows that the capacitor battery prepared in Example 5 retains 64.2% of its 0.2C capacity at a high rate of 10C, demonstrating excellent rate performance. Comparative Example 1, on the other hand, only retains 28.6% of its capacity at a rate of 10C, indicating that the hierarchical porous structure and ultrathin manganese dioxide nanosheet design of the cathode material of this invention significantly improve the rate performance. The rate performance of Comparative Examples 2-4 is between that of Example 5 and Comparative Example 1, indicating that improvements in the anode, separator, and electrolyte also make a significant contribution to the rate performance.

[0019] Self-discharge performance test After charging the capacitor batteries prepared in Example 5 and Comparative Examples 1-4 to 1.8V, they were left to stand at 25°C for 24h, 48h and 72h respectively, and the voltage retention rate and capacity retention rate were recorded. Table 3. Self-discharge performance test results

[0020] Analysis of Table 3 shows that the capacitor battery prepared in Example 5 maintained a voltage of 1.68V after standing for 72 hours, with a capacity retention rate as high as 85.2%, demonstrating excellent self-discharge performance. In contrast, the voltage of Comparative Example 1 dropped to 1.42V after standing for 72 hours, with a capacity retention rate of only 52.6%, indicating that the bromine anchoring design of the cathode material of this invention effectively suppressed the halogen shuttle effect. Comparative Example 3, using a common separator, had a capacity retention rate of 79.3%, lower than the 85.2% of Example 5.

[0021] High and low temperature performance testing The capacitor batteries prepared in Example 5 and Comparative Examples 1-4 were charged and discharged at a current density of 1C at temperatures of -20°C, 25°C and 60°C, respectively, and the capacity retention rate at each temperature was recorded (based on the capacity at 25°C). Table 4. High and low temperature performance test results

[0022] As can be seen from the analysis of Table 4, the capacitor battery prepared in Example 5 still retains 76.5% of its room temperature capacity at -20℃, demonstrating excellent low-temperature performance; while the comparative example in Example 1 only retains 42.3% at low temperature, indicating that the hierarchical porous structure of the cathode material of the present invention is beneficial for ion transport at low temperatures.

[0023] Energy density and power density testing Energy density and power density were calculated for the capacitor batteries prepared in Example 5 and Comparative Examples 1-4. Based on the mass of the positive electrode active material, the maximum energy density and the energy retention rate at the corresponding power density were recorded. Table 5. Test results of energy density and power density

[0024] Analysis of Table 5 shows that the maximum energy density of the capacitor battery prepared in Example 5 reached 185Wh / kg, which is significantly higher than that of Comparative Example 1 (98Wh / kg). At a high power density of 1000W / kg, Example 5 still maintained 76.5% of the energy density, demonstrating excellent energy-power synergy characteristics. Comparative Example 1, on the other hand, had an energy retention rate of only 48.3% at high power, indicating that the cathode material of the present invention effectively improved the power performance.

[0025] Coulomb efficiency test The capacitor batteries prepared in Example 5 and Comparative Examples 1-4 were cycled 100 times at a current density of 1C, and the average coulombic efficiency and the first-cycle coulombic efficiency were recorded. Table 6. Results of Coulomb efficiency test

[0026] Analysis of Table 6 shows that the coulombic efficiency of the capacitor battery prepared in Example 5 reached 93.5% in the first cycle and 99.2% in the average cycle, indicating its excellent reversibility. The coulombic efficiency of Comparative Example 1 was only 78.6% in the first cycle, indicating that conventional cathode materials have serious irreversible reactions. The coulombic efficiency of Example 5 increased to 99.5% in the 100th cycle, indicating that as the cycle progresses, the self-healing interface layer gradually stabilizes and further suppresses side reactions.

[0027] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A porous carbon-supported hybrid capacitor battery, characterized in that, It consists of a porous carbon-supported bromine-manganese dioxide composite positive electrode, an electrodeposited zinc carbon cloth negative electrode, a glass fiber composite membrane, and an aqueous electrolyte.

2. The porous carbon-supported hybrid capacitor battery according to claim 1, characterized in that, The preparation method of the porous carbon-supported bromine-manganese dioxide composite cathode includes the following steps: A1: Place durian shells and coconut shells in a vacuum drying oven, set the temperature to 80℃ and the vacuum degree to -0.08MPa, and dry for 12 hours. The mass ratio of durian shells to coconut shells is 1:

1. After drying, transfer them to a pulverizer for crushing and pass them through a 60-mesh sieve to obtain biomass powder. Mix choline chloride and urea and add them to a reaction vessel, heat to 80℃ and stir to dissolve to obtain a eutectic solvent. The molar ratio of choline chloride to urea is 1:

2. Add the biomass powder to the eutectic solvent. The mass ratio of biomass powder to eutectic solvent is 1:

10. Set the stirrer speed to 200rpm and stir for 3 hours under a 90℃ water bath. After treatment, filter and wash three times with deionized water to obtain a pretreated biomass filter cake. A2: Transfer the pretreated biomass filter cake to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12h to obtain pretreated biomass. Transfer the pretreated biomass to a hydrothermal reactor, add deionized water, wherein the mass ratio of pretreated biomass to deionized water is 1:8, set the reaction temperature to 200℃, and the reaction time to 8h. After the reaction is completed, allow it to cool naturally to room temperature, filter and collect the solid product, wash it 3 times with deionized water to obtain hydrothermal coke. A3: Transfer the hydrothermal coke to a vacuum drying oven, set the temperature to 80℃ and the vacuum degree to -0.08MPa, and dry for 12h. After drying, transfer it to a tube furnace and heat it to 850℃ at a heating rate of 5℃ / min under nitrogen protection. Then switch to CO2 atmosphere, gas flow rate of 150ml / min, and activate at a constant temperature for 1.5h. After activation, allow it to cool naturally to room temperature to obtain hierarchical porous biomass carbon powder. Add the hierarchical porous biomass carbon powder to 0.05mol / L Tris-HCl buffer solution with a pH of 8.5, where the mass ratio of hierarchical porous biomass carbon powder to Tris-HCl buffer solution is 1:

50. Disperse the solution by sonication for 15min to obtain a carbon dispersion. A4: Add dopamine hydrochloride to the carbon dispersion, wherein the mass ratio of multi-porous biomass carbon powder to dopamine hydrochloride is 5:

1. Set the stirrer speed to 300 rpm and stir the reaction at room temperature for 8 hours. After the reaction is completed, centrifuge and wash three times with deionized water to obtain polydopamine-modified carbon material. Add the polydopamine-modified carbon material to 0.02 mol / L potassium permanganate solution, wherein the mass ratio of polydopamine-modified carbon material to potassium permanganate solution is 1:

80. Set the stirrer speed to 200 rpm and stir the reaction at 60℃ water bath for 3 hours. After the reaction is completed, centrifuge and wash three times with deionized water to obtain manganese dioxide-carbon composite material. A5: Transfer the manganese dioxide-carbon composite material to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12h to obtain the primary composite material. Dissolve 1-ethyl-3-methylimidazolium bromide in anhydrous ethanol to prepare an ionic liquid ethanol solution with a concentration of 0.2mol / L. Transfer the primary composite material to a vacuum dryer, set the vacuum degree to -0.09MPa, and vacuum for 30min. Under vacuum, slowly drip the ionic liquid ethanol solution into the vacuum dryer through a constant pressure dropping funnel to completely wet the primary composite material. The mass ratio of the primary composite material to the ionic liquid ethanol solution is 1:

10. A6: Maintain vacuum for 3 hours of soaking. After soaking, slowly restore normal pressure and continue soaking for 8 hours. After soaking, filter and wash 3 times with anhydrous ethanol. Then transfer the filter cake to a vacuum drying oven, set the temperature to 60℃ and the vacuum degree to -0.08MPa, and dry for 12 hours to obtain the intermediate composite material. A7: Weigh the intermediate composite material, conductive carbon black, and polyvinylidene fluoride, add them to the reactor, set the reactor stirrer speed to 300 rpm, and stir for 15 min to obtain a solid mixture, wherein the mass ratio of intermediate composite material, conductive carbon black, and polyvinylidene fluoride is 80:10:

10. Then add N-methylpyrrolidone, wherein the mass ratio of solid mixture to N-methylpyrrolidone is 1:5, set the stirrer speed to 800 rpm, and stir for 2 h to obtain the positive electrode slurry; A8: Transfer the positive electrode slurry to a vacuum degassing machine, set the vacuum level to -0.09 MPa, and degas for 30 minutes. After degassing, use a coating machine to evenly coat the slurry onto the titanium foil current collector, controlling the coating thickness to 150 μm. Transfer the coated electrode to a vacuum drying oven, set the temperature to 80℃, the vacuum level to -0.08 MPa, and dry for 12 hours. After drying, use a roller press to compact the material, controlling the compaction density to 1.2 g / cm³. 3 A porous carbon-supported bromine-manganese dioxide composite positive electrode sheet was obtained.

3. A porous carbon-supported hybrid capacitor battery according to claim 1, characterized in that, The method for preparing the electrodeposited zinc carbon cloth negative electrode includes the following steps: B1: After the carbon cloth is cut, it is immersed in acetone and ultrasonically cleaned for 15 minutes. After ultrasonic cleaning in acetone, it is transferred to anhydrous ethanol and ultrasonically cleaned for 15 minutes. After ultrasonic cleaning in anhydrous ethanol, it is transferred to deionized water and ultrasonically cleaned for 15 minutes again. After cleaning, it is transferred to a vacuum drying oven, the temperature is set to 60℃, and it is dried for 6 hours to obtain the pretreated carbon cloth. B2: An electrodeposition electrolyte was prepared by mixing 1 mol / L zinc sulfate solution and 1 mol / L sodium sulfate solution, with a volume ratio of 1:

1. Pretreated carbon cloth was used as the working electrode, and zinc foil as both the counter and reference electrodes. Constant current electrodeposition was employed, with a current density of 10 mA / cm². 2 The electrodeposition time was 30 min, and the electrolyte was continuously stirred slowly at a stirring rate of 50 rpm during the electrodeposition process. B3: After electrodeposition, the carbon cloth is removed, washed three times with deionized water, and then transferred to a vacuum drying oven at 40℃ for 4 hours to obtain electrodeposited zinc carbon cloth. Pyrrole is added to deionized water to prepare a 0.1 mol / L pyrrole solution, and ammonium persulfate is added to deionized water to prepare a 0.05 mol / L ammonium persulfate solution. The pyrrole solution and ammonium persulfate solution are mixed and stirred for 10 minutes to obtain the polymerization reaction solution, wherein the volume ratio of pyrrole solution to ammonium persulfate solution is 1:

1. B4: Immerse the electrodeposited zinc carbon cloth in the polymerization reaction solution, set the ice-water bath to control the reaction temperature at 4℃, and polymerize for 2 hours. After the reaction is complete, take out the carbon cloth, wash it 3 times with deionized water, and then transfer it to a vacuum drying oven, set the temperature at 40℃, and dry for 4 hours to obtain the electrodeposited zinc carbon cloth negative electrode.

4. A porous carbon-supported hybrid capacitor battery according to claim 1, characterized in that, The method for preparing the glass fiber composite diaphragm includes the following steps: C1: Glass fiber filter paper with a thickness of 0.3 mm and a pore size of 1 μm is selected as the substrate. After cutting, it is transferred to a vacuum drying oven, the temperature is set to 60℃, and it is dried for 4 hours to obtain a pretreated glass fiber membrane. C2: Weigh nano-silica, polyvinylidene fluoride and sodium carboxymethyl cellulose, add them to the reaction vessel, set the stirring speed of the reaction vessel to 300 rpm, and stir for 15 min to obtain a mixture, wherein the mass ratio of nano-silica, polyvinylidene fluoride and sodium carboxymethyl cellulose is 80:15:

5. Then add N-methylpyrrolidone, wherein the mass ratio of the mixture to N-methylpyrrolidone is 1:10, set the stirring speed to 800 rpm, and stir for 2 h to obtain the coating slurry; C3: Transfer the coating slurry to a vacuum degassing machine, set the vacuum degree to -0.09MPa, and degas for 30 minutes. After degassing, use a coating machine to evenly coat the slurry on one side of the pretreated glass fiber membrane. The coating thickness is controlled at 10µm. Transfer the coated membrane to a vacuum drying oven, set the temperature to 60℃, the vacuum degree to -0.08MPa, and dry for 12 hours. After drying, the primary glass fiber composite membrane is obtained. C4: Sulfonated polyether ether ketone was dissolved in dimethylacetamide to prepare a 5% casting solution. The stirrer was set to 400 rpm and stirred and dissolved in a 60°C water bath for 4 hours to obtain a homogeneous casting solution. Then, it was transferred to a vacuum degassing machine and degassed for 1 hour with a vacuum of -0.09 MPa. C5: After degassing, pour the casting solution into the coating tank and use a scraper to evenly coat the uncoated surface of the glass fiber filter paper composite membrane with the casting solution. The coating thickness is controlled at 20 μm. After coating, let it stand in the air for 30 seconds, and then immerse it in a deionized water coagulation bath. The coagulation bath temperature is 25°C and the film formation time in the coagulation bath is 10 min. C6: After the film is formed in the coagulation bath, it is washed three times with deionized water and then transferred to a vacuum drying oven. The temperature is set at 60℃ and the vacuum degree is -0.08MPa. After drying for 12 hours, a glass fiber composite membrane is obtained.

5. A porous carbon-loaded hybrid capacitor battery according to claim 1, characterized in that, The aqueous electrolyte is composed of the following components by mass percentage: 80% deionized water, 13.5% zinc sulfate, 5% zinc bromide, 1% manganese sulfate, 0.3% polyvinylpyrrolidone, and 0.2% sodium dodecyl sulfate.

6. A porous carbon-loaded hybrid capacitor battery according to claim 1, characterized in that, The method for preparing the aqueous electrolyte includes the following steps: D1: Weigh zinc sulfate, zinc bromide and manganese sulfate and add them to the reaction vessel. Add 90% of the total amount of deionized water according to the formula. Set the stirrer speed to 400 rpm and stir to dissolve for 30 minutes at room temperature to obtain the basic electrolyte. D2: Weigh sodium dodecyl sulfate and add it to 5% of the total amount of deionized water in the formula. Heat to 40°C and stir to dissolve to obtain a surfactant solution. Slowly add the surfactant solution to the basic electrolyte and continue stirring for 15 minutes to obtain the secondary electrolyte. D3: Add polyvinylpyrrolidone to 5% of the total amount of the formula in deionized water, stir and dissolve for 5 minutes to obtain a polyvinylpyrrolidone solution. Add the polyvinylpyrrolidone solution to the secondary electrolyte and continue stirring for 10 minutes. After stirring, filter through a 0.45 μm filter membrane to obtain an aqueous electrolyte.

7. The method for preparing a porous carbon-supported hybrid capacitor battery according to claim 1, characterized in that, Includes the following steps: S1: Cut the porous carbon-supported bromine-manganese dioxide composite positive electrode sheet and the electrodeposited zinc carbon cloth negative electrode sheet into the required sizes respectively. The positive electrode size is 50mm×50mm, the negative electrode size is 52mm×52mm, and the glass fiber filter paper composite diaphragm is cut into 60mm×60mm. S2: Stack the positive electrode, glass fiber filter paper composite diaphragm and negative electrode in sequence, with the functional coating of the diaphragm facing the positive electrode. Weld nickel tabs to the positive and negative electrode respectively, and encapsulate them with aluminum-plastic film, leaving a liquid injection port. S3: Transfer the packaged battery to a vacuum oven, set the temperature to 60℃ and the vacuum degree to -0.09MPa, and dry for 12 hours. After drying, transfer it to a glove box. S4: In the glove box, inject 2ml of aqueous electrolyte through the injection port. After the injection is completed, seal the glove box with a vacuum sealer and let it stand for 12 hours to obtain a porous carbon-loaded hybrid capacitor battery.

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