CN-122000207-A - Porous carbon-loaded hybrid capacitor battery and preparation method thereof

CN122000207ACN 122000207 ACN122000207 ACN 122000207ACN-122000207-A

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 invention discloses a porous carbon-loaded hybrid capacitor battery, which consists of a porous carbon-loaded bromine-manganese dioxide composite material positive electrode, an electrodeposited zinc carbon cloth negative electrode, a glass fiber filter paper composite diaphragm and a water-based electrolyte, wherein a physical limit of bromine species is realized through multistage porous biomass carbon, a self-repairing interface is formed by dynamically capturing halogen polymers through biomimetic mineralization growth of manganese dioxide nano sheets, a shuttle effect is restrained by anchoring the bromine species through low-pressure impregnation of ionic liquid, 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 water-based zinc ion hybrid capacitor battery by matching with a multidimensional synergistic design of dendrite inhibition by negative electrode coating, modified diaphragm ion selection and electrolyte bromine source supplementation.

Inventors

YAN XIA
RONG YU
Jia Qiuhan
WANG PENG
WANG MIN
Zhou Bochen
LI DONGMING
LV XIANG

Assignees

固安海若斯新材料科技有限公司

Dates

Publication Date: 20260508
Application Date: 20260325

Claims (7)

1. A porous carbon-loaded hybrid capacitor battery is characterized by comprising a porous carbon-loaded bromine-manganese dioxide composite positive electrode, an electrodeposited zinc carbon cloth negative electrode, a glass fiber composite diaphragm and an aqueous electrolyte.
2. The porous carbon-supported hybrid capacitor battery of claim 1, wherein the preparation method of the porous carbon-supported bromine-manganese dioxide composite positive electrode comprises the following steps: A1, placing durian shells and coconut shells in a vacuum drying oven, setting the temperature to be 80 ℃, the vacuum degree to be-0.08 MPa, and drying for 12 hours, wherein the mass ratio of the durian shells to the coconut shells is 1:1, transferring the durian shells to a pulverizer for pulverization after drying, sieving the pulverized product with a 60-mesh screen to obtain biomass powder, mixing choline chloride and urea into a reaction kettle, heating the mixture to 80 ℃ for stirring and dissolving to obtain a eutectic solvent, wherein the molar ratio of the choline chloride to the urea is 1:2, adding the biomass powder into the eutectic solvent, setting the mass ratio of the biomass powder to the eutectic solvent to be 1:10, setting the rotating speed of a stirrer to be 200rpm, stirring and treating the mixture for 3 hours under the water bath condition of 90 ℃, filtering the mixture after the treatment, and washing the mixture with deionized water for 3 times to obtain a pretreated biomass filter cake; A2, transferring the pretreated biomass filter cake into a vacuum drying oven, setting the temperature to be 60 ℃, the vacuum degree to be-0.08 MPa, drying for 12 hours to obtain pretreated biomass, transferring the pretreated biomass into a hydrothermal reaction kettle, adding deionized water, wherein the mass ratio of the pretreated biomass to the deionized water is 1:8, setting the reaction temperature to be 200 ℃, the reaction time to be 8 hours, naturally cooling to room temperature after the reaction is finished, filtering and collecting a solid product, and washing 3 times with the deionized water to obtain hydrothermal coke; A3, transferring the hydrothermal coke into a vacuum drying oven, setting the temperature to be 80 ℃, the vacuum degree to be-0.08 MPa, drying for 12 hours, transferring into a tube furnace after drying, heating to 850 ℃ at a temperature rising rate of 5 ℃ per minute under the protection of nitrogen, then switching to a CO 2 atmosphere, activating at a constant temperature for 1.5 hours at a gas flow rate of 150ml per minute, naturally cooling to room temperature after the activation is completed, obtaining multi-level porous biomass carbon powder, adding the multi-level porous biomass carbon powder into a Tris-HCl buffer solution with the pH of 8.5, wherein the mass ratio of the multi-level porous biomass carbon powder to the Tris-HCl buffer solution is 1:50, and performing ultrasonic dispersion for 15 minutes to obtain carbon dispersion; adding dopamine hydrochloride into the carbon dispersion liquid, wherein the mass ratio of the multi-pore biomass carbon powder to the dopamine hydrochloride is 5:1, setting the rotating speed of a stirrer to be 300rpm, stirring at room temperature for reaction for 8 hours, centrifuging after the reaction is finished, washing with deionized water for 3 times to obtain a polydopamine modified carbon material, adding the polydopamine modified carbon material into 0.02mol/L potassium permanganate solution, wherein the mass ratio of the polydopamine modified carbon material to the potassium permanganate solution is 1:80, setting the rotating speed of the stirrer to be 200rpm, stirring at 60 ℃ for reaction for 3 hours under the water bath condition, centrifuging after the reaction is finished, washing with deionized water for 3 times to obtain a manganese dioxide-carbon composite material; A5, transferring the manganese dioxide-carbon composite material into a vacuum drying oven, setting the temperature to be 60 ℃, the vacuum degree to be-0.08 MPa, and drying for 12 hours to obtain a primary composite material, dissolving 1-ethyl-3-methylimidazole bromide salt into absolute ethyl alcohol to prepare an ionic liquid ethanol solution with the concentration of 0.2mol/L, transferring the primary composite material into the vacuum drying oven, setting the vacuum degree to be-0.09 MPa, vacuumizing for 30 minutes, and slowly dripping the ionic liquid ethanol solution into the vacuum drying oven through a constant-pressure dropping funnel in the vacuum state to completely infiltrate the primary composite material, wherein the mass ratio of the primary composite material to the ionic liquid ethanol solution is 1:10; A6, keeping a vacuum state for soaking for 3 hours, slowly recovering normal pressure after soaking for 8 hours, filtering after soaking, washing for 3 times by using absolute ethyl alcohol, transferring a filter cake into a vacuum drying oven, setting the temperature to be 60 ℃, and drying for 12 hours at the vacuum degree of minus 0.08MPa to obtain a medium-grade composite material; A7, weighing the intermediate composite material, the conductive carbon black and the polyvinylidene fluoride, adding the intermediate composite material, the conductive carbon black and the polyvinylidene fluoride into a reaction kettle, setting the rotating speed of a stirrer of the reaction kettle to be 300rpm, stirring for 15min to obtain a solid mixture, wherein the mass ratio of the intermediate composite material to the conductive carbon black to the polyvinylidene fluoride is 80:10:10, then adding N-methylpyrrolidone, wherein the mass ratio of the solid mixture to the N-methylpyrrolidone is 1:5, setting the rotating speed of the stirrer to be 800rpm, and stirring and mixing for 2h to obtain anode slurry; A8, transferring the anode slurry into a vacuum deaeration machine, setting the vacuum degree to be-0.09 MPa, deaerating for 30min, uniformly coating the slurry on a titanium foil current collector by using a coating machine after deaeration is completed, controlling the coating thickness to be 150um, transferring the coated pole piece into a vacuum drying box, setting the temperature to be 80 ℃, setting the vacuum degree to be-0.08 MPa, drying for 12h, compacting by using a roller press after drying is completed, and controlling the compaction density to be 1.2g/cm 3 , thus obtaining the porous carbon-supported bromine-manganese dioxide composite anode pole piece.
3. The porous carbon-supported hybrid capacitor battery according to claim 1, wherein the preparation method of the electrodeposited zinc-carbon cloth negative electrode comprises the following steps: b1, soaking carbon cloth into acetone for ultrasonic cleaning for 15min after cutting, transferring the carbon cloth into absolute ethyl alcohol after ultrasonic cleaning in the acetone is finished, repeating ultrasonic cleaning for 15min, transferring the carbon cloth into deionized water after ultrasonic cleaning in the absolute ethyl alcohol is finished, performing ultrasonic cleaning for 15min again, transferring the carbon cloth into a vacuum drying oven after cleaning, setting the temperature to be 60 ℃, and drying for 6h to obtain pretreated carbon cloth; B2, uniformly mixing 1mol/L zinc sulfate solution and 1mol/L sodium sulfate solution to prepare an electrodeposited electrolyte, wherein the volume ratio of the zinc sulfate solution to the sodium sulfate solution is 1:1, pretreated carbon cloth is used as a working electrode, zinc foil is used as a counter electrode and a reference electrode, constant current electrodepositing is adopted, the current density is set to be 10mA/cm 2 , the electrodepositing time is 30min, and the electrolyte is continuously stirred slowly at the stirring speed of 50rpm in the electrodepositing process; Taking out the carbon cloth after the electro-deposition is finished, washing the carbon cloth with deionized water for 3 times, then transferring the carbon cloth into a vacuum drying oven, setting the temperature to 40 ℃, and drying for 4 hours to obtain electro-deposited zinc carbon cloth, adding pyrrole into the deionized water to prepare a pyrrole solution of 0.1mol/L, adding ammonium persulfate into the deionized water to prepare a ammonium persulfate solution of 0.05mol/L, and mixing and stirring the pyrrole solution and the ammonium persulfate solution for 10 minutes to obtain a polymerization reaction solution, wherein the volume ratio of the pyrrole solution to the ammonium persulfate solution is 1:1; and B4, immersing the electrodeposited zinc carbon cloth in a polymerization reaction liquid, setting an ice-water bath to control the reaction temperature to be 4 ℃, carrying out polymerization reaction for 2 hours, taking out the carbon cloth after the reaction is finished, washing the carbon cloth with deionized water for 3 times, transferring the carbon cloth into a vacuum drying oven, setting the temperature to be 40 ℃, and drying the carbon cloth for 4 hours to obtain the electrodeposited zinc carbon cloth negative electrode.
4. The porous carbon-loaded hybrid capacitor cell of claim 1, wherein the method for preparing the glass fiber composite separator comprises the following steps: Selecting glass fiber filter paper with the thickness of 0.3mm and the aperture of 1um as a base material, transferring the base material into a vacuum drying oven after cutting, setting the temperature to be 60 ℃, and drying for 4 hours to obtain a pretreated glass fiber diaphragm; Weighing nano silicon dioxide, polyvinylidene fluoride and sodium carboxymethyl cellulose, adding the nano silicon dioxide, the polyvinylidene fluoride and the sodium carboxymethyl cellulose into a reaction kettle, setting the rotating speed of a stirrer of the reaction kettle to be 300rpm, stirring for 15min to obtain a mixed material, wherein the mass ratio of the nano silicon dioxide to the polyvinylidene fluoride to the sodium carboxymethyl cellulose is 80:15:5, then adding N-methylpyrrolidone, wherein the mass ratio of the mixed material to the N-methylpyrrolidone is 1:10, setting the rotating speed of the stirrer to be 800rpm, and stirring and mixing for 2h to obtain a coating slurry; Transferring the coating slurry into a vacuum deaeration machine, setting the vacuum degree to be-0.09 MPa, deaerating for 30min, uniformly coating the slurry on one side surface of a pretreated glass fiber diaphragm by using a coating machine after deaeration is completed, controlling the coating thickness to be 10um, transferring the coated diaphragm into a vacuum drying oven, setting the temperature to be 60 ℃, setting the vacuum degree to be-0.08 MPa, drying for 12h, and obtaining a primary glass fiber composite diaphragm after drying; dissolving sulfonated polyether-ether-ketone in dimethylacetamide to prepare 5% casting solution, setting the rotating speed of a stirrer to be 400rpm, stirring and dissolving for 4 hours under the water bath condition of 60 ℃ to obtain homogeneous casting solution, then transferring the homogeneous casting solution into a vacuum deaeration machine, setting the vacuum degree to be-0.09 MPa, and performing deaeration treatment for 1 hour; Pouring the casting solution into a coating tank after the defoaming is finished, uniformly coating the casting solution on an uncoated surface of the glass fiber filter paper composite membrane by using a scraper, controlling the coating thickness to be 20 mu m, standing for 30s in air after the coating is finished, and then immersing in deionized water for coagulating bath, wherein the coagulating bath temperature is 25 ℃, and the coagulating bath film forming time is 10min; And C6, washing 3 times by using deionized water after the coagulation bath film forming is finished, transferring into a vacuum drying oven, setting the temperature to be 60 ℃, setting the vacuum degree to be minus 0.08MPa, and drying for 12 hours to obtain the glass fiber composite membrane.
5. The porous carbon-loaded hybrid capacitor battery according to claim 1, wherein the aqueous electrolyte comprises, by mass, 80% deionized water, 13.5% zinc sulfate, 5% zinc bromide, 1% manganese sulfate, 0.3% polyvinylpyrrolidone, and 0.2% sodium dodecyl sulfate.
6. The porous carbon-supported hybrid capacitor cell of claim 1, wherein the method for preparing the aqueous electrolyte comprises the steps of: d1, weighing zinc sulfate, zinc bromide and manganese sulfate, adding the zinc sulfate, the zinc bromide and the manganese sulfate into a reaction kettle, adding deionized water accounting for 90% of the total formula, setting the rotating speed of a stirrer to be 400rpm, and stirring and dissolving for 30min at room temperature to obtain a basic electrolyte; d2, weighing sodium dodecyl sulfate, adding the sodium dodecyl sulfate into deionized water accounting for 5 percent of the total formula, heating to 40 ℃, stirring and dissolving to obtain a surfactant solution, slowly adding the surfactant solution into a basic electrolyte, and continuously stirring for 15 minutes to obtain a secondary electrolyte; And D3, adding polyvinylpyrrolidone into deionized water accounting for 5% of the total formula, stirring and dissolving for 5min to obtain polyvinylpyrrolidone solution, adding the polyvinylpyrrolidone solution into the secondary electrolyte, continuously stirring for 10min, and filtering through a 0.45um filter membrane after stirring is completed to obtain the water-based electrolyte.
7. The method for preparing a porous carbon-supported hybrid capacitor cell according to claim 1, comprising the steps of: S1, respectively cutting a porous carbon bromine-manganese dioxide loaded composite material positive electrode plate and an electrodeposited zinc carbon cloth negative electrode plate into required sizes, wherein the positive electrode size is 50mm multiplied by 50mm, the negative electrode size is 52mm multiplied by 52mm, and a glass fiber filter paper composite diaphragm is cut into 60mm multiplied by 60mm; S2, sequentially stacking a positive electrode plate, a glass fiber filter paper composite diaphragm and a negative electrode plate, wherein a functional coating of the diaphragm faces the positive electrode plate, the positive electrode plate and the negative electrode plate are respectively welded with nickel lugs, an aluminum plastic film is adopted for packaging, and a liquid injection port is reserved; S3, transferring the packaged battery into a vacuum oven, setting the temperature to be 60 ℃, and drying the battery for 12 hours under the vacuum degree of-0.09 MPa, and transferring the battery into a glove box after the drying is finished; and S4, injecting water-based electrolyte into the glove box through a liquid injection port, wherein the liquid injection amount is 2ml, sealing by using a vacuum sealing machine after the liquid injection is completed, and standing for 12 hours to obtain the porous carbon-loaded mixed capacitor battery.

Description

Porous carbon-loaded hybrid capacitor battery and preparation method thereof Technical Field 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. Background In the field of water-based zinc ion capacitor batteries, manganese dissolution and halogen shuttle effect of a positive electrode material are two core problems restricting development of the water-based zinc ion capacitor battery, manganese ions are easily dissolved out due to Jahn-Teller effect in the charging and discharging process of a manganese dioxide positive electrode, capacity is fast attenuated, and circulation stability is poor, and when halogen conversion reaction is introduced to improve energy density, generated halogen polymers easily diffuse to a negative electrode through a diaphragm, serious shuttle effect is caused, coulomb efficiency is reduced and self-discharging is aggravated, so that the dual requirements of high energy density and long circulation life are difficult to be met by a traditional single modification strategy. The research shows that the physical limiting area, the chemical anchoring area and the electrochemical capturing area are cooperatively designed on the electrode material, so that the limitation of the traditional modification technology can be effectively broken through, however, the existing technical scheme adopts a simple blending and layering coating mode, the accurate integration and orderly cooperation of all mechanisms cannot be realized, and particularly, a multistage pore carrier capable of integrally constructing a halogen anchoring site, a manganese-based active substance and a self-repairing interface is lacked, so that all functional modules mutually interfere in the circulation process, and the cooperation fails, cannot be synchronously and orderly activated in the electrochemical environment and exert the cooperation effect, and severely restricts the practical process of the water system zinc ion capacitor battery. The present invention provides a solution to the above problems. Disclosure of Invention The invention aims to provide a porous carbon-loaded hybrid capacitor battery and a preparation method thereof, which have the remarkable advantages of excellent performance and ultra-long cycle life. The invention adopts the following technical scheme that the porous carbon-loaded mixed capacitor battery consists of a porous carbon-loaded bromine-manganese dioxide composite positive electrode, an electrodeposited zinc carbon cloth negative electrode, a glass fiber composite diaphragm and an aqueous electrolyte; further, the preparation method of the porous carbon-supported bromine-manganese dioxide composite anode comprises the following steps: A1, placing durian shells and coconut shells in a vacuum drying oven, setting the temperature to be 80 ℃, the vacuum degree to be-0.08 MPa, and drying for 12 hours, wherein the mass ratio of the durian shells to the coconut shells is 1:1, transferring the durian shells to a pulverizer for pulverization after drying, sieving the pulverized product with a 60-mesh screen to obtain biomass powder, mixing choline chloride and urea into a reaction kettle, heating the mixture to 80 ℃ for stirring and dissolving to obtain a eutectic solvent, wherein the molar ratio of the choline chloride to the urea is 1:2, adding the biomass powder into the eutectic solvent, setting the mass ratio of the biomass powder to the eutectic solvent to be 1:10, setting the rotating speed of a stirrer to be 200rpm, stirring and treating the mixture for 3 hours under the water bath condition of 90 ℃, filtering the mixture after the treatment, and washing the mixture with deionized water for 3 times to obtain a pretreated biomass filter cake; A2, transferring the pretreated biomass filter cake into a vacuum drying oven, setting the temperature to be 60 ℃, the vacuum degree to be-0.08 MPa, drying for 12 hours to obtain pretreated biomass, transferring the pretreated biomass into a hydrothermal reaction kettle, adding deionized water, wherein the mass ratio of the pretreated biomass to the deionized water is 1:8, setting the reaction temperature to be 200 ℃, the reaction time to be 8 hours, naturally cooling to room temperature after the reaction is finished, filtering and collecting a solid product, and washing 3 times with the deionized water to obtain hydrothermal coke; A3, transferring the hydrothermal coke into a vacuum drying oven, setting the temperature to be 80 ℃, the vacuum degree to be-0.08 MPa, drying for 12 hours, transferring into a tube furnace after drying, heating to 850 ℃ at a temperature rising rate of 5 ℃ per minute under the protection of nitrogen, then switching to a CO 2 atmosphere, activating at a constant temperature for 1.5 hours at a gas flow rate of 150ml per minute, naturally cooling to room temperature after the activation is completed, obtaini