CN111508725A - Preparation of self-supporting carbon material and water system hybrid high-voltage capacitor prepared from self-supporting carbon material - Google Patents
Preparation of self-supporting carbon material and water system hybrid high-voltage capacitor prepared from self-supporting carbon material Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 44
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000011787 zinc oxide Substances 0.000 claims description 22
- 239000007772 electrode material Substances 0.000 claims description 20
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- -1 zinc oxide compound Chemical class 0.000 claims description 11
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
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- 238000005520 cutting process Methods 0.000 claims description 5
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- 238000007605 air drying Methods 0.000 claims description 4
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- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
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- 238000007664 blowing Methods 0.000 claims description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 238000011065 in-situ storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 229910052573 porcelain Inorganic materials 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000010406 cathode material Substances 0.000 description 1
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- 239000003989 dielectric material Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses a preparation method of a self-supporting carbon material and a symmetrical water system hybrid high-voltage capacitor prepared by the same; the invention firstly prepares the self-supporting carbon material through hydrothermal reaction, solution dipping and high-temperature carbonization, and then adopts the processes of solution soaking, rotary evaporation and ice water quenching to prepare the carbon-polymer composite electrode. The carbon-polymer dielectric composite electrode can effectively isolate the contact of electrons and water, thereby improving the working voltage of a water system electrolyte, simultaneously, the dielectric layer can enhance the capacitance performance of the capacitor in the charging and discharging processes, and the carbon-polymer dielectric composite electrode is suitable for preparing a high-energy density capacitor.The carbon-polymer composite electrode is assembled into a novel symmetrical water system hybrid high-voltage capacitor, and the voltage window can be improved to 2V at 0.4mA/cm2The specific area capacity of the current reaches 333.3mF/cm2Compared with the carbon material electrode without the polymer electrolyte, the energy density of the novel capacitor is improved by 1300%.
Description
Technical Field
The invention belongs to the technical field of energy storage material preparation, relates to preparation of a carbon material and a high-voltage capacitor prepared from the carbon material, and particularly relates to preparation of a self-supporting carbon material and a symmetric water system hybrid high-voltage capacitor prepared from the self-supporting carbon material.
Background
With the rise of electronic automobiles, the safety and the quick charging performance of energy storage devices become more and more important. The super capacitor has the advantages of high power density, long cycle life, short charging time and the like, and is the most promising secondary battery to replace an energy storage device at present. Importantly, water-based electrolytes would be a better choice for supercapacitors than flammable organic solutions and expensive ionic liquid electrolytes, in view of safety, cost and recycling issues. However, the low energy density of water-based supercapacitors remains a great challenge, limiting their spread in practical applications.
According to the formula of the energy density of the capacitor,the energy density (E) is dependent on the specific capacitance (C) and the operating voltage (V). Increasing the energy density of a supercapacitor can only be achieved by increasing the capacitor capacity or operating voltage. Since the theoretical water decomposition voltage is 1.23V, it is critical to realize a high-pressure water system supercapacitor to suppress water decomposition. At present, there are three methods for increasing the operating voltage of an aqueous capacitor. The method comprises the following steps: using highly concentrated salt solutions, e.g. 1M Na2SO4The working voltage can reach 1.8V (Feng H, Hu H, et al. high structural carbon derived from baseband water: a simple and effective synthesis and its improved performance for high-performance supercapacitors [ J]Journal of Power Sources,302(2016), pp.164-173 method 2. Using asymmetric anode and cathode materials, water decomposition is inhibited, and the working voltage can be usually more than 2V (Xiong T, Teck L eong Tan, et al, harmonic energy and power sensitivity heated 2.7V of asymmetric aqueous supercapacitors [ J]Advanced Energy materials.2018,8,1702630). The method 3 comprises the following steps: the high-concentration salt-in-water solution is used for reducing the kinetics of the water splitting reaction, and the voltage can even reach more than 3V (Yuki Yamada, Kenji Usui, Keit)aroSodeyama,Hydrate-melt electrolytes for high-energy-density aqueous batteries[J]Nature Energy,2016,1: 16129). However, for carbon materials, the only commercial capacitor electrode materials, only methods 1 and 3 are applicable. The high salt solution concentration of method 1 generally results in low specific capacitance and low conductivity, reducing the electrochemical performance of the capacitor. In the method 3, the salt-coated aqueous solution has high viscosity and large ion cluster size, so that the method has low capacity and high resistance, and is extremely high in cost, so that the method is not suitable for wide production at present. Prior to the present invention, there was no method to assemble symmetric supercapacitors from carbon materials in 6M KOH conventional electrolyte to achieve operating voltages above 1V.
Disclosure of Invention
The invention provides a self-supporting carbon material preparation method and a symmetrical water system hybrid high-voltage capacitor prepared by the self-supporting carbon material, aiming at the problems that a water system capacitor is low in energy density and difficult to practically apply. The invention prepares a brand new hybrid super capacitor for the first time so as to improve the energy density of the water system super capacitor. Firstly, the dielectric prevents the contact of water and electrons in the process of charging and discharging to inhibit the decomposition of water, thereby improving the working voltage; meanwhile, the dielectric material can store energy through dipole overturning in the charging and discharging processes. It is worth noting that the polarized polymer chain segment can be used as an active site for ion adsorption, thereby improving the capacitance of the capacitor. PVDF and PVDF-based copolymers have high dielectric constants and high breakdown strengths, and are considered ideal candidates for next-generation polymer capacitors. The invention prepares the electrode material of the hybrid capacitor by using a carbon material and PVDF-based dielectric polymer composite electrode. The invention has higher use value and is the optional development direction of the next generation double high capacitor.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a self-supporting carbon material with high openness and high specific surface, which comprises the following steps:
A. growing zinc oxide of a nano array on the surface of the hydrophilic carbon cloth through a hydrothermal reaction (the specific method is referred to as ACSAppl. Mater. interfaces 2018,10, 3549-3561); the zinc oxide of the nano array can be used as a template and an activator for the in-situ growth of a carbon material in the next step;
B. b, soaking the carbon cloth zinc oxide compound grown in the step A in a carbon source solution for a certain time, and then taking out and drying;
C. heating the dried carbon cloth zinc oxide compound to 150-plus-180 ℃ in the inert gas atmosphere, preserving heat (melting a carbon source to uniformly coat the surface of the zinc oxide), then heating to 800-plus-1000 ℃, preserving heat (preparing a carbon material by carbonization), naturally cooling to room temperature, and taking out;
D. and D, putting the carbon cloth zinc oxide compound taken out in the step C into an acid solution again to wash away zinc oxide, and repeatedly washing the carbon cloth zinc oxide compound to be neutral through deionized water to obtain the self-supporting carbon material.
The self-supporting carbon material prepared by the method has the characteristics of high open specific surface area, high conductivity and integration of an active material and a current collector, and does not need to use a binder.
Preferably, in the step B, the concentration of the carbon source solution is 1M, and the soaking time is 12 hours; the drying temperature is 80 ℃, and the drying time is 1 hour.
Preferably, in the step C, the inert gas is argon, the introduction amount is 40m L/min, the heating rate for heating to 150-.
Preferably, in step B, the carbon source solution is a glucose solution.
Preferably, in the step C, the temperature is maintained at 150-180 ℃ for 1 hour, and at 800-1000 ℃ for 2 hours.
Preferably, in step D, the acid solution is at least one of a hydrochloric acid solution and a sulfuric acid solution.
The present invention provides a highly open, high specific surface area, self-supporting carbon material prepared according to the aforementioned method.
The invention provides a carbon-polymer composite electrode material prepared from the self-supporting carbon material, which comprises the self-supporting carbon material and a polymer dielectric layer coated on the self-supporting carbon material.
The invention provides a preparation method of the carbon-polymer composite electrode material, which comprises the following steps:
s1, cutting the self-supporting carbon material into an electrode shape;
s2, adding the fluorine-containing polymer into the N, N-dimethylformamide solution, stirring and dissolving to obtain a solution a;
s3, putting the sheared self-supporting carbon material into the solution a for soaking, performing rotary evaporation under a vacuum condition until the solution is dried to obtain a composite material, and then naturally drying;
and S4, drying the composite material processed in the step S3 by air blowing, taking out, and quenching in ice water to obtain the carbon-polymer composite electrode material.
Preferably, in step S2, the fluoropolymer includes PVDF-HFP, PVDF; the temperature for stirring and dissolving is 80 ℃;
in step S3, the temperature of the rotary evaporation is 80 ℃; the natural drying time is 24 hours;
in step S4, the temperature of the forced air drying was 200 ℃ and the drying time was 10 minutes.
The invention firstly prepares the self-supporting carbon material through hydrothermal reaction, solution impregnation and high-temperature carbonization, and then prepares the carbon-polymer composite electrode material by adopting the processes of solution soaking, rotary evaporation and ice water quenching. Firstly, growing a zinc oxide rod array on the surface of carbon cloth through hydrothermal reaction, wherein the zinc oxide rod can be used as a template and an activator for in-situ growth of a carbon material in the next step, the obtained carbon material has a mutually connected and fluctuant carbon sheet structure, and then forming a compact and hydrophobic dielectric layer on the surface of the carbon material by using a polymer. The carbon-polymer dielectric composite electrode prepared by the invention can effectively isolate the contact of electrons and water, thereby improving the working voltage of a water system electrolyte, and meanwhile, the dielectric layer can enhance the capacitance performance of the capacitor in the charging and discharging processes, so that the carbon-polymer dielectric composite electrode is suitable for preparing a high-energy density capacitor.
The invention provides a novel symmetrical water system hybrid high-voltage capacitor containing the carbon-polymer composite electrode material, which comprises the step of assembling the carbon-polymer composite electrode material, KOH electrolyte and a cellulose diaphragm to obtain the symmetrical water system hybrid high-voltage capacitor.
Compared with the prior art, the invention has the following beneficial effects:
1. the template carbon material grows on the surface of the carbon cloth in situ, the obtained carbon material has the self-supporting characteristic, can be directly used as an electrode material, and avoids the use of a binder compared with a commercial powdery carbon material. Meanwhile, the continuously opened surface is more beneficial to the adhesion of polymer dielectric, the surface area of dielectric energy storage is increased, and the capacity of the capacitor is further increased.
2. The fluoropolymer dielectric effectively blocks electrons from contacting water, increasing the operating voltage of the capacitor. Meanwhile, in the charging and discharging process, the fluoropolymer dielectric has a high dielectric constant, energy can be stored through dipole turnover, and in addition, the polymer after dipole turnover can be used as an active site for ion adsorption, so that the capacitance of the capacitor is improved.
3. As an electrode material of a capacitor, the carbon-polymer composite electrode shows good electrochemical performance, and in 6M KOH electrolyte, the working voltage can reach 2V and is 0.4mA/cm2The specific volume of the alloy reaches 333.3mF/cm under the current density2(ii) a Compared with a pure carbon material electrode without the polymer dielectric medium, the working voltage is improved by 2.5 times, the capacity is improved by 2.14 times, and the energy density is improved by 13 times.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a scanning electron microscope image of a rod array of zinc oxide grown on a carbon cloth prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a self-supporting carbon material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope of the cross section of the carbon-PVDF-HFP composite electrode prepared in example 1 of the present invention;
FIG. 4 is an optical photograph of the soft-package symmetrical water-based hybrid high-voltage capacitor prepared in example 1 of the present invention;
FIG. 5 is a scanning electron microscope image of a carbon-PVDF composite electrode prepared in example 2 of the present invention before quenching;
FIG. 6 is a scanning electron microscope image of a carbon-PVDF composite electrode prepared in example 2 of the present invention after quenching;
fig. 7 is a graph of energy power density for a carbon-polymer composite electrode and a pure carbon electrode prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The specific preparation process of the carbon-PVDF-HFP symmetrical water system hybrid high-voltage capacitor is as follows:
1. preparation of self-supporting carbon materials
1.1 measuring 70m L deionized water, adding 10m L30% wt hydrogen peroxide solution and 10m L28% wt ammonia solution to prepare solution A, and cutting carbon cloth into 3 x 3cm pieces2Taking 4 tablets, adding the tablets into the solution A, packaging by using a preservative film, heating at 80 ℃ for 12 hours, taking out, repeatedly washing by using deionized water, and putting into a beaker filled with the deionized water for use;
1.2 soaking a carbon cloth in 0.005M zinc acetate for 30 minutes, then transferring the carbon cloth to a 200 ℃ forced air drying oven for 30 minutes to form a ZnO seed layer, preparing 80M L0.05M hexamethylenetetramine and 0.05M zinc nitrate hexahydrate solution, adding 2M L ammonia water, stirring the solution for 30 minutes to form a solution B, putting the dried carbon cloth into the solution B, transferring the solution B to a hydrothermal reaction kettle, and placing the hydrothermal reaction kettle in the 90 ℃ forced air drying oven for 4 hours;
1.3 soaking the grown carbon cloth zinc oxide compound in 100M L and 1M glucose solution for 12 hours, taking out and placing in a blast drying oven, and drying at 80 ℃ for 1 hour;
1.4 putting the dried carbon cloth zinc oxide compound into a porcelain boat, placing the porcelain boat in a tube furnace, heating to 160 ℃ under 40m L/min argon atmosphere at a heating rate of 1 ℃/min for 1 hour, then heating to 900 ℃, at a heating rate of 5 ℃/min for 2 hours, naturally cooling to room temperature, and taking out;
1.5 the carbon cloth zinc oxide compound taken out of the tube furnace is put into 200M L and 1M HCl for 12 hours to wash away the zinc oxide, and then the compound is repeatedly washed by deionized water to be neutral, and the compound is naturally dried to obtain the self-supporting carbon material (the scanning electron microscope picture is shown in figure 2).
2. Preparation of carbon-PVDF-HFP composite electrode
2.1 cutting the carbon material prepared in step 1 into the shape of an electrode (1.5 x 2.8 cm)2);
2.2 taking 0.15g of PVDF-HFP, adding the PVDF-HFP into a 20m L N, N-dimethylformamide solution, and stirring and dissolving at the temperature of 80 ℃ to obtain a solution a;
2.3 soaking the electrode material in the solution a, performing rotary evaporation at 80 ℃ until the solution becomes dry, taking out the obtained composite material, placing the composite material in a glass culture dish, and naturally drying for 24 hours;
2.4 placing the composite material in a vacuum drying oven at 200 ℃ for 10 minutes, taking out, immediately putting into ice water, and quenching to obtain the carbon-polymer composite electrode material (the scanning electron microscope image of which is shown in figure 3).
3. Assembly of symmetric water system hybrid high-voltage capacitor
And (3) packaging the carbon-PVDF-HFP composite material obtained in the step (2) by using a cellulose diaphragm and an aluminum plastic film, and assembling a soft-package symmetrical water system hybrid high-voltage capacitor by using 6M KOH as an electrolyte (an optical photograph is shown in FIG. 4).
4. Preparation of comparative sample carbon supercapacitor
And (3) assembling the soft-package symmetrical water system hybrid high-voltage capacitor by using the carbon material obtained in the step (1) as an electrode, using a cellulose diaphragm, packaging by using an aluminum plastic film and using 6MKOH as an electrolyte.
As shown in FIG. 7, in 6M KOH electrolyteCompared with a carbon material electrode without the polymer electrolyte, the energy density of the capacitor with the composite dielectric is increased by 1300 percent; the working voltage can reach 2V and is 0.4mA/cm2The specific volume of the alloy reaches 333.3mF/cm under the current density2(ii) a The voltage window of the carbon material without the polyelectrolyte is only 0.8V, and the specific volume under the same current density is only 156.5mF/cm2. Compared with a pure carbon material electrode without the polymer dielectric, the working voltage is improved by 2.5 times, and the capacity is improved by 2.14 times.
Example 2
The specific preparation process of the carbon-PVDF symmetrical water system hybrid high-voltage capacitor is as follows:
1. the preparation of the self-supporting carbon material was consistent with example 1.
2. Preparation of carbon-PVDF composite electrode
2.1 cutting the carbon material prepared in step 1 into the shape of an electrode (1.5 x 2.8 cm)2);
2.2 taking 0.15g of PVDF, adding the PVDF into a 20m L N, N-dimethylformamide solution, stirring and dissolving at the temperature of 80 ℃ to obtain a solution b;
2.3 soaking the electrode material in the solution b, performing rotary evaporation at 80 ℃ until the solution becomes dry, taking out the obtained composite material, placing the composite material in a glass culture dish, and naturally drying for 24 hours (the scanning electron microscope image is shown in figure 5);
2.4 placing the composite material in a vacuum drying oven at 200 ℃ for 10 minutes, taking out, immediately putting into ice water, and quenching to obtain the carbon-polymer composite electrode material (the scanning electron microscope image of which is shown in FIG. 6).
3. Assembly of symmetric water system hybrid high-voltage capacitor
And (3) taking the carbon-PVDF composite material obtained in the step (2) as an electrode, using a cellulose diaphragm, packaging by using an aluminum plastic film, and assembling into a soft-package symmetrical water system hybrid high-voltage capacitor by taking 6MKOH as electrolyte.
The soft-package symmetrical water system hybrid high-voltage capacitor prepared in the embodiment has the working voltage of 2V and 0.4mA/cm in 6M KOH electrolyte2Under the current density, the specific volume reaches 298.2mF/cm2(ii) a Compared with pure carbon material without added polymer dielectricThe working voltage of the material electrode is improved by 2.5 times, the capacity is improved by 1.9 times, and the energy density is improved by 11.8 times.
It should be noted that such a capacitor cannot be prepared without using the self-supporting carbon material prepared by the method of this embodiment, because the entire electrode is coated with the fluoropolymer material in the method, and if the conventional carbon material is used, the current collector cannot be coated, and the hydrogen evolution and oxygen evolution reactions occur on the current collector.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A preparation method of an integrated self-supporting carbon material with a high open specific surface area is characterized by comprising the following steps:
A. growing zinc oxide of a nano array on the surface of the hydrophilic carbon cloth through a hydrothermal reaction;
B. b, soaking the carbon cloth zinc oxide compound grown in the step A in a carbon source solution for a certain time, and then taking out and drying;
C. heating the dried carbon cloth zinc oxide compound to 150-;
D. and D, putting the carbon cloth zinc oxide compound taken out in the step C into an acid solution again to wash away zinc oxide, and repeatedly washing the carbon cloth zinc oxide compound to be neutral through deionized water to obtain the self-supporting carbon material.
2. The method for preparing a highly open, high specific surface area, self-supporting carbon material as claimed in claim 1, wherein in step B, the concentration of the carbon source solution is 1M, and the soaking time is 12 hours; the drying temperature is 80 ℃, and the drying time is 1 hour.
3. The method for preparing the self-supporting carbon material with high degree of opening and high specific surface area as claimed in claim 1, wherein in step C, the inert gas is argon, the flow rate is 40m L/min, the heating rate for heating to 150-180 ℃ is 1 ℃/min, and the heating rate for heating to 800-1000 ℃ is 5 ℃/min.
4. The method for preparing a highly open, high specific surface area, self-supporting carbon material according to claim 1 or 2, wherein in step B, the carbon source solution is a glucose solution.
5. The method for preparing highly open self-supporting carbon material with high specific surface area as claimed in claim 1, wherein in step C, the temperature is maintained at 150-180 ℃ for 1 hour and at 800-1000 ℃ for 2 hours.
6. The method for preparing a highly open, high specific surface area, self-supporting carbon material according to claim 1, wherein in step D, the acid solution is at least one of a hydrochloric acid solution and a sulfuric acid solution.
7. A carbon-polymer composite electrode material comprising the self-supporting carbon material prepared by the method of claim 1 and a polymer dielectric layer coated on the self-supporting carbon material.
8. A method for preparing a carbon-polymer composite electrode material according to claim 7, comprising the steps of:
s1, cutting the self-supporting carbon material prepared by the method in claim 1 into an electrode shape;
s2, adding the fluorine-containing polymer into the N, N-dimethylformamide solution, stirring and dissolving to obtain a solution a;
s3, putting the sheared self-supporting carbon material into the solution a for soaking, performing rotary evaporation under a vacuum condition until the solution is dried to obtain a composite material, and then naturally drying;
and S4, drying the composite material processed in the step S3 by air blowing, taking out, and quenching in ice water to obtain the carbon-polymer composite electrode material.
9. The method for producing a carbon-polymer composite electrode material according to claim 8, wherein in step S2, the fluorine-containing polymer includes PVDF-HFP, PVDF; the temperature for stirring and dissolving is 80 ℃;
in step S3, the temperature of the rotary evaporation is 80 ℃; the natural drying time is 24 hours;
in step S4, the temperature of the forced air drying was 200 ℃ and the drying time was 10 minutes.
10. A novel symmetrical water-based hybrid high-voltage capacitor comprising the carbon-polymer composite electrode material of claim 7, wherein the capacitor is obtained by assembling the carbon-polymer composite electrode material, KOH electrolyte and cellulose diaphragm.
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