CN113871211A - High-energy-density super capacitor - Google Patents
High-energy-density super capacitor Download PDFInfo
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- CN113871211A CN113871211A CN202111080192.8A CN202111080192A CN113871211A CN 113871211 A CN113871211 A CN 113871211A CN 202111080192 A CN202111080192 A CN 202111080192A CN 113871211 A CN113871211 A CN 113871211A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention provides a high-energy-density supercapacitor, which relates to the technical field of supercapacitors and comprises a first electrode, a second electrode, an organic electrolyte, a diaphragm and a shell, wherein the first electrode and the second electrode are both boron-zinc composite porous derived carbon materials, the boron-zinc composite porous derived carbon materials are prepared by calcining boric acid-zinc-based MOF in one step, the boric acid-zinc-based MOF is prepared by thermal conversion and recombination of boric acid and zinc-based MOF, and the preparation method of the high-energy-density supercapacitor comprises the following steps: (1) synthesizing zinc-based MOF borate, (2) calcining; (3) assembling the super capacitor; according to the invention, boron and zinc are compounded into the carbon matrix in one step to obtain the compound of boron and zinc and a high specific surface area and large micropore structure, the capacity of the super capacitor is improved by the cooperation of the boron and zinc, and the high specific surface area and the large micropore structure, and the television window of the capacitor is also improved, so that the energy density of the super capacitor is also greatly improved.
Description
Technical Field
The invention relates to the technical field of super capacitors, in particular to a super capacitor with high energy density.
Background
The super capacitor is a physical secondary power supply with super power storage capacity and capable of providing strong pulsating power. If the super capacitor is mainly divided into three types according to the energy storage mechanism: double electric layer capacitance generated by charge separation on the interface of carbon electrode and electrolyte; secondly, metal oxide is used as an electrode, oxidation-reduction reaction is carried out on the surface and bulk phase of the electrode to generate a Faraday capacitance of reversible chemical adsorption; a capacitor which takes redox reaction by using conductive polymer as an electrode; the energy density of the super capacitor is about 20% of that of a lead-acid battery, and if the same energy is stored, the volume and the weight of the super capacitor are much larger than those of a storage battery.
Energy density (E), calculated as follows: e-1/2 CV2Therefore, it is important to improve the potential window and capacitance of the capacitor to improve the energy density thereof, and porous carbon is widely used as an electrode material of a supercapacitor in the prior art due to its high surface area, good conductivity and excellent chemical stability. However, the high surface area of the carbon material is generally caused by micropores, some of which may not be contacted by electrolyte ions due to connectivity and closing characteristics, and the large pore size reduces the specific surface area, so that it is urgently needed to develop a supercapacitor made of a porous electrode material having a high specific surface area, a suitable pore size, excellent conductivity, and a high energy density, which is simple to prepare.
Chinese patent publication No. CN105778749A discloses a MOF structure porous carbon material, a flexible supercapacitor, and preparation methods and applications thereof. The MOF-structure porous carbon material comprises a stack of aromatic heterocyclic two-dimensional planar layered structures, and the aromatic heterocyclic two-dimensional planar layered structures mainly comprise carbon elements and nitrogen elements. The flexible supercapacitor comprises first and second electrodes, at least one of which comprises a MOF structure porous carbon material, and an electrolyte. The flexible super capacitor provided by the invention has excellent performance, has great application prospect in the fields of intelligent wearable electronic equipment, energy storage and the like, but the highest energy density of the super capacitor provided by the invention only reaches 50.94Wh/kg-1And the pore diameter range of the MOF structure porous material is larger, so that the specific surface area is lower.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a super capacitor with high energy density, and solves the problem that the energy density is improved as the aperture of a porous carbon-based electrode of the super capacitor is too small or too large.
(II) technical scheme
In order to solve the above problems, the present invention provides the following technical solutions:
the super capacitor with high energy density is composed of a first electrode, a second electrode, an organic electrolyte, a diaphragm and a shell, wherein the first electrode and the second electrode are both boron-zinc compounded porous derivative carbon materials which are prepared in one step by calcining boric acid-zinc-based MOF, and the boric acid-zinc-based MOF is prepared by thermal conversion and recombination of boric acid and zinc-based MOF.
Preferably, the organic electrolyte is any one of gel-like propylene carbonate and ethyl methyl carbonate, and is obtained by soaking in a conductive salt solution for 6-8h, wherein the conductive salt solution is any one of tetraethylammonium tetrafluoroborate solution and triethylammonium tetrafluoroborate solution with the concentration of 0.45-0.6M.
Preferably, the shell is made of ABS resin plastics, the rectangular groove is formed in the shell, the conductive interface is arranged on the side face of the shell, the edge of the shell is packaged through an adhesive, and the adhesive is any one of styrene butadiene rubber and polytetrafluoroethylene.
The preparation method of the supercapacitor with high energy density comprises the following steps:
(1) adding zinc-based MOF and boric acid into a mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into a high-pressure kettle lined with polytetrafluoroethylene, putting the high-pressure kettle into an oil bath kettle for reaction, cooling, filtering, washing the obtained precipitate with the mixed solution of the deionized water and the ethanol, and drying to obtain boric acid-zinc-based MOF;
(2) putting the boric acid-zinc-based MOF obtained in the step (1) into a crucible, putting the crucible into a tube furnace, heating the crucible to 150 ℃ in a nitrogen atmosphere for activation for 2 hours, then changing nitrogen into ammonia, heating and continuously calcining to obtain a boron-zinc composite porous derived carbon material;
(3) pressing a boron-zinc compounded porous derived carbon material and a polytetrafluoroethylene preparation into two mixed films through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of a groove of a shell, assembling an organic electrolyte and a diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the supercapacitor with high energy density.
Preferably, the reaction condition in the step (1) is heating to 120-140 ℃ for 12-16h, and the drying condition in the step (1) is drying in an oven at 60 ℃ for 8-12 h.
Preferably, the zinc-based MOF in the step (1) is a mixture of ZIF-8 and MOF-5, the mass ratio of the zinc-based MOF to the MOF-5 is 1:1, and the volume ratio of the deionized water to the ethanol in the mixed solution of the deionized water and the ethanol is 1: 1.
Preferably, the mass ratio of the zinc-based MOF to the boric acid to the mixed solution in the step (1) is 3-5:1: 100.
Preferably, the calcination condition in the step (2) is calcination at 800-.
Preferably, the mass ratio of the boron-zinc compounded porous derived carbon material to the polytetrafluoroethylene preparation in the step (3) is 5-8:3, and the size of the mixed membrane in the step (3) is 2.5cm × 2cm × 5 nm.
The invention has the beneficial effects that:
(1) the invention provides a high-energy-density supercapacitor, boric acid, ZIF-8 and MOF-5 are recombined in a high-temperature thermal conversion process of the ZIF-8, the MOF-5 and the boric acid, and carboxyl on the boric acid and the MOF-5 can be recombined with Zn2+And the nitrogen atoms on the ZIF-8 are coordinated to obtain an MOF structure rich in boron groups and zinc ions, then the MOF structure is calcined in ammonia gas at high temperature, boric acid can form boron trioxide at high temperature, and boron oxide is dispersed in a carbon matrix at elevated temperature, so that the large-micropore boron-zinc composite porous derivative carbon material taking the MOF structure as a sacrificial template is obtained in one step, and the large-micropore boron-zinc composite porous derivative carbon material has large specific surface area and pore structure, and is finally assembled with an organic electrolyte, a diaphragm and a shell as main materials of a first electrode and a second electrode of a supercapacitor, and the large-micropore structure in the boron-zinc composite porous derivative carbon material not only provides an effective ion channel for ions to rapidly permeate into micropores in the boron-zinc composite porous derivative carbon material, is favorable for the diffusion of the electrolyte, but also provides a continuous electron channel, and keeps good conductivity.
(2) According to the high-energy-density supercapacitor provided by the invention, boron and zinc are compounded into a carbon base in one step to obtain a boron-zinc compound and high-specific-surface-area and large-micropore structure, and as boric acid subjected to high-temperature calcination forms boron trioxide and is uniformly dispersed into the carbon base, B-O on the surface of the boron-zinc compound is greatly increased, and the groups can participate in an oxidation reduction process, so that the electrochemical active surfaces of the boron-zinc compound are increased, and meanwhile, the television window of the capacitor is also improved, so that the energy density of the capacitor is also greatly improved.
Detailed Description
The invention is further illustrated by the following examples, which are intended to illustrate, but not to limit the invention further. The technical means used in the following examples are conventional means well known to those skilled in the art, and all raw materials are general-purpose materials.
Example 1
A preparation method of a high-energy-density super capacitor comprises the following steps:
(1) adding 4.5g of ZIF-8, 4.5g of MOF-5 and 3g of boric acid into 300ml of a mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into an autoclave lined with polytetrafluoroethylene, putting the autoclave into an oil bath pot, heating to 120 ℃, keeping for 16h, cooling, filtering, washing the obtained precipitate with the mixed solution of the deionized water and the ethanol, and drying in an oven at 60 ℃ for 8h to obtain boric acid-zinc-based MOF;
(2) putting the boric acid-zinc-based MOF obtained in the step (1) into a crucible, putting the crucible into a tube furnace, heating the crucible to 150 ℃ in a nitrogen atmosphere for activating for 2h, then changing nitrogen into ammonia, and calcining for 4h at 800 ℃ at the heating rate of 5 ℃/min to obtain the boron-zinc composite porous derived carbon material;
(3) pressing 1g of boron-zinc compounded porous derivative carbon material and 0.6g of polytetrafluoroethylene preparation into two mixed films with the size of 2.5cm multiplied by 2cm multiplied by 5nm through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of a groove of a shell, assembling an organic electrolyte and a diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the supercapacitor with high energy density.
The shell in the embodiment is made of ABS resin plastic through a traditional process, the shell is internally provided with a rectangular groove, the side face of the shell is provided with a conductive interface, the edge of the shell is packaged by polytetrafluoroethylene, and the organic electrolyte is obtained by soaking gelatinous ethyl methyl carbonate in 0.45M triethyl ammonium tetrafluoroborate solution for 6 hours.
Example 2
A preparation method of a high-energy-density super capacitor comprises the following steps:
(1) adding 6g of ZIF-8, 6g of MOF-5 and 3g of boric acid into 300ml of a mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into an autoclave lined with polytetrafluoroethylene, putting the autoclave into an oil bath, heating to 130 ℃, keeping for 14h, cooling, filtering, washing the obtained precipitate with the mixed solution of the deionized water and the ethanol, and drying in an oven at 60 ℃ for 10h to obtain boric acid-zinc-based MOF;
(2) putting the boric acid-zinc-based MOF obtained in the step (1) into a crucible, putting the crucible into a tube furnace, heating the crucible to 150 ℃ in a nitrogen atmosphere for activating for 2h, then changing nitrogen into ammonia, and calcining for 4h at 880 ℃ at a heating rate of 5 ℃/min to obtain a boron-zinc composite porous derived carbon material;
(3) pressing 1.2g of boron-zinc compounded porous derivative carbon material and 0.6g of polytetrafluoroethylene preparation into two mixed films with the size of 2.5cm multiplied by 2cm multiplied by 5nm through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of a groove of a shell, assembling an organic electrolyte and a diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastics, the interior of the shell is provided with a rectangular groove, the side face of the shell is provided with a conductive interface, the edge of the shell is packaged by polytetrafluoroethylene, and the organic electrolyte is prepared by soaking gel propylene carbonate in tetraethylammonium tetrafluoroborate solution with the concentration of 0.45M for 6 hours.
Example 3
A preparation method of a high-energy-density super capacitor comprises the following steps:
(1) adding 6.8g of ZIF-8, 6.8g of MOF-5 and 3g of boric acid into 300ml of a mixed solution of deionized water and ethanol, uniformly mixing by ultrasonic waves, putting the mixture into an autoclave lined with polytetrafluoroethylene, putting the autoclave into an oil bath pot, heating to 135 ℃, keeping for 12h, cooling, filtering, washing the obtained precipitate by the mixed solution of the deionized water and the ethanol, and drying in an oven at 60 ℃ for 12h to obtain boric acid-zinc-based MOF;
(2) putting the boric acid-zinc-based MOF obtained in the step (1) into a crucible, putting the crucible into a tube furnace, heating the crucible to 150 ℃ in a nitrogen atmosphere for activating for 2h, then changing nitrogen into ammonia, and calcining for 4h at 1000 ℃ at the heating rate of 5 ℃/min to obtain the boron-zinc composite porous derived carbon material;
(3) and pressing 1.5g of boron-zinc compounded porous derivative carbon material and 0.6g of polytetrafluoroethylene preparation into two mixed films with the size of 2.5cm multiplied by 2cm multiplied by 5nm through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of the groove of the shell, assembling the organic electrolyte and the diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastic through a traditional process, the shell is internally provided with a rectangular groove, the side face of the shell is provided with a conductive interface, the edge of the shell is packaged through styrene butadiene rubber, and the organic electrolyte is obtained by soaking gelatinous ethyl methyl carbonate in 0.5M triethylammonium tetrafluoroborate solution for 8 hours.
Example 4
A preparation method of a high-energy-density super capacitor comprises the following steps:
(1) adding 7.5g of ZIF-8, 7.5g of MOF-5 and 3g of boric acid into 300ml of a mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into an autoclave lined with polytetrafluoroethylene, putting the autoclave into an oil bath pot, heating to 140 ℃, keeping for 12h, cooling, filtering, washing the obtained precipitate with the mixed solution of the deionized water and the ethanol, and drying in an oven at 60 ℃ for 12h to obtain boric acid-zinc-based MOF;
(2) putting the boric acid-zinc-based MOF obtained in the step (1) into a crucible, putting the crucible into a tube furnace, heating the crucible to 150 ℃ in a nitrogen atmosphere for activating for 2h, then changing nitrogen into ammonia, and calcining for 4h at 1000 ℃ at the heating rate of 5 ℃/min to obtain the boron-zinc composite porous derived carbon material;
(3) pressing 1.6g of boron-zinc compounded porous derivative carbon material and 0.6g of polytetrafluoroethylene preparation into two mixed films with the size of 2.5cm multiplied by 2cm multiplied by 5nm through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of a groove of a shell, assembling an organic electrolyte and a diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastic through a traditional process, the rectangular groove is formed in the shell, the conductive interface is formed in the side face of the shell, the edge of the shell is packaged through styrene butadiene rubber, and the organic electrolyte is obtained by soaking gel-like propylene carbonate in 0.6M tetraethylammonium tetrafluoroborate solution in a conductive salt solution for 8 hours.
Comparative example 1
A preparation method of a supercapacitor with a porous carbon-based electrode comprises the following steps:
(1) putting the zinc-based MOF into a crucible, and calcining for 4h at 1000 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere to obtain the porous derivative carbon material;
(2) pressing 1.5g of porous derivative carbon material and 0.6g of polytetrafluoroethylene preparation into two mixed films with the size of 2.5cm multiplied by 2cm multiplied by 5nm through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of a groove of a shell, assembling an organic electrolyte and a diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the supercapacitor with high energy density.
In the comparative example, the shell is made of ABS resin plastic through a traditional process, the interior of the shell is provided with a rectangular groove, the side face of the shell is provided with a conductive interface, the edge of the shell is packaged through styrene butadiene rubber, and the organic electrolyte is obtained by soaking gel-like propylene carbonate in 0.6M tetraethylammonium tetrafluoroborate solution in a conductive salt solution for 8 hours.
Comparative example 2
A preparation method of a super capacitor comprises the following steps:
(1) putting 10g of a mixture of MOF-5 and 3g of boric acid into a crucible, putting the crucible into a tube furnace, heating the crucible to 150 ℃ in a nitrogen atmosphere, activating the crucible for 2h, and calcining the mixture for 4h at 1000 ℃ at a heating rate of 5 ℃/min in an ammonia atmosphere to obtain a boron-zinc loaded porous derived carbon material;
(2) pressing 1.5g of porous derivative carbon material loaded with boron and zinc and 0.6g of polytetrafluoroethylene preparation into two mixed films with the size of 2.5cm multiplied by 2cm multiplied by 5nm through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of a groove of a shell, assembling an organic electrolyte and a diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastic through a traditional process, the rectangular groove is formed in the shell, the conductive interface is formed in the side face of the shell, the edge of the shell is packaged through styrene butadiene rubber, and the organic electrolyte is obtained by soaking gel-like propylene carbonate in 0.6M tetraethylammonium tetrafluoroborate solution in a conductive salt solution for 8 hours.
The supercapacitors prepared in examples 1-4 and comparative examples 1-2 were passed through CV measurements at a constant scan rate of 100mv/s over different potential windows of 0-1, 0-1.2, 0-1.5V, and the area under the CV curve of the potential of 0-1.5V was found to be the largest, so the following electrical performance tests were all performed at 1.5V.
1) The electrochemical performance of the supercapacitors made according to examples 1-4 and comparative examples 1-2 was tested by Cyclic Voltammetry (CV) and constant current charging and discharging (GCD), and table 1 shows the energy density at different power densities.
Table 1:
and (4) analyzing results: from examples 1 to 4, it can be known that the super capacitor prepared by the invention is enhanced along with the reduction of the power density, the highest energy density is 72Wh/kg under the power density of 2500W/kg, and the highest energy density of the super capacitor prepared by comparative examples 1 and 2 under the power density of 2500W/kg is only 51Wh/kg, which shows that the super capacitor prepared by the invention combines boron and zinc into carbon base in one step, the obtained boron and zinc are combined, and the high specific surface area and the large micropore structure cooperate to improve the capacitance of the super capacitor, and simultaneously, the television window of the capacitor is also improved, so that the energy density is also greatly improved.
2) The test method comprises the following steps: in order to evaluate the specific capacitance of the supercapacitors prepared according to the invention, the specific capacitance of the supercapacitors of examples 1-4 and comparative examples 1-3 was measured by cyclic voltammetry at different current densities, the results of which are shown in table 2.
Table 2:
and (4) analyzing results: as can be seen from Table 2, the maximum specific capacitance of the supercapacitors prepared in examples 1-4 at a current density of 5A/g was 216.5F/g, the maximum specific capacitance at a current density of 100A/g was 173.1F/g, while the maximum specific capacitance of the supercapacitors prepared in comparative examples 1-2 at a current density of 5A/g was only 188.5F/g, and the maximum specific capacitance at a current density of 100A/g was 121.2F/g, indicating that the high-energy supercapacitors prepared according to the present invention can synergistically increase the capacitance of the supercapacitors by compounding boron and zinc into a carbon-based species as an electrode.
3) The porous carbon-based materials prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention were characterized by a low-temperature nitrogen adsorption method, and 100mg of the porous carbon-based materials prepared in examples 1 to 4 and comparative examples 1 to 2 were weighed, respectively, and their specific surface areas and pore size ranges were measured, and the results of the measurements are shown in table 3.
Table 3:
and (4) analyzing results: as is clear from Table 3, the average specific surface area of the boron-zinc composite porous derivatized carbon material prepared in examples 1 to 4 was 2300m2The pore size is between 0.45 and 1.92nm, which shows that the boron-zinc composite porous derivative carbon material has high specific surface area and large micropore structure, and the specific surface area of the porous derivative carbon material prepared in comparative example 1-2 is 1382m2G and 1758m2And/g, and their pore size is between 0.4 and 87nm, too large a pore size may not contribute to increasing the capacitance and energy density of the supercapacitor.
Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (9)
1. The supercapacitor with high energy density is characterized by consisting of a first electrode, a second electrode, an organic electrolyte, a diaphragm and a shell, wherein the first electrode and the second electrode are both boron-zinc composite porous derivative carbon materials which are prepared in one step by calcining boric acid-zinc-based MOF, and the boric acid-zinc-based MOF is prepared by boric acid and zinc-based MOF through thermal transformation and recombination.
2. The supercapacitor according to claim 1, wherein the organic electrolyte is any one of propylene carbonate and ethyl methyl carbonate in gel form, and is obtained by soaking the organic electrolyte in a conductive salt solution for 6 to 8 hours, and the conductive salt solution is any one of tetraethylammonium tetrafluoroborate solution and triethylammonium tetrafluoroborate solution with the concentration of 0.45 to 0.6M.
3. The supercapacitor according to claim 1, wherein the housing is made of ABS resin plastic with rectangular grooves inside and conductive interfaces on the sides by a conventional process, and the edges of the housing are encapsulated by an adhesive, which is one of styrene butadiene rubber and polytetrafluoroethylene.
4. The method for preparing the supercapacitor with high energy density according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) adding zinc-based MOF and boric acid into a mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into a high-pressure kettle lined with polytetrafluoroethylene, putting the high-pressure kettle into an oil bath kettle for reaction, cooling, filtering, washing the obtained precipitate with the mixed solution of the deionized water and the ethanol, and drying to obtain boric acid-zinc-based MOF;
(2) putting the boric acid-zinc-based MOF obtained in the step (1) into a crucible, putting the crucible into a tube furnace, heating the crucible to 150 ℃ in a nitrogen atmosphere for activation for 2 hours, then changing nitrogen into ammonia, heating and continuously calcining to obtain a boron-zinc composite porous derived carbon material;
(3) pressing a boron-zinc compounded porous derived carbon material and a polytetrafluoroethylene preparation into two mixed films through a film making machine to obtain a first electrode and a second electrode, respectively attaching the first electrode and the second electrode to the inner wall of a groove of a shell, assembling an organic electrolyte and a diaphragm into a sandwich structure, wrapping the sandwich structure through the shell with the first electrode and the second electrode, and then packaging to obtain the high-energy-density supercapacitor.
5. The method as claimed in claim 4, wherein the reaction condition in step (1) is heating to 120-140 ℃ for 12-16h, and the drying condition in step (1) is drying in an oven at 60 ℃ for 8-12 h.
6. The method for preparing the supercapacitor with high energy density according to claim 4, wherein the zinc-based MOF in the step (1) is a mixture of ZIF-8 and MOF-5, the mass ratio of the zinc-based MOF to the MOF-5 is 1:1, and the volume ratio of the deionized water to the ethanol in the mixed solution of the deionized water and the ethanol is 1: 1.
7. The method for preparing the high-energy-density supercapacitor according to claim 4, wherein the mass ratio of the zinc-based MOF to the boric acid to the mixed solution in the step (1) is 3-5:1: 100.
8. The method as claimed in claim 4, wherein the calcination condition in step (2) is calcination at 800-.
9. The method for preparing a high energy density supercapacitor according to claim 4, wherein the mass ratio of the boron-zinc compounded porous derived carbon material to the polytetrafluoroethylene preparation in step (3) is 5-8:3, and the size of the mixed membrane in step (3) is 2.5cm x 2cm x 5 nm.
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