CN113871211B - Super capacitor with high energy density - Google Patents
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- CN113871211B CN113871211B CN202111080192.8A CN202111080192A CN113871211B CN 113871211 B CN113871211 B CN 113871211B CN 202111080192 A CN202111080192 A CN 202111080192A CN 113871211 B CN113871211 B CN 113871211B
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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
- H01G11/32—Carbon-based
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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
Abstract
The invention provides a super capacitor with high energy density, which relates to the technical field of super capacitors, and comprises a first electrode, a second electrode, organic electrolyte, a diaphragm and a shell, wherein the first electrode and the second electrode are porous derivative carbon materials compounded by boron and zinc, the porous derivative carbon materials compounded by boron and zinc are prepared by calcining boric acid-zinc-based MOF (metal organic framework) in one step, the boric acid-zinc-based MOF is prepared by thermal conversion recombination of boric acid and zinc-based MOF, and the preparation method of the super capacitor with high energy density comprises the following steps: (1) synthesizing boric acid-zinc based MOF, (2) calcining; (3) assembling the super capacitor; according to the invention, the boron and zinc are compounded into the carbon base in one step, so that the boron and zinc compound, the high specific surface area and the large micropore structure are obtained, the capacitance of the super capacitor is cooperatively improved, 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 supercapacitors, in particular to a high-energy-density supercapacitor.
Background
The super capacitor is a physical secondary power supply with super power storage capacity and capable of providing strong pulsating power. Super capacitors are mainly classified into three types according to energy storage mechanism: (1) an electric double layer capacitor generated by charge separation at the interface between the carbon electrode and the electrolyte; (2) adopting metal oxide as an electrode, and generating oxidation-reduction reaction on the surface of the electrode and the bulk phase to generate reversible chemisorption Faraday capacitance; (3) a capacitance in which a redox reaction occurs by using a 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 CV 2 Therefore, increasing the potential window, capacitance of the capacitor is critical to increasing its energy density, and porous carbon is widely used as an electrode material of super capacitors 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 closure characteristics, and too large pore size reduces the specific surface area, so that development of a material having high specific surface area, suitable pore size, and conductivity is desiredExcellent and simple preparation of the porous electrode material.
The patent with the Chinese patent publication number of CN105778749A discloses a porous carbon material with a MOF structure, a flexible supercapacitor, a preparation method and application thereof. The MOF structure porous carbon material comprises a stacked body of aromatic heterocyclic two-dimensional plane layered structures, wherein the aromatic heterocyclic two-dimensional plane layered structures mainly comprise carbon elements and nitrogen elements. The flexible supercapacitor includes first and second electrodes, at least one of which includes a MOF structured porous carbon material, and an electrolyte. The flexible supercapacitor provided by the invention has excellent performance and huge application prospect in the fields of intelligent wearable electronic equipment, energy storage and the like, however, the maximum energy density of the supercapacitor of the invention only reaches 50.94Wh/kg -1 And the pore size range of the MOF structure porous material is larger, so that the specific surface area of the MOF structure porous material is lower.
Disclosure of Invention
(one) solving the technical problems
The invention aims to provide a super capacitor with high energy density, which solves the problems that the pore diameter of a porous carbon-based electrode of the super capacitor is too small or too low, and the energy density is improved.
(II) technical scheme
In order to solve the problems, the invention provides the following technical scheme:
the super capacitor with high energy density consists 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 porous derivative carbon materials composited by boron and zinc, the porous derivative carbon materials composited by boron and zinc are prepared by calcining boric acid-zinc-based MOF (metal organic framework) in one step, and the boric acid-zinc-based MOF is prepared by thermal conversion recombination of boric acid and zinc-based MOF.
Preferably, the organic electrolyte is any one of gel propylene carbonate and ethyl methyl carbonate, and is obtained by soaking the gel propylene carbonate and ethyl methyl carbonate in a conductive salt solution for 6-8 hours, 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 plastic, a rectangular groove is formed in the shell through a traditional process, a conductive interface is formed in the side face of the shell, the edge of the shell is encapsulated through an adhesive, and the adhesive is any one of styrene-butadiene rubber and polytetrafluoroethylene.
The preparation method of the super capacitor 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 an autoclave lined with polytetrafluoroethylene, placing the autoclave into an oil bath pot for reaction, cooling, filtering, washing the obtained precipitate with a mixed solution of deionized water and ethanol, and drying to obtain boric acid-zinc-based MOF;
(2) Placing the boric acid-zinc-based MOF obtained in the step (1) into a crucible, placing the crucible into a tube furnace, heating to 150 ℃ in a nitrogen atmosphere, activating for 2 hours, then changing nitrogen into ammonia, and heating to continue calcination to obtain the boron-zinc composite porous derivative carbon material;
(3) And pressing the boron-zinc composite porous derivative carbon material and the polytetrafluoroethylene preparation into two mixed films by 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 by the shell with the first electrode and the second electrode, and packaging to obtain the supercapacitor with high energy density.
Preferably, the reaction condition in the step (1) is heating to 120-140 ℃ and maintaining for 12-16h, and the drying condition in the step (1) is drying in a 60 ℃ oven for 8-12h.
Preferably, in the step (1), the zinc-based MOF is a mixture of ZIF-8 and MOF-5, the mass ratio of the zinc-based MOF to the MOF is 1:1, and the volume ratio of deionized water to ethanol in the mixed solution of deionized water and ethanol is 1:1.
Preferably, in the step (1), the mass ratio of the zinc-based MOF, the boric acid and the mixed solution is 3-5:1:100.
Preferably, the calcination condition in the step (2) is calcination at 800-1000 ℃ for 4 hours at a temperature rising rate of 5 ℃/min.
Preferably, the mass ratio of the boron-zinc composite porous derivative carbon material to the polytetrafluoroethylene preparation in the step (3) is 5-8:3, and the size of the mixed film in the step (3) is 2.5cm multiplied by 2cm multiplied by 5nm.
The beneficial effects of the invention are as follows:
(1) The super capacitor with high energy density provided by the invention has the advantages that boric acid and ZIF-8, MOF-5 are recombined in the high-temperature heat conversion process, and boric acid and carboxyl on the MOF-5 can be recombined with Zn 2+ And the nitrogen atoms on the ZIF-8 are coordinated to obtain a MOF structure rich in boron and zinc ions, boric acid can form boron trioxide at high temperature through high-temperature calcination in ammonia gas, and the boron oxide is dispersed into a carbon matrix at elevated temperature to obtain the macroporous boron-zinc composite porous derivative carbon material taking the MOF structure as a sacrificial template in one step, the porous derivative carbon material has large specific surface area and pore structure, and finally the main materials of the first electrode and the second electrode of the super capacitor are assembled with organic electrolyte, a diaphragm and a shell to obtain the porous derivative carbon material with the large microporous structure in the boron-zinc composite porous derivative carbon material, so that an effective ion path is provided for the ions to quickly permeate into micropores in the porous derivative carbon material, the diffusion of electrolyte is facilitated, a continuous electronic path is provided, and good conductivity is maintained.
(2) According to the super capacitor with high energy density, boron and zinc are compounded into the carbon base in one step, the obtained boron and zinc are compounded, the obtained boron and zinc have a high specific surface area and a large micropore structure, and boric acid after high-temperature calcination forms boron trioxide and is uniformly dispersed into the carbon base, the B-O on the surface of the boron and zinc is greatly increased, and the groups can participate in the oxidation-reduction process, so that the electrochemical active surface of the boron and zinc is increased, and meanwhile, the television window of the capacitor is also improved, so that the energy density of the super capacitor is also greatly improved.
Detailed Description
The invention will be further illustrated with reference to the following specific embodiments, which are intended to illustrate the invention and not to limit it further. The technical means used in the examples below are conventional means well known to those skilled in the art, all starting materials being general materials.
Example 1
The preparation method of the super capacitor with high energy density comprises the following steps:
(1) Adding 4.5g ZIF-8, 4.5g MOF-5 and 3g boric acid into 300ml mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into an autoclave lined with polytetrafluoroethylene, heating to 120 ℃ in an oil bath kettle, keeping for 16 hours, cooling, filtering, washing the obtained precipitate with mixed solution of deionized water and ethanol, and drying in an oven at 60 ℃ for 8 hours to obtain boric acid-zinc-based MOF;
(2) Placing the boric acid-zinc-based MOF obtained in the step (1) into a crucible, placing the crucible into a tube furnace, heating to 150 ℃ in a nitrogen atmosphere, activating for 2 hours, then changing nitrogen into ammonia, and calcining for 4 hours at 800 ℃ at a heating rate of 5 ℃/min to obtain a boron-zinc composite porous derivative carbon material;
(3) And (3) pressing 1g of boron-zinc composite 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 packaging to obtain the supercapacitor with high energy density.
The shell in the embodiment is made of ABS resin plastic, a rectangular groove is formed in the shell through a traditional process, a conductive interface is arranged on the side face of the shell, the edge of the shell is encapsulated through polytetrafluoroethylene, and the organic electrolyte is obtained by soaking gel ethyl methyl carbonate in triethylammonium tetrafluoroborate solution with the concentration of 0.45M for 6 hours.
Example 2
The preparation method of the super capacitor with high energy density comprises the following steps:
(1) Adding 6g ZIF-8, 6g MOF-5 and 3g boric acid into 300ml mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into an autoclave lined with polytetrafluoroethylene, heating to 130 ℃ in an oil bath kettle, keeping for 14 hours, cooling, filtering, washing the obtained precipitate with mixed solution of deionized water and ethanol, and drying in an oven at 60 ℃ for 10 hours to obtain boric acid-zinc-based MOF;
(2) Placing the boric acid-zinc-based MOF obtained in the step (1) into a crucible, placing the crucible into a tube furnace, heating to 150 ℃ in a nitrogen atmosphere, activating for 2 hours, then changing nitrogen into ammonia, and calcining for 4 hours at 880 ℃ at a heating rate of 5 ℃/min to obtain a boron-zinc composite porous derivative carbon material;
(3) And (3) pressing 1.2g of boron-zinc composite 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 packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastic, a rectangular groove is formed in the shell through a traditional process, a conductive interface is formed in the shell, the edge of the shell is encapsulated through polytetrafluoroethylene, and the organic electrolyte is prepared by soaking gel-like propylene carbonate in a tetraethylammonium tetrafluoroborate solution with the concentration of 0.45M for 6 hours.
Example 3
The preparation method of the super capacitor with high energy density comprises the following steps:
(1) Adding 6.8g ZIF-8, 6.8g MOF-5 and 3g boric acid into 300ml mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into an autoclave lined with polytetrafluoroethylene, heating to 135 ℃ in an oil bath, keeping for 12 hours, cooling, filtering, washing the obtained precipitate with mixed solution of deionized water and ethanol, and drying in an oven at 60 ℃ for 12 hours to obtain boric acid-zinc-based MOF;
(2) Placing the boric acid-zinc-based MOF obtained in the step (1) into a crucible, placing the crucible into a tube furnace, heating to 150 ℃ in a nitrogen atmosphere, activating for 2 hours, then changing nitrogen into ammonia, and calcining for 4 hours at 1000 ℃ at a heating rate of 5 ℃/min to obtain a boron-zinc composite porous derivative carbon material;
(3) And then, pressing 1.5g of boron-zinc composite 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 on 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 packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastic, a rectangular groove is formed in the shell through a traditional process, a conductive interface is formed in the side face of the shell, the edge of the shell is encapsulated through styrene-butadiene rubber, and the organic electrolyte is obtained by soaking gel ethyl methyl carbonate in triethylammonium tetrafluoroborate solution with the concentration of 0.5M for 8 hours.
Example 4
The preparation method of the super capacitor with high energy density comprises the following steps:
(1) Adding 7.5g ZIF-8, 7.5g MOF-5 and 3g boric acid into 300ml mixed solution of deionized water and ethanol, carrying out ultrasonic mixing uniformly, putting the mixture into an autoclave lined with polytetrafluoroethylene, heating to 140 ℃ in an oil bath kettle, keeping for 12 hours, cooling, filtering, washing the obtained precipitate with mixed solution of deionized water and ethanol, and drying in an oven at 60 ℃ for 12 hours to obtain boric acid-zinc-based MOF;
(2) Placing the boric acid-zinc-based MOF obtained in the step (1) into a crucible, placing the crucible into a tube furnace, heating to 150 ℃ in a nitrogen atmosphere, activating for 2 hours, then changing nitrogen into ammonia, and calcining for 4 hours at 1000 ℃ at a heating rate of 5 ℃/min to obtain a boron-zinc composite porous derivative carbon material;
(3) And (3) pressing 1.6g of boron-zinc composite 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 packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastic, a rectangular groove is formed in the shell and conductive interfaces are arranged on the side face of the shell through a traditional process, the edge of the shell is encapsulated through styrene-butadiene rubber, and the organic electrolyte is obtained by soaking gel propylene carbonate in a tetraethylammonium tetrafluoroborate solution with the concentration of 0.6M in a conductive salt solution for 8 hours.
Comparative example 1
A method of making a supercapacitor having a porous carbon-based electrode, comprising the steps of:
(1) Placing the zinc-based MOF into a crucible, and calcining for 4 hours at the temperature of 1000 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere to obtain a porous derivative carbon material;
(2) And (3) pressing 1.5g of porous derived 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 packaging to obtain the supercapacitor with high energy density.
In the comparative example, the shell is made of ABS resin plastic, a rectangular groove is formed in the shell and conductive interfaces are arranged on the side face of the shell through a traditional process, the edge of the shell is encapsulated through styrene-butadiene rubber, and the organic electrolyte is obtained by soaking tetraethyl ammonium tetrafluoroborate solution with the concentration of gel propylene carbonate in a conductive salt solution of 0.6M for 8 hours.
Comparative example 2
The preparation method of the super capacitor comprises the following steps:
(1) Placing 10g of MOF-5 and 3g of boric acid mixture into a crucible, placing the crucible into a tube furnace, heating to 150 ℃ in a nitrogen atmosphere, activating for 2h, and calcining for 4h at 1000 ℃ at a heating rate of 5 ℃/min in an ammonia atmosphere to obtain a boron-zinc-loaded porous derivative carbon material;
(2) And (3) 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 packaging to obtain the supercapacitor with high energy density.
In the embodiment, the shell is made of ABS resin plastic, a rectangular groove is formed in the shell and conductive interfaces are arranged on the side face of the shell through a traditional process, the edge of the shell is encapsulated through styrene-butadiene rubber, and the organic electrolyte is obtained by soaking gel propylene carbonate in a tetraethylammonium tetrafluoroborate solution with the concentration of 0.6M in a conductive salt solution for 8 hours.
The supercapacitors prepared in examples 1 to 4 and comparative examples 1 to 2 were tested for CV at a constant scan rate of 100mV/s through different potential windows of 0 to 1, 0 to 1.2 and 0 to 1.5V, and found that the area under CV curve of the potential of 0 to 1.5V was the largest, so that the following electrical property tests were all conducted at 1.5V.
1) The electrochemical properties of the supercapacitors made in examples 1-4, comparative examples 1-2 were tested by Cyclic Voltammetry (CV) and constant current charge-discharge (GCD), and Table 1 shows the energy densities at different power densities.
Table 1:
analysis of results: it can be seen from examples 1-4 that the super capacitor prepared by the method is enhanced along with the reduction of the power density, the highest energy density at the power density of 2500W/kg is 72Wh/kg, and the super capacitor prepared by comparative examples 1 and 2 is only 51Wh/kg, which shows that the energy density is greatly improved by compositing boron and zinc into a carbon base in one step, and the obtained boron and zinc composite, high specific surface area and large micropore structure synergistically improve the capacitance of the super capacitor and simultaneously improve the television window of the capacitor.
2) The testing method comprises the following steps: to evaluate the specific capacities of the supercapacitors prepared according to the present invention, the supercapacitors of examples 1 to 4 and comparative examples 1 to 3 were measured by cyclic voltammetry at different current densities, and the measurement results are shown in Table 2.
Table 2:
analysis of results: as can be seen from Table 2, the supercapacitors prepared in examples 1-4 had a maximum specific capacitance of 216.5F/g at a current density of 5A/g, a maximum specific capacitance of 173.1F/g at a current density of 100A/g, and the supercapacitors prepared in comparative examples 1-2 had a maximum specific capacitance of only 188.5F/g at a current density of 5A/g, and a maximum specific capacitance of 121.2F/g at a current density of 100A/g, indicating that the high-energy supercapacitors prepared in the present invention were capable of synergistically increasing the capacitance of the supercapacitors by one-step complexing boron and zinc to carbon-based species as electrodes.
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 detection results are shown in Table 3.
Table 3:
analysis of results: as can be seen from Table 3, the average specific surface area of the boron-zinc composite porous derivative carbon materials prepared in examples 1 to 4 was 2300m 2 About/g, pore size of 0.45-1.92nm, indicating that the boron-zinc composite porous derivative carbon materialHas high specific surface area and large micropore structure, and the specific surface area of the porous derivative carbon material prepared in the comparative example 1-2 is 1382m 2 /g and 1758m 2 /g, while their pore size is between 0.4-87nm, pore size too large may not contribute to increasing the capacitance and energy density of the supercapacitor.
Finally, it should be noted that: the above embodiments are only for illustrating the present invention and not for limiting the technical solution described in the present invention; it will be understood by those skilled in the art that the present invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Claims (9)
1. The super capacitor with high energy density is characterized by comprising a first electrode, a second electrode, an organic electrolyte, a diaphragm and a shell, wherein the first electrode and the second electrode are both porous derivative carbon materials composited by boron and zinc, the porous derivative carbon materials composited by boron and zinc are prepared by calcining boric acid-zinc-based MOF (metal organic framework) in one step, and the boric acid-zinc-based MOF is prepared by thermal conversion recombination of boric acid and zinc-based MOF;
the zinc-based MOF is a mixture of ZIF-8 and MOF-5, and the mass ratio of the zinc-based MOF to the MOF is 1:1; the mass ratio of the zinc-based MOF to the boric acid is 3-5:1.
2. The super capacitor with high energy density according to claim 1, wherein the organic electrolyte is any one of gel propylene carbonate and ethyl methyl carbonate, and is obtained by soaking the gel propylene carbonate and ethyl methyl carbonate in a conductive salt solution for 6-8 hours, and the conductive salt solution is any one of tetraethylammonium tetrafluoroborate solution and triethylammonium tetrafluoroborate solution with a concentration of 0.45-0.6M.
3. The super capacitor of claim 1, wherein said outer shell is made of ABS resin plastic with rectangular grooves inside and conductive interfaces on the sides by conventional process, and the edges are encapsulated by adhesive, said adhesive being any one of styrene-butadiene rubber and polytetrafluoroethylene.
4. A method of manufacturing a high energy density supercapacitor according to any one of claims 1 to 3 comprising the steps of:
(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 an autoclave lined with polytetrafluoroethylene, placing the autoclave into an oil bath pot for reaction, cooling, filtering, washing the obtained precipitate with a mixed solution of deionized water and ethanol, and drying to obtain boric acid-zinc-based MOF;
(2) Placing the boric acid-zinc-based MOF obtained in the step (1) into a crucible, placing the crucible into a tube furnace, heating to 150 ℃ in a nitrogen atmosphere, activating for 2 hours, then changing nitrogen into ammonia, and heating to continue calcination to obtain the boron-zinc composite porous derivative carbon material;
(3) And pressing the boron-zinc composite porous derivative carbon material and the polytetrafluoroethylene preparation into two mixed films by 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 the shell, assembling the organic electrolyte and the diaphragm into a sandwich structure, and packaging after wrapping the sandwich structure by the shell with the first electrode and the second electrode to obtain the super capacitor with high energy density.
5. The method for manufacturing a super capacitor with high energy density as claimed in claim 4, wherein said reaction condition in said step (1) is heating to 120-140 ℃ for 12-16 hours, and said drying condition in said step (1) is drying in an oven at 60 ℃ for 8-12 hours.
6. The method for manufacturing a super capacitor with high energy density according to claim 4, wherein in the step (1), the zinc-based MOF is a mixture of ZIF-8 and MOF-5 in a mass ratio of 1:1, and the volume ratio of deionized water and ethanol in the mixed solution of deionized water and ethanol is 1:1.
7. The method for manufacturing a super capacitor with high energy density according to claim 4, wherein the mass ratio of the zinc-based MOF, the boric acid and the mixed solution in the step (1) is 3-5:1:100.
8. The method of manufacturing a super capacitor having a high energy density as claimed in claim 4, wherein the calcination condition in the step (2) is calcination at a temperature rise rate of 5 ℃/min for 4 hours at 800-1000 ℃.
9. The method of manufacturing a super capacitor with high energy density according to claim 4, wherein the mass ratio of the boron-zinc composite porous derivative carbon material to the polytetrafluoroethylene preparation in the step (3) is 5-8:3, and the size of the mixed film in the step (3) is 2.5cm x 2cm x 5nm.
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