CN108257795B - Method for improving capacitance of super capacitor - Google Patents
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- CN108257795B CN108257795B CN201810022581.7A CN201810022581A CN108257795B CN 108257795 B CN108257795 B CN 108257795B CN 201810022581 A CN201810022581 A CN 201810022581A CN 108257795 B CN108257795 B CN 108257795B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910021389 graphene Inorganic materials 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 20
- 238000005286 illumination Methods 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- -1 1-butyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
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- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
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- 239000011734 sodium Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
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- 239000002041 carbon nanotube Substances 0.000 claims description 2
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- 229920005614 potassium polyacrylate Polymers 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 11
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- 238000004146 energy storage Methods 0.000 abstract description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 6
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- 229920000144 PEDOT:PSS Polymers 0.000 description 4
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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
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention relates to a method for improving the capacitance of a super capacitor, which increases the temperature of the super capacitor by illuminating the super capacitor and utilizing the photo-thermal effect, thereby improving the capacitance of the super capacitor and improving the energy density and the power density. The method is simple, convenient, environment-friendly and pollution-free, does not need to be heated by an external power supply, and is suitable for energy storage application and application of solar energy conversion.
Description
Technical Field
The invention relates to the field of photo-thermal conversion and energy storage, in particular to a method for improving capacitance of a super capacitor by using photo-thermal effect.
Background
Solar energy is a renewable energy source which has rich resources, can be used freely, does not need transportation and has no pollution to the environment. Solar conversion technologies such as photovoltaics, photocatalysis, artificial photosynthesis, photothermal conversion, etc. are rapidly developed, and among them, the photothermal conversion technology has advantages of high conversion efficiency and low cost, and thus has received much attention. Heretofore, the photothermal conversion technique has been applied to various fields such as solar water purification, photothermal therapy and the like, and the application field thereof is expected to be further expanded.
Energy storage devices are indispensable elements in people's life in the world today. The super capacitor is an important energy storage device and has the advantages of high power density, high charge-discharge rate, long cycle life and the like. Supercapacitors generally include electric double layer supercapacitors, pseudocapacitive supercapacitors and hybrid supercapacitors. The double-layer super capacitor is mainly based on an ion adsorption/desorption mechanism, the pseudo-capacitor super capacitor is mainly based on a rapid Faraday reaction mechanism, and the composite super capacitor combines the double-layer super capacitor and the pseudo-capacitor super capacitor into a device (generally, one electrode is an electric double-layer electrode and the other electrode is a pseudo-capacitor electrode). Similar to other energy storage devices, such as batteries, the capacitance, energy density and power density of ultracapacitors generally decrease as temperature decreases. Therefore, there is a need to find an environmentally friendly and pollution-free method for improving the capacitance of a super capacitor at low ambient temperature to solve the performance degradation problem of the super capacitor at low temperature, and there is a need to develop a multifunctional super capacitor, such as a super capacitor that can respond to temperature or light.
Disclosure of Invention
The invention provides a method for improving the capacitance of a super capacitor, which can improve the temperature of the super capacitor by using the photo-thermal effect, thereby improving the capacitance of the super capacitor and improving the energy density and the power density along with the capacitance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for improving the capacitance of a super capacitor, which comprises the step of irradiating the super capacitor with light to increase the temperature of the super capacitor so as to improve the capacitance of the super capacitor.
According to one embodiment of the invention, the supercapacitor is an electric double layer supercapacitor, a pseudocapacitive supercapacitor or a composite supercapacitor, the composite supercapacitor having an electric double layer electrode and a pseudocapacitive electrode.
According to one embodiment of the invention, the electrode material of the supercapacitor should be a material with a photothermal conversion efficiency of more than 70%.
According to one embodiment of the invention, the electrode material of the supercapacitor is selected from one of three-dimensional graphene, carbon nanotubes or activated carbon.
According to one embodiment of the invention, the electrolyte of the supercapacitor is selected from the group consisting of polyvinyl alcohol/(acid, base, alkaline,salt) electrolyte, potassium polyacrylate/sulfuric acid electrolyte, or ionic liquid electrolyte, including but not limited to polyvinyl alcohol/phosphoric acid (PVA/H)3PO4) Electrolyte, polyvinyl alcohol/sulfuric acid (PVA/H)2SO4) One of an electrolyte, a polyvinyl alcohol/potassium hydroxide (PVA/KOH) electrolyte, or a polyvinyl alcohol/sodium chloride (PVA/NaCl) electrolyte, including but not limited to 1-butyl-3-methylimidazolium hexafluorophosphate.
According to one embodiment of the invention, the temperature of the supercapacitor reached after the illumination does not exceed the failure temperature of the electrode material, electrolyte or active substance used.
According to an embodiment of the present invention, the light source for illuminating the super capacitor includes but is not limited to one of sunlight, sodium lamp light, xenon lamp light or other illumination light source, preferably sunlight, sodium lamp light or xenon lamp light.
According to one embodiment of the invention, the illumination intensity of the super capacitor is 0.1-100 kW/m2。
According to one embodiment of the invention, the supercapacitor is located in an ambient temperature of-200 ℃ to 100 ℃.
According to one embodiment of the invention, the active material used for the pseudocapacitive electrode in the pseudocapacitive supercapacitor or the composite supercapacitor is selected from one of polymer active materials or oxide active materials, preferably poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), Polyaniline (PANI) or manganese dioxide (MnO)2)。
According to one embodiment of the present invention, the structure of the super capacitor is a planar structure, a sandwich structure or a cylindrical structure.
According to the above technical solution, the principle of capacitance improvement of the super capacitor in light is as follows: under illumination, due to the photothermal effect, the temperature of the supercapacitor is increased, so that the Faraday reaction rate is increased, the dielectric constant of an electrolyte is increased, the internal resistance of the supercapacitor is reduced, the capacitance of the supercapacitor is increased, and the power density and the energy density are also increased accordingly.
Compared with the prior art, the invention has the beneficial effects that:
the method is environment-friendly and pollution-free, the super capacitor is irradiated without heating by an external power supply, and the temperature of the super capacitor is increased by utilizing the photo-thermal effect generated by irradiation, so that the capacitance, the energy density and the power density of the super capacitor are increased, and the method is suitable for energy storage application and application of solar energy conversion.
Drawings
FIG. 1 shows a PVA/H solution containing three-dimensional graphene as an electrode used in example 1 of the present invention3PO4The structure of the double electric layer super capacitor is shown as a schematic diagram.
Fig. 2 shows the increase in capacitance of the electric double layer supercapacitor according to example 1 of the present invention when exposed to different solar radiation intensities at an ambient temperature of 25 ℃.
FIG. 3 shows the three-dimensional graphene used in example 2 as an electrode, PEDOT: PSS as an active material, PVA/H3PO4Temperature response curve of a supercapacitor, electrolyte, when exposed to 1 sun's illumination intensity at ambient temperature of 25 ℃.
Figure 4 is the equilibrium temperature reached by the supercapacitor of example 2 when irradiated with different intensities of solar radiation at an ambient temperature of 25 c.
FIG. 5a is the case of no illumination and the increase in the supercapacitor capacitance with increasing illumination intensity in example 2;
FIG. 5b shows the case where the power density and the energy density were increased with the increase of the intensity of light without light irradiation (the DC charging/discharging current density was 3.3 mA/cm) in example 2-3)。
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and the advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all without departing from the spirit and scope of the present disclosure. Moreover, all ranges and values herein are inclusive and combinable. Any number or point within the ranges set forth herein, e.g., any integer, may be treated as the minimum or maximum value to derive a lower range, etc.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1: preparation of double electric layer super capacitor and influence of illumination on performance of double electric layer super capacitor
The method for preparing the electric double layer super capacitor comprises the following steps:
(1) cutting a large three-dimensional graphene into a plurality of small pieces with the size of 10mm multiplied by 5 mm;
(2) placing the two small pieces of three-dimensional graphene in the step (1) on a (polyethylene terephthalate) PET substrate, and connecting the two small pieces of three-dimensional graphene with wires by silver paste respectively;
(3) enclosing the three-dimensional graphene in the step (2) by using a thick adhesive tape or silica gel;
(4) mixing liquid PVA/H3PO4Pouring electrolyte into the three-dimensional graphene enclosed in the step (3);
(5) putting the part obtained in the step (4) into an oven, and drying at 60 ℃;
(6) and (5) removing the thick adhesive tape or silica gel from the dried part in the step (5), and removing the PET substrate to obtain the double electric layer super capacitor, wherein the structure of the double electric layer super capacitor is shown in figure 1.
Irradiating the prepared electric double layer super capacitor with simulated sunlight at 25 deg.C, wherein the illumination intensity of sunlight can be adjusted by condenser lens and filter lens, as shown in FIG. 2, the capacitance of the electric double layer super capacitor is increased under 1 sunlight (light intensity: 1 kW/m)2) During irradiation, the temperature of the super capacitor is raised to the equilibrium temperature of about 64 ℃ within 4 minutes, the capacitance and energy density are improved by about 3.7 times, and the power is increasedThe density increased by a factor of about 4.
Example 2: preparation of pseudo-capacitor super capacitor and influence of illumination on performance of pseudo-capacitor super capacitor
The method for preparing the pseudocapacitance super capacitor comprises the following steps:
(1) infiltrating a large piece of three-dimensional graphene with 0.54% of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) aqueous solution, and then drying at 70 ℃;
(2) cutting the large three-dimensional graphene coated with PEDOT (PSS) dried in the step (1) into a plurality of small pieces with the size of 10mm multiplied by 5 mm;
(3) placing the two small pieces of three-dimensional graphene in the step (2) on a PET substrate, and connecting the two small pieces of three-dimensional graphene with wires respectively by using silver paste;
(4) enclosing the three-dimensional graphene in the step (3) by using a thick adhesive tape or silica gel;
(5) mixing liquid PVA/H2SO4Pouring electrolyte into the three-dimensional graphene enclosed in the step (4);
(6) putting the part obtained in the step (5) into an oven, and drying at 60 ℃;
(7) and (4) removing the thick adhesive tape or silica gel from the dried part in the step (6), and removing the PET substrate to obtain the pseudocapacitance super capacitor.
The manufactured pseudocapacitance super capacitor is irradiated under simulated sunlight at the environment temperature of 25 ℃, the illumination intensity of the sunlight can be adjusted through a condensing lens and a filter lens, fig. 3 is a temperature response curve of the pseudocapacitance super capacitor under the irradiation of 1 solar illumination intensity, fig. 4 is photo-thermal equilibrium temperature reached by the pseudocapacitance super capacitor under the irradiation of different solar illumination intensities, fig. 5a is the change condition that the pseudocapacitance super capacitor is not irradiated and the capacitance is increased along with the illumination intensity, and fig. 5b is the change condition that the pseudocapacitance super capacitor is not irradiated and the energy density and the power density are increased along with the illumination intensity (wherein, the direct current charging and discharging current density is 3.3mA/cm-3) It can be seen that as the intensity of illumination increases, the temperature of the pseudocapacitive supercapacitor increases, thereby increasing the capacitance, energy density and power density。
Example 3: preparation of composite super capacitor and influence of illumination on performance of composite super capacitor
The method for preparing the composite super capacitor comprises the following steps:
(1) cutting a large three-dimensional graphene into a plurality of small pieces with the size of 10mm multiplied by 5 mm;
(2) soaking large three-dimensional graphene with 0.54% of PEDOT (PEDOT: PSS) aqueous solution, and drying at 70 ℃;
(3) cutting the large three-dimensional graphene coated with PEDOT (PSS) dried in the step (2) into a plurality of small pieces with the size of 10mm multiplied by 5 mm;
(4) placing the small piece of three-dimensional graphene in the step (1) and the small piece of three-dimensional graphene in the step (3) on a PET substrate, and connecting the two small pieces of three-dimensional graphene with wires respectively by using silver paste;
(5) enclosing the three-dimensional graphene in the step (4) by using a thick adhesive tape or silica gel;
(6) mixing liquid PVA/H2SO4Pouring electrolyte into the three-dimensional graphene enclosed in the step (5);
(7) putting the part obtained in the step (6) into an oven, and drying at 60 ℃;
(8) removing the thick adhesive tape or silica gel from the part dried in the step (7), and removing the PET substrate to obtain the composite super capacitor;
the prepared composite super capacitor is irradiated by sunlight at the ambient temperature of 25 ℃, so that the temperature of the super capacitor is increased, and the capacitance, the energy density and the power density are increased.
The above embodiments are merely illustrative, and not restrictive, of the invention. Modifications and variations can be made to the above-described embodiments by those of ordinary skill in the art without departing from the spirit and scope of the present invention. Therefore, the scope of the present invention is defined by the appended claims, and is intended to be covered by the technical disclosure unless it does not affect the effect and the practical purpose of the present invention.
Claims (8)
1. A method of increasing the capacitance of an ultracapacitor, the method comprising illuminating the ultracapacitor with light to increase the temperature of the ultracapacitor to increase the capacitance of the ultracapacitor; the electrode material of the super capacitor is selected from one of three-dimensional graphene, carbon nanotubes or activated carbon; the super capacitor is an electric double layer super capacitor, a pseudo capacitor super capacitor or a composite super capacitor, and the composite super capacitor is provided with an electric double layer electrode and a pseudo capacitor electrode; the electrolyte of the super capacitor is selected from one of potassium polyacrylate/sulfuric acid electrolyte, polyvinyl alcohol/phosphoric acid electrolyte, polyvinyl alcohol/sulfuric acid electrolyte, polyvinyl alcohol/potassium hydroxide electrolyte, polyvinyl alcohol/sodium chloride electrolyte and 1-butyl-3-methylimidazole hexafluorophosphate.
2. The method for improving the capacitance of a supercapacitor according to claim 1, wherein the pseudocapacitive electrode material in the pseudocapacitive supercapacitor or the composite supercapacitor is further doped with an active material, and the active material is selected from one of a polymer active material and an oxide active material.
3. The method of increasing the capacitance of a supercapacitor of claim 2, wherein the active material is poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, polyaniline, or manganese dioxide.
4. A method of increasing the capacitance of a supercapacitor according to claim 2 or claim 3, wherein the temperature reached by the supercapacitor after illumination does not exceed the failure temperature of the electrode material, electrolyte or active material.
5. The method for increasing the capacitance of a supercapacitor according to claim 1, wherein the light source for illuminating the supercapacitor is sunlight, sodium light or xenon light.
6. The method for improving the capacitance of an ultracapacitor as in claim 1The method is characterized in that the illumination intensity of the super capacitor is 0.1-100 kW/m2。
7. The method for improving the capacitance of a supercapacitor according to claim 1, wherein the supercapacitor is exposed to an ambient temperature of-200 ℃ to 100 ℃.
8. The method according to claim 1, wherein the structure of the super capacitor is a planar structure, a sandwich structure or a cylindrical structure.
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