CN113066671A - Thermoelectric flexible super capacitor and preparation method thereof - Google Patents
Thermoelectric flexible super capacitor and preparation method thereof Download PDFInfo
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- CN113066671A CN113066671A CN202110227979.6A CN202110227979A CN113066671A CN 113066671 A CN113066671 A CN 113066671A CN 202110227979 A CN202110227979 A CN 202110227979A CN 113066671 A CN113066671 A CN 113066671A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 12
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 4
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polydimethylsiloxane Polymers 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- 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
- H01G11/74—Terminals, e.g. extensions of current collectors
-
- 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
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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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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract
The invention belongs to the technical field of energy conversion and storage, and particularly relates to a thermoelectric flexible supercapacitor and a preparation method thereof. The thermoelectric flexible super capacitor comprises a capacitor main body and a packaging shell thereof, wherein the capacitor main body comprises two electrode layers and a solid electrolyte layer filled between the two electrode layers, and positive and negative leads are respectively led out of the two electrode layers to the outside of the packaging shell; the electrode layer comprises a flexible substrate layer, a current collecting layer and a PEDOT film layer which are sequentially stacked; the PEDOT film layers of the two electrode layers are respectively attached to two sides of the electrolyte layer. The thermoelectric flexible super capacitor can convert and store solar heat or heat generated in industrial production, and can play a certain role in energy crisis to a certain extent.
Description
Technical Field
The invention belongs to the technical field of energy conversion and storage, and particularly relates to a thermoelectric flexible supercapacitor and a preparation method thereof.
Background
With the continuous development of human society, traditional energy resources such as oil resources reserved on the earth are being exploited and consumed in large quantities, and the energy crisis has become one of the focuses of international society. Heat energy is ubiquitous energy, for example, solar energy is inexhaustible energy; furthermore, it is well known that much heat is also generated in the process of industrial production; the body temperature of a human body can also be counted as heat energy. If the heat energy can be stored and utilized, the energy crisis can be relieved to a certain extent.
Based on this, a supercapacitor has come into play, and for example, patent document CN105161316B discloses a flexible supercapacitor. Therefore, how to develop a thermoelectric super capacitor to directly realize the conversion and storage of thermal energy.
Disclosure of Invention
Based on the above-mentioned disadvantages and shortcomings of the prior art, it is an object of the present invention to at least solve one or more of the above-mentioned problems of the prior art, in other words, to provide a thermoelectric flexible supercapacitor and a method for manufacturing the same which satisfy one or more of the above-mentioned needs.
In order to achieve the purpose, the invention adopts the following technical scheme:
a thermoelectric flexible super capacitor comprises a capacitor body and a packaging shell thereof, wherein the capacitor body comprises two electrode layers and a solid electrolyte layer filled between the two electrode layers, and positive and negative leads are respectively led out of the two electrode layers to the outside of the packaging shell;
the electrode layer comprises a flexible substrate layer, a current collecting layer and a PEDOT film layer which are sequentially stacked;
the PEDOT film layers of the two electrode layers are respectively attached to two sides of the electrolyte layer.
Preferably, the flexible substrate layer is made of PDMS, and the thickness of the flexible substrate layer is 100-150 mm.
Preferably, the current collecting layer is an inert metal layer, and the thickness of the current collecting layer is 100-150 nm.
Preferably, the inert metal layer is gold or platinum.
Preferably, the solid electrolyte layer is polystyrene sulfonic acid.
The invention also provides a preparation method of the thermoelectric flexible supercapacitor, which comprises the following steps:
(1) sputtering and depositing inert metal on the flexible substrate layer to form a current collecting layer on the surface of the flexible substrate layer to obtain the flexible substrate layer/current collecting layer;
(2) plating a PEDOT film layer on the surface of the flexible substrate layer/the current collecting layer by using an electrodeposition method to obtain an electrode layer;
(3) filling a solid electrolyte layer between the two electrode layers for packaging; and simultaneously, leading out the anode and the cathode of the super capacitor through leads to obtain the thermoelectric flexible super capacitor.
Preferably, before the step (1), the flexible substrate layer is washed with acetone and deionized water and dried.
Preferably, in the step (1), the sputtering deposition adopts a PECVD vapor deposition method, and the vacuum degree reaches 10- 4Pa, introducing argon atmosphere, and sputtering by using direct current with the power of 100W.
Preferably, the step (2) includes:
sequentially adding SDS and EDOT into a sulfuric acid solution, uniformly stirring, and then heating the solution in a water bath to 60 ℃ to be used as electroplating solution;
a three-electrode working system is adopted for electrodeposition, a flexible substrate layer/current collecting layer is used as a working electrode, Ag/AgCl is used as a reference electrode, and Pt is used as a counter electrode.
Preferably, the concentration ratio of SDS to EDOT in the solution is 1: 1.
compared with the prior art, the invention has the beneficial effects that:
the thermoelectric flexible super capacitor can convert and store solar heat or heat generated in industrial production, and can play a certain role in energy crisis to a certain extent.
The preparation method of the thermoelectric flexible supercapacitor is simple in process and suitable for large-scale production.
Drawings
FIG. 1 is a schematic structural diagram of a thermoelectric flexible supercapacitor according to embodiment 1 of the present invention;
FIG. 2 is a graph of performance test curves of the thermoelectric flexible supercapacitor of example 1 of the present invention;
fig. 3 is a current-voltage test chart of the thermoelectric flexible supercapacitor according to embodiment 1 of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention, the following description will explain the embodiments of the present invention with reference to the accompanying drawings. It is obvious that the drawings in the following description are only some examples of the invention, and that for a person skilled in the art, other drawings and embodiments can be derived from them without inventive effort.
Example 1:
as shown in fig. 1, the method for preparing a thermoelectric flexible supercapacitor of the embodiment includes the following steps:
the method comprises the following steps: selecting PDMS as flexible substrate layers for manufacturing an upper electrode layer 4 and a lower electrode layer 5 of the thermoelectric flexible super capacitor;
specifically, the thickness of the selected PDMS substrate is 100mm, and then the PDMS substrate is washed once or several times with acetone, deionized water, and dried.
Step two: plating metal on the surfaces of the flexible substrate layers of the upper electrode layer 4 and the lower electrode layer 5 by a sputtering deposition method to generate a metal layer thereon as a current collecting layer, so as to obtain the flexible substrate layers/current collecting layers of the upper electrode layer 4 and the lower electrode layer 5;
specifically, PECVD vapor deposition method (vacuum degree up to 10) is used-4Pa, introducing argon gas, depositing inert metal with the thickness of about 100nm, such as gold, platinum and the like, by using direct current sputtering under the condition that the power is 100W), and plating the inert metal on the flexible substrate layer to form a current collecting layer on the surface of the flexible substrate layer so as to obtain the flexible substrate layer/current collecting layer.
Step three: firstly, preparing a sulfuric acid solution with the concentration of 1M/L by taking a certain amount of concentrated sulfuric acid, then adding a proper amount of EDOT and SDS into the sulfuric acid solution, wherein the concentration of EDOT in the prepared solution is 10mM/L, and the concentration of SDS is 10 mM/L; then stirring the solution for 3 minutes to form a clear solution, and finally heating the solution to 60 ℃ in a water bath;
step four: and D, respectively carrying out electrodeposition PEDOT on the flexible substrate layers/current collecting layers of the upper electrode layer 4 and the lower electrode layer 5 in the solution prepared in the step three, so that a PEDOT film is grown on the current collecting layers, and the upper electrode layer 4 and the lower electrode layer 5 are obtained.
Among them, the PEDOT film is grown to increase the conductivity of the electrode. The solution needs to be kept at a certain temperature during electrodeposition, the preferred temperature is 60 ℃, a three-electrode working system is adopted during electrodeposition, Ag/AgCl is used as a reference electrode, and Pt is used as a counter electrode; the flexible substrate/current collector layers of the upper electrode layer 4 and the lower electrode layer 5, respectively, serve as working electrodes.
Step five: filling polystyrene sulfonic acid (PSS) (namely the solid electrolyte layer 3) between PEDOT film layers of the upper electrode layer 4 and the lower electrode layer 5, and then packaging; meanwhile, the positive and negative electrodes of the super capacitor are led out through a conducting wire, and the positive and negative leads 1 and 2 are led out of the packaging shell; and obtaining the thermoelectric flexible super capacitor.
As shown in fig. 2, the charging and discharging characteristics of the thermoelectric flexible supercapacitor of the present embodiment at the temperature difference of 15 ℃ illustrate that the device can directly convert thermal energy into electric energy, and the stored electric energy can be directly utilized.
As shown in fig. 3, the current-voltage test of the thermoelectric flexible supercapacitor of the present example shows that the device has good electric double layer supercapacitor characteristics.
Example 2:
the thermoelectric flexible supercapacitor of the present embodiment is different from embodiment 1 in that:
the flexible substrate layer can be made of PDMS (polydimethylsiloxane) material, the thickness of the flexible substrate layer can be 120mm, 130mm, 150mm and the like, and the thickness of the current collecting layer can be 120mm, 130mm, 150mm and the like.
Other structures and preparation procedures can be referred to example 1.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (10)
1. A thermoelectric flexible super capacitor is characterized by comprising a capacitor main body and a packaging shell thereof, wherein the capacitor main body comprises two electrode layers and a solid electrolyte layer filled between the two electrode layers, and positive and negative leads are respectively led out of the two electrode layers to the outside of the packaging shell;
the electrode layer comprises a flexible substrate layer, a current collecting layer and a PEDOT film layer which are sequentially stacked;
the PEDOT film layers of the two electrode layers are respectively attached to two sides of the electrolyte layer.
2. The thermoelectric flexible supercapacitor according to claim 1, wherein the flexible substrate layer is made of PDMS, and the thickness of the flexible substrate layer is 100-150 mm.
3. The thermoelectric flexible supercapacitor according to claim 1, wherein the current collecting layer is an inert metal layer and has a thickness of 100 to 150 nm.
4. A thermoelectric flexible supercapacitor according to claim 3, wherein the inert metal layer is gold or platinum.
5. A thermoelectric flexible supercapacitor according to claim 1, wherein the solid electrolyte layer is polystyrene sulfonic acid.
6. A method of making a thermoelectric flexible supercapacitor according to any one of claims 1 to 5, comprising the steps of:
(1) sputtering and depositing inert metal on the flexible substrate layer to form a current collecting layer on the surface of the flexible substrate layer to obtain the flexible substrate layer/current collecting layer;
(2) plating a PEDOT film layer on the surface of the flexible substrate layer/the current collecting layer by using an electrodeposition method to obtain an electrode layer;
(3) filling a solid electrolyte layer between the two electrode layers for packaging; and simultaneously, leading out the anode and the cathode of the super capacitor through leads to obtain the thermoelectric flexible super capacitor.
7. The method of claim 6, wherein the flexible substrate layer is washed with acetone and deionized water and dried before the step (1).
8. The method according to claim 6, wherein in the step (1), the sputtering deposition is performed by PECVD vapor deposition in a vacuum degree of 10-4Pa, introducing argon atmosphere, and sputtering by using direct current with the power of 100W.
9. The method according to claim 6, wherein the step (2) comprises:
sequentially adding SDS and EDOT into a sulfuric acid solution, uniformly stirring, and then heating the solution in a water bath to 60 ℃ to be used as electroplating solution;
a three-electrode working system is adopted for electrodeposition, a flexible substrate layer/current collecting layer is used as a working electrode, Ag/AgCl is used as a reference electrode, and Pt is used as a counter electrode.
10. The method according to claim 9, wherein the concentration ratio of SDS to EDOT in the solution is 1: 1.
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| CN202110227979.6A CN113066671B (en) | 2021-03-02 | 2021-03-02 | Thermoelectric flexible supercapacitor and preparation method thereof |
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Citations (6)
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|---|---|---|---|---|
| CN102568865A (en) * | 2012-02-22 | 2012-07-11 | 华中科技大学 | Preparation method of flexible super capacitor based on paper and application thereof |
| KR101577541B1 (en) * | 2014-07-30 | 2015-12-15 | 서울대학교산학협력단 | Flexible supercapacitor and wearable energy device comprising the same |
| CN108122688A (en) * | 2017-11-24 | 2018-06-05 | 西安工业大学 | A kind of preparation method of flexible electrochemical electrode available for all-solid-state power storage device |
| CN108470645A (en) * | 2018-04-09 | 2018-08-31 | 济南大学 | A kind of flexible miniature ultracapacitor and preparation method thereof |
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| CN109346337A (en) * | 2018-10-24 | 2019-02-15 | 南通科技职业学院 | A kind of preparation method of combination electrode material |
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- 2021-03-02 CN CN202110227979.6A patent/CN113066671B/en active Active
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| CN102568865A (en) * | 2012-02-22 | 2012-07-11 | 华中科技大学 | Preparation method of flexible super capacitor based on paper and application thereof |
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| CN108470645A (en) * | 2018-04-09 | 2018-08-31 | 济南大学 | A kind of flexible miniature ultracapacitor and preparation method thereof |
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