CN111883370A - Asymmetric printed super capacitor and preparation method thereof - Google Patents
Asymmetric printed super capacitor and preparation method thereof Download PDFInfo
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- CN111883370A CN111883370A CN202010703123.7A CN202010703123A CN111883370A CN 111883370 A CN111883370 A CN 111883370A CN 202010703123 A CN202010703123 A CN 202010703123A CN 111883370 A CN111883370 A CN 111883370A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 238000007650 screen-printing Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002861 polymer material Substances 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 229920000144 PEDOT:PSS Polymers 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000007639 printing Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000003892 spreading Methods 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- -1 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000011245 gel electrolyte Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 11
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 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
- H01G11/84—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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of an asymmetric printed super capacitor, which comprises the following steps: the first step is as follows: printing a silver electrode on a flexible substrate by utilizing a screen printing technology, and then processing the silver electrode into conductivity to obtain a silver electrode; the second step is that: screen-printing poly (3, 4-ethylenedioxythiophene) (polystyrene sulfonate) ink on a flexible substrate to obtain a thin-layer electrode; uniformly spreading the conjugated porous polymer material on the obtained thin-layer electrode to obtain a composite electrode, and then processing the composite electrode to obtain conductivity; the third step: and (3) relatively superposing the silver electrode obtained in the first step and the composite electrode obtained in the second step, coating an electrolyte in the middle, and drying to obtain the asymmetric printed supercapacitor with the sandwich structure. The invention adopts the screen printing process for processing, and the obtained capacitor has excellent cycle stability and mechanical flexibility; technical support is provided for the development and application of conjugated porous polymer materials for electrochemical energy storage.
Description
Technical Field
The invention belongs to the technical field of flexible printed electronics, and particularly relates to an asymmetric printed supercapacitor and a preparation method thereof.
Background
Through research, it is found that the introduction of heteroatoms such as N, O, B into materials such as conjugated porous polymers can effectively improve the electroactive surface area, the conductivity and the wettability of the porous materials, and can also enhance the pseudocapacitance performance of the materials. Although the porous material is applied to a plurality of different fields such as gas storage, heterogeneous catalysis and the like, the porous material can be fully utilized in the field of electrochemical energy storage due to the structural advantages of the material.
The current devices of conjugated porous polymer materials have relatively few applications, which may be related to the state of the material. Generally, the resultant conjugated porous polymer materials are insoluble powdered particles, which are disadvantageous for electronic device applications. Therefore, it is crucial to explore how to process materials into devices with functionality and flexibility, and those skilled in the art are working on developing an asymmetric printed supercapacitor based on conjugated porous polymer materials.
Disclosure of Invention
The invention aims to provide an asymmetric printing super capacitor and a preparation method thereof, and solves the problem of how to apply a powder form conjugated porous polymer material to the super capacitor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing an asymmetric printed supercapacitor, comprising the steps of:
the first step is as follows: printing a silver electrode on a flexible substrate by utilizing a screen printing technology, and then processing the silver electrode into conductivity to obtain a silver electrode;
the second step is that: screen-printing poly (3, 4-ethylenedioxythiophene) (polystyrene sulfonate) ink on a flexible substrate to obtain a thin-layer electrode; uniformly spreading the conjugated porous polymer material on the obtained thin-layer electrode to obtain a composite electrode, and then processing the composite electrode to obtain conductivity;
the third step: and (3) relatively superposing the silver electrode obtained in the first step and the composite electrode obtained in the second step, coating an electrolyte in the middle, and drying to obtain the asymmetric printed supercapacitor with the sandwich structure.
In the first step, the flexible substrate is one of polyethylene terephthalate, polyimide, polyurethane, or polydimethylsiloxane.
In the first step, the electrical conductivity of the electrode is treated by thermal annealing at the temperature of 100-150 ℃ for 8-10 min.
In the second step, the conjugated porous polymer material PDI-CMP has a structural formula shown as a formula (I):
in the second step, the electrical conductivity of the composite electrode is treated by thermal annealing at the temperature of 100 ℃ and 150 ℃ for 8-10 min.
In the third step, the electrolyte is an ionic gel electrolyte.
The ionic gel electrolyte is LiCl neutral electrolyte.
The asymmetric printed supercapacitor prepared by the method has the structure Ag// PEDOT: PSS @ PDI-CMP.
Has the advantages that:
the screen printing technology has the advantages of simplicity, practicability, low cost and the like, effectively avoids complex manufacturing process, and can simply and quickly prepare the asymmetric printing super capacitor based on the conjugated porous polymer material. The supercapacitors prepared according to the invention exhibit mechanical flexibility and integratability.
Drawings
Fig. 1 is an optical photograph and a photograph in a bent state of an asymmetrically printed supercapacitor prepared in example.
Detailed Description
The following detailed description of embodiments of the present application is provided in connection with the accompanying drawings. The reagents used in the following examples are commercially available or can be prepared by conventional methods known to those skilled in the art, and the laboratory instruments used are commercially available. The embodiments will aid those skilled in the art in further understanding the present application, but are not intended to limit the present application in any way. It should be noted that various changes and modifications can be made by one skilled in the art without departing from the spirit of the application. All falling within the scope of protection of the present application.
Example (b):
the first step is as follows: adopting a flexible substrate, obtaining a printed Ag electrode by utilizing a screen printing technology, and then putting the electrode on a 120 ℃ hot bench for annealing for 10 min;
the second step is that: and screen printing PEDOT (PSS) ink on a PET (polyethylene terephthalate) substrate to obtain a thin-layer electrode, and uniformly paving a conjugated porous polymer material PDI-CMP on the PEDOT (PSS) to obtain the PEDOT (PSS @ PDI-CMP) composite electrode. Then the composite electrode is placed on a 120 ℃ hot bench for annealing for 10min, and the composite electrode has conductivity after being dried;
the third step: relatively superposing the Ag electrode in the first step and the PEDOT: PSS @ PDI-CMP composite electrode in the second step in the same size, then leaving the edge position, coating an electrolyte in the middle, and drying to obtain the all-solid-state flexible supercapacitor with the Ag/PEDOT: PSS @ PDI-CMP asymmetric sandwich structure, wherein the area specific capacitance is 5.39mF cm-2。
Comparative example 1:
the first step is as follows: adopting a flexible substrate, obtaining a printed Ag electrode by utilizing a screen printing technology, and then putting the electrode on a 120 ℃ hot bench for annealing for 10 min;
the second step is that: screen printing PEDOT (PSS) ink on a PET substrate to obtain a thin layer electrode, and adding MnO2Uniformly spreading the material on PEDOT PSS to obtain PEDOT PSS @ MnO2And (3) a composite electrode. Then the composite electrode is placed on a 120 ℃ hot bench for annealing for 10min, and the composite electrode has conductivity after being driedElectrical property;
the third step: the Ag electrode in the first step and the PEDOT PSS @ MnO in the second step are of the same size2The edge position of the composite electrode is left after the composite electrode is relatively overlapped, the electrolyte is coated in the middle, and the Ag/PEDOT: PSS @ MnO is obtained after drying2The all-solid-state flexible super capacitor with an asymmetric sandwich structure has the area specific capacitance of 2.04mF cm-2。
Comparative example 2:
the first step is as follows: adopting a flexible substrate, obtaining a printed Ag electrode by utilizing a screen printing technology, and then putting the electrode on a 120 ℃ hot bench for annealing for 10 min;
the second step is that: screen-printing PEDOT (PSS) ink on a PET substrate to obtain a thin-layer electrode, then putting the PEDOT (PSS) electrode on a 120 ℃ hot table for annealing for 10min, and drying to obtain the conductive material;
the third step: the Ag electrode in the first step and the PEDOT and PSS electrode in the second step are oppositely overlapped in the same size, the edge position is left, the electrolyte is coated in the middle, and the all-solid-state flexible supercapacitor with the Ag/PEDOT and PSS asymmetric sandwich structure is obtained after drying, wherein the area specific capacitance is 1.94mF cm-2。
TABLE 1 test results of the sheet resistance of the electrode and the specific capacitance of the capacitor in examples and comparative examples
The invention is not the best known technology.
While the invention has been illustrated in connection with specific embodiments thereof, it will be appreciated by those skilled in the art that changes and modifications may be made thereto without departing from the spirit and scope of the invention as defined in the following claims.
Claims (8)
1. A preparation method of an asymmetric printed super capacitor is characterized by comprising the following steps: the method comprises the following steps:
the first step is as follows: printing a silver electrode on a flexible substrate by utilizing a screen printing technology, and then processing the silver electrode into conductivity to obtain a silver electrode;
the second step is that: screen-printing poly (3, 4-ethylenedioxythiophene) (polystyrene sulfonate) ink on a flexible substrate to obtain a thin-layer electrode; uniformly spreading the conjugated porous polymer material on the obtained thin-layer electrode to obtain a composite electrode, and then processing the composite electrode to obtain conductivity;
the third step: and (3) relatively superposing the silver electrode obtained in the first step and the composite electrode obtained in the second step, coating an electrolyte in the middle, and drying to obtain the asymmetric printed supercapacitor with the sandwich structure.
2. The method of claim 1 for making an asymmetric printed supercapacitor, comprising: in the first step, the flexible substrate is one of polyethylene terephthalate, polyimide, polyurethane, or polydimethylsiloxane.
3. The method of claim 1 for making an asymmetric printed supercapacitor, comprising: in the first step, the electrical conductivity of the electrode is treated by thermal annealing at the temperature of 100-150 ℃ for 8-10 min.
4. The method of claim 1 for making an asymmetric printed supercapacitor, comprising: in the second step, the conjugated porous polymer material PDI-CMP has a structural formula shown as a formula (I):
5. the method of claim 1 for making an asymmetric printed supercapacitor, comprising: in the second step, the electrical conductivity of the composite electrode is treated by thermal annealing at the temperature of 100 ℃ and 150 ℃ for 8-10 min.
6. The method of claim 1 for making an asymmetric printed supercapacitor, comprising: in the third step, the electrolyte is an ionic gel electrolyte.
7. The method of claim 6, wherein the method comprises the steps of: the ionic gel electrolyte is LiCl neutral electrolyte.
8. An asymmetric printed supercapacitor made by the method of any one of claims 1 to 7 having the structure Ag// PEDOT: PSS @ PDI-CMP.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010703123.7A CN111883370B (en) | 2020-07-21 | 2020-07-21 | Asymmetric printed super capacitor and preparation method thereof |
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| CN202010703123.7A CN111883370B (en) | 2020-07-21 | 2020-07-21 | Asymmetric printed super capacitor and preparation method thereof |
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| CN111883370B CN111883370B (en) | 2022-02-08 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101989499A (en) * | 2009-07-29 | 2011-03-23 | 美国纳米股份有限公司 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN106750293A (en) * | 2016-12-29 | 2017-05-31 | 南京邮电大学 | One kind conjugation porous polymer capacitance material and preparation method and application |
| US20180062219A1 (en) * | 2016-08-24 | 2018-03-01 | Dst Innovations Limited | Rechargeable Power Cells |
| CN110783665A (en) * | 2018-07-30 | 2020-02-11 | 通用汽车环球科技运作有限责任公司 | Capacitor assisted solid state battery |
-
2020
- 2020-07-21 CN CN202010703123.7A patent/CN111883370B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101989499A (en) * | 2009-07-29 | 2011-03-23 | 美国纳米股份有限公司 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| US20180062219A1 (en) * | 2016-08-24 | 2018-03-01 | Dst Innovations Limited | Rechargeable Power Cells |
| CN106750293A (en) * | 2016-12-29 | 2017-05-31 | 南京邮电大学 | One kind conjugation porous polymer capacitance material and preparation method and application |
| CN110783665A (en) * | 2018-07-30 | 2020-02-11 | 通用汽车环球科技运作有限责任公司 | Capacitor assisted solid state battery |
Non-Patent Citations (3)
| Title |
|---|
| DONGDONG LI等: "A Simple Strategy towards Highly Conductive Silver-Nanowire Inks for Screen-Printed Flexible Transparent Conductive Films and Wearable Energy-Storage Devices", 《ADVANCED MATERIALS TECHNOLOGIES》 * |
| YAN KOU等: "Supercapacitive Energy Storage and Electric Power Supply Using an Aza-Fused p-Conjugated Microporous Framework", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| 翁洁娜等: "共轭多孔聚合物材料与能源存储应用", 《高分子通报》 * |
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