CN113035590A - Preparation method of asymmetric three-dimensional fork comb micro-column array electrode structure super capacitor - Google Patents
Preparation method of asymmetric three-dimensional fork comb micro-column array electrode structure super capacitor Download PDFInfo
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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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a super capacitor with an asymmetric three-dimensional fork comb micro-column array electrode structure, which belongs to the field of micro super capacitors. Through the interdigital micro-column array electrode structure, the specific surface area of the electrode is effectively improved, meanwhile, an asymmetric super capacitor system can synthesize an electric double layer capacitor and a pseudo capacitor energy storage mechanism, an electrochemical stability window can be widened, the energy storage density of a device is improved, and the asymmetric super capacitor system can be applied to the fields of node power sources of the Internet of things, personal electronic products and the like.
Description
Technical Field
The invention belongs to the field of miniature supercapacitors, and particularly relates to a method for preparing a supercapacitor with an asymmetric three-dimensional fork comb micro-column array electrode structure.
Background
With the continuous development of the MEMS technology, the volume of the microsystem is continuously reduced, and the intelligent degree is continuously improved. However, miniaturization of the devices presents significant challenges to the power supply system. Micro energy technology has recently received high attention from governments of various countries as one of the key technologies of MEMS systems. At present, researchers adopt a micro energy collecting system for developing multi-source compounding of photovoltaic, vibration, temperature difference and the like to obtain higher energy density, however, with the miniaturization of the system volume, the defects of low output power and short cycle life of a thin film lithium battery and a micro nickel-zinc battery are gradually highlighted, and the working requirement of high-power output of a micro system is difficult to realize.
As an important component of micro energy storage technology, the micro super capacitor can make up the deficiency of the micro battery, and is widely concerned by various scholars. The micro super capacitor has the advantages of small volume, high energy storage density, high power density, long cycle life and the like, and has strong application prospect in fields of micro electronic devices, implantable sensors, intelligent dust particles, wireless sensor networks, micro aircrafts and the like.
At present, the micro super capacitor mainly focuses on further improving the energy storage density and power density, and research is often conducted on the aspects of materials and structures. On the basis of materials, composite materials with a three-dimensional structure, which are higher in specific surface area and higher in electrode activity, are prepared through composite modification of different electrode materials, and the comprehensive performance of the electrode materials is improved by using a special micro-nano structure and a micro-nano effect while the specific surface area is increased through preparing a three-dimensional structure electrode with a high depth-to-width ratio. In application number 2016112187543, in a preparation method of an asymmetric supercapacitor, cuprous oxide is used as a sacrificial template, cobalt hydroxide is obtained by stirring at normal temperature, and then the cobalt hydroxide is vulcanized by a hydrothermal method to obtain hollow cobalt sulfide powder, the hollow structure can shorten the diffusion distance of ions and improve the utilization rate of active substances, so that the specific capacitance of the material is improved, and the asymmetric supercapacitor is prepared by assembling the cobalt sulfide powder as a positive electrode and a porous carbon material as a negative electrode; however, the method is still limited by a complex structure processing technology and an electrode film preparation technology, and cannot meet the requirements of the current MEMS technology development on the volume of a microsystem, the energy density and the power density of a capacitor; the conventional super capacitor still mainly uses comb electrodes, most of the comb electrodes are patterned electrode films processed in a planar structure, the thickness of the electrode films is still low, and a real three-dimensional structure electrode is not realized. In addition, the problem of cracking and peeling of the electrode material in the film preparation process is still a critical problem to be solved.
Disclosure of Invention
The invention aims to provide a preparation method of a supercapacitor with an asymmetric three-dimensional fork comb micro-column array electrode structure; the super capacitor adopts micro-nano processing technologies such as ICP etching, laser engraving and the like to design and prepare a fork comb type micro-column array electrode structure, a layer of gold is sputtered on the surface of a microstructure to serve as a current collector, pseudo-capacitance and double electric layer capacitance material films are deposited on the surfaces of a positive electrode microstructure and a negative electrode microstructure respectively, and the asymmetric micro-MEMS super capacitor is prepared; the preparation process of the three-dimensional fork comb type micro-column array electrode structure is characterized by comprising the following steps:
(a) preparing an SOI (silicon on insulator) wafer: selecting SOI sheets with the thicknesses of 80 microns, 2 microns and 400 microns, performing microscopic examination on the SOI sheets by using a UV lamp and a microscope, and cleaning;
(b) spin coating a photoresist: the thickness of the photoresist is 5 mu m plus or minus 0.5 mu m;
(c) photoetching: photoetching a micro-column array shape, wherein the diameter of the micro-column is 70 mu m +/-0.5 mu m;
(d) ICP etching: etching depth of 80 μm + -0.5 μm to obtain micro-column array, and removing photoresist;
(e) performing magnetron sputtering of Au: the thickness is 80nm plus or minus 2 nm;
(f) laser engraving with a depth of 5 μm + -1 μm, etching to form a fork comb structure, and cleaning.
The anode material is a pseudocapacitance active material and comprises manganese oxide, ruthenium oxide, nickel oxide and polypyrrole.
The positive electrode material is prepared into a positive electrode film through an electrochemical deposition process, or the positive electrode film is prepared through the composite codeposition of the positive electrode material, the carbon nano tube and the graphene; the preparation process of the manganese oxide positive electrode film comprises the following steps: performing constant-current pulse deposition by using CHI660D electrochemical workstation, wherein the deposition solution is manganese acetate solution with concentration of0.2mol/L and the impressed current of the anode is 10mA/cm2The corresponding electrifying time is 20s, and the impressed current of the cathode is 10mA/cm2After deposition is finished, washing the electrode by deionized water, and then placing the electrode in a normal-temperature air atmosphere for drying for 2 hours; obtaining a positive electrode film; the constant current pulse electrodeposition process is carried out in MnO2A microscopic conductive network is formed on the surface of the electrode, so that the utilization rate of active substances is improved, and the electrode material with more excellent electrochemical performance is obtained.
The negative electrode material is an electric double layer active electrode material and comprises graphene and carbon nanotubes.
The negative double electric layer active electrode material is subjected to an electrochemical deposition process to obtain an electrode film; cleaning the three-dimensional microstructure by using an acetone solution, and then ultrasonically cleaning for 15min by using deionized water; oxidizing the carbon nano tube by using an acetone solution; preparing carbon nanotube electrode film by electrophoretic deposition method with electrochemical workstation, deposition voltage of 50V, deposition time of 15min, and electrolyte of 0.05 mg/ml Al (NO)3)3And (3) ethanol solution, washing the electrode with deionized water after deposition is finished, and then placing the electrode in a normal-temperature air atmosphere for drying for 2 hours.
The electrolyte for testing the micro MEMS super capacitor is composed of 6mol/L KOH solution and 1mol/L LiOH solution.
The invention has the beneficial effects that: by adopting micro-nano processing technologies such as ICP (inductively coupled plasma) etching, laser engraving, magnetron sputtering and the like, the fork-comb type micro-column array electrode structure is designed and prepared, the specific surface area of an electrode can be effectively increased, and the electron transmission distance is reduced, so that the electrode impedance is reduced, and the power density of a device is improved; the asymmetric micro MEMS super capacitor is prepared by respectively depositing pseudo-capacitor and double-electric-layer capacitor material films on the surfaces of the positive electrode microstructure and the negative electrode microstructure, the double-electric-layer capacitor and pseudo-capacitor energy storage mechanism can be integrated, the electrochemical stability window can be widened, the energy storage density of the device is improved, and the prepared asymmetric MEMS super capacitor can be applied to the fields of node power sources of the Internet of things, personal electronic products and the like.
Drawings
FIG. 1 is a schematic diagram of a micro MEMS supercapacitor structure.
FIG. 2 is a flow chart of a supercapacitor structure processing process.
Reference numbers in the figures: 1 is a current collector at two sides of the electrode, 2 is a fork comb anode, 3 is a micro-column array, and 4 is a fork comb cathode.
Detailed Description
The invention provides a preparation method of a supercapacitor with an asymmetric three-dimensional array electrode structure; the invention is further described below with reference to the following figures and examples:
the micro supercapacitor structure shown in fig. 1 is composed of a fork-comb anode 2, a fork-comb cathode 4 and current collectors 1 on two sides of the electrode. Wherein the fork comb anode 2 and the fork comb cathode 4 are both provided with a micro-column array 3; each microcolumn has a diameter of 70 μm and a height of 60 μm; the micro-column spacing is 80 μm, and the comb width is 80 μm.
Fig. 2 is a flow chart of a processing process of a supercapacitor electrode microstructure, which mainly comprises processes such as ICP plasma etching and sputter coating, and the specific process flow comprises:
(a) and SOI preparation: selecting an SOI (silicon on insulator) wafer, which can effectively control the etching precision of a subsequent etching process and ensure the consistency of microstructures, selecting an SOI silicon wafer with the thickness of 80 microns, 2 microns or 400 microns, performing microscopic examination on the SOI wafer by using a UV (ultraviolet) lamp and a microscope, checking whether the quality problem exists or not, and cleaning the SOI wafer;
(b) spin-coating a photoresist: the thickness of the photoresist is 5 mu m plus or minus 0.5 mu m;
(c) and (3) photoetching: developing and exposing to obtain micro-column array shape with diameter of 70 μm + -0.5 μm;
(d) ICP etching: etching the micro-column array by using a plasma etching method, wherein the etching depth is 80 microns +/-0.5 microns, and removing the photoresist;
(e) and (3) magnetron sputtering Au: sputtering gold as a current collector for subsequent electrode material deposition, wherein the sputtering thickness is 80nm +/-2 nm;
(f) laser engraving with a depth of 5 +/-1 microns, etching to form a fork-comb structure, and cleaning.
The anode material is a pseudocapacitance active material and comprises manganese oxide, ruthenium oxide, nickel oxide and polypyrrole.
The anode material is a pseudocapacitance active material and comprises manganese oxide, ruthenium oxide, nickel oxide and polypyrrole.
The positive electrode material is prepared into a positive electrode film through an electrochemical deposition process, or the positive electrode film is prepared through the composite codeposition of the positive electrode material, the carbon nano tube and the graphene;
the preparation process of the cathode film with the cathode material selected from manganese oxide comprises the following steps: cleaning the three-dimensional microcolumn with acetone solution, ultrasonically cleaning with deionized water for 15min, and performing constant current pulse deposition with CHI660D electrochemical workstation to obtain manganese acetate solution with concentration of 0.2mol/L and anode impressed current of 10mA/cm2The corresponding electrifying time is 20s, and the impressed current of the cathode is-10 mA/cm2And the corresponding electrifying time is 5s, the electrode is washed by deionized water after deposition is finished, and then the electrode is placed in the air atmosphere at the normal temperature and dried for 2 hours. Obtaining a positive electrode film, the constant current pulse electrodeposition process being in MnO2A microscopic conductive network is formed on the surface of the electrode, so that the utilization rate of active substances is improved, and the electrode material with more excellent electrochemical performance is obtained.
The preparation process of the anode film made of polypyrrole comprises the following steps: adopting an electrochemical workstation, and preparing an active electrode film by electrodeposition by using a double-electrode direct-current cathode deposition method, wherein a silicon-based microstructure is used as a cathode and a working electrode, and a platinum electrode is used as an anode and an auxiliary electrode; cleaning the three-dimensional microstructure with acetone solution, and ultrasonically cleaning with deionized water for 15min to obtain the deposit solution of sodium p-toluenesulfonate (C)7H7SO3Na) and polypyrrole (C)4H4N) of sodium p-toluenesulfonate, sodium p-toluenesulfonate (C)7H7SO3Na) concentration of 0.6mol/L, polypyrrole (C)4H4N) concentration of 0.6mol/L, adjusting pH of the solution to 4.0 with dilute sulfuric acid, and setting the deposition current density to 500 mA/cm2The deposition time is 1000 seconds, and after the deposition is finished, the electrode is washed by deionized water and then is placed in the atmosphere of normal temperature air to be dried for 2 hours.
The negative electrode material is an electric double layer active electrode material and comprises graphene and carbon nanotubes.
The negative double electric layer active electrode material is subjected to an electrochemical deposition process to obtain an electrode film; cleaning the three-dimensional microstructure by using an acetone solution, and then ultrasonically cleaning for 15min by using deionized water; oxidizing the carbon nano tube by using an acetone solution; preparing carbon nanotube electrode film by electrophoretic deposition method with electrochemical workstation, deposition voltage of 50V, deposition time of 15min, and electrolyte of 0.05 mg/ml Al (NO)3)3And (3) ethanol solution, washing the electrode with deionized water after deposition is finished, and then placing the electrode in a normal-temperature air atmosphere for drying for 2 hours.
According to the micro MEMS super capacitor, a water-based salt solution is adopted as a test electrolyte, and for a manganese dioxide film serving as a positive electrode, an electrolyte consisting of 6mol/L KOH solution and 1mol/L LiOH solution can be selected.
The miniature super capacitor can adopt solid electrolyte to carry out tube shell packaging.
The invention designs and adopts an SOI silicon chip to prepare a forked micro-column array electrode structure, can ensure the etching consistency of microstructures, effectively improve the specific surface area of a super capacitor electrode, is favorable for improving the energy storage density and the power density of a micro super capacitor, prepares an asymmetric micro MEMS super capacitor by respectively depositing pseudo-capacitance and double electric layer capacitance material films on the surfaces of a positive electrode microstructure and a negative electrode microstructure, can synthesize a double electric layer capacitance and pseudo-capacitance energy storage mechanism, can widen an electrochemical stability window, and improves the energy storage density of a device.
The invention has strong transportability and wide electrode material application range, the electrolyte can be suitable for water systems, organic systems and solid electrolyte systems, and the prepared MEMS super capacitor can be reliably integrated with other MEMS devices and has wide application prospect in the fields of personal electronic products, Internet of things nodes and the like.
Claims (7)
1. A preparation method of a supercapacitor with an asymmetric three-dimensional fork comb micro-column array electrode structure is disclosed; the super capacitor adopts micro-nano processing technologies such as ICP etching, laser engraving and the like to design and prepare a fork comb type micro-column array electrode structure, a layer of gold is sputtered on the surface of a microstructure to serve as a current collector, pseudo-capacitance and double electric layer capacitance material films are deposited on the surfaces of a positive electrode microstructure and a negative electrode microstructure respectively, and the asymmetric micro-MEMS super capacitor is prepared; the preparation process of the three-dimensional fork comb type micro-column array electrode structure is characterized by comprising the following steps:
(a) preparing an SOI (silicon on insulator) wafer: selecting SOI sheets with the thicknesses of 80 microns, 2 microns and 400 microns, performing microscopic examination on the SOI sheets by using a UV lamp and a microscope, and cleaning;
(b) spin coating a photoresist: the thickness of the photoresist is 5 mu m plus or minus 0.5 mu m;
(c) photoetching: photoetching a micro-column array shape, wherein the diameter of the micro-column is 70 mu m +/-0.5 mu m;
(d) ICP etching: etching depth of 80 μm + -0.5 μm to obtain micro-column array, and removing photoresist;
(e) performing magnetron sputtering of Au: the thickness is 80nm plus or minus 2 nm;
(f) laser engraving with a depth of 5 μm + -1 μm, etching to form a fork comb structure, and cleaning.
2. The preparation method of the asymmetric three-dimensional interdigitated and microcolumn array electrode structure supercapacitor according to claim 1, wherein the positive electrode material is a pseudocapacitive active material comprising manganese oxide, ruthenium oxide, nickel oxide and polypyrrole.
3. The preparation method of the asymmetric three-dimensional interdigitated micro-cylinder array electrode structure supercapacitor as claimed in claim 2, wherein the positive electrode material is prepared into a positive electrode film by an electrochemical deposition process, or the positive electrode material is prepared into the positive electrode film by composite codeposition with carbon nanotubes and graphene; the preparation process of the manganese oxide positive electrode film comprises the following steps: performing constant current pulse deposition by using CHI660D electrochemical workstation, wherein the deposition solution is manganese acetate solution with concentration of 0.2mol/L, and the applied current of the anode is 10mA/cm2The corresponding electrifying time is 20s, and the impressed current of the cathode is 10mA/cm2After deposition is finished, washing the electrode by deionized water, and then placing the electrode in a normal-temperature air atmosphere for drying for 2 hours; obtaining a positive electrode film;
the constant current pulse electrodeposition process is carried out in MnO2A microscopic conductive network is formed on the surface of the electrode, so that the utilization rate of active substances is improved, and the electrode material with more excellent electrochemical performance is obtained.
4. The preparation method of the asymmetric three-dimensional interdigitated micro-cylinder array electrode structure supercapacitor as claimed in claim 2 or 3, wherein the preparation process of the positive electrode film made of polypyrrole is as follows: adopting an electrochemical workstation, and preparing an active electrode film by electrodeposition by using a double-electrode direct-current cathode deposition method, wherein a silicon-based microstructure is used as a cathode and a working electrode, and a platinum electrode is used as an anode and an auxiliary electrode; cleaning the three-dimensional microstructure with acetone solution, and ultrasonically cleaning with deionized water for 15min to obtain the deposit solution of sodium p-toluenesulfonate (C)7H7SO3Na) and polypyrrole (C)4H4N) of sodium p-toluenesulfonate, sodium p-toluenesulfonate (C)7H7SO3Na) concentration of 0.6mol/L, polypyrrole (C)4H4N) concentration of 0.6mol/L, adjusting pH of the solution to 4.0 with dilute sulfuric acid, and setting the deposition current density to 500 mA/cm2The deposition time is 1000 seconds, and after the deposition is finished, the electrode is washed by deionized water and then is placed in the atmosphere of normal temperature air to be dried for 2 hours.
5. The method for preparing the supercapacitor with the asymmetric three-dimensional interdigitated and microcolumn array electrode structure according to claim 1, wherein the negative electrode material is an electric double layer active electrode material comprising graphene and carbon nanotubes.
6. The preparation method of the asymmetric three-dimensional interdigitated micro-pillar array electrode structure supercapacitor according to claim 5, wherein the negative electrode double layer active electrode material is subjected to an electrochemical deposition process to obtain an electrode film; cleaning the three-dimensional microstructure by using an acetone solution, and then ultrasonically cleaning for 15min by using deionized water; oxidizing the carbon nano tube by using an acetone solution; preparing carbon nanotube electrode film by electrophoretic deposition method using electrochemical workstation, and depositingThe pressure is 50V, the deposition time is 15min, and the electrolyte is 0.05 mg/ml Al (NO)3)3And (3) washing the electrode with deionized water after the deposition of the ethanol solution is finished, and then placing the electrode in a normal-temperature air atmosphere for drying for 2 hours to obtain the negative electrode film.
7. The preparation method of the asymmetric three-dimensional interdigitated and microcolumn array electrode structure supercapacitor according to claim 1, wherein the test electrolyte of the micro-MEMS supercapacitor is an electrolyte composed of 6mol/L KOH solution and 1mol/L LiOH solution.
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