CN102709071B - Conducting polymer modified super capacitor and manufacturing method thereof - Google Patents
Conducting polymer modified super capacitor and manufacturing method thereof Download PDFInfo
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- CN102709071B CN102709071B CN201210179910.1A CN201210179910A CN102709071B CN 102709071 B CN102709071 B CN 102709071B CN 201210179910 A CN201210179910 A CN 201210179910A CN 102709071 B CN102709071 B CN 102709071B
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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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Abstract
The invention relates to a conducting polymer modified super capacitor and a manufacturing method thereof, belonging to the technical field of super capacitors. In the invention, a plurality of micro capacitors are integrated in one single silicon substrate by using the MEMS (Micro Electro Mechanical Systems) technology, and the multiple micro capacitors are connected in parallel (or connected first in series and then in parallel) to form the super capacitor. Each micro capacitor comprises a pair of micro grooves, one isolation column is arranged between two micro grooves, and the height of the isolation column is smaller than the depth of the micro grooves; a metal electrode layer and a conducting polymer film are deposited on the groove walls of the micro grooves; and the micro grooves are filled with an electrolyte and then encapsulated. During the manufacturing process of the micro capacitor, the simple and effective conducting polymer film is directly and chemically polymerized on the metal electrode layer to modify capacitor electrodes, so that the specific capacity of micro electrodes is increased and the equivalent series resistance is reduced. The conducting polymer modified super capacitor provided by the invention has the characteristics of large specific capacity and high integration level and can be used as various power or energy storage devices.
Description
Technical field
The invention belongs to ultracapacitor technical field, particularly conducting polymer modified ultracapacitor and preparation method thereof.
Background technology
Along with socioeconomic development, people more and more pay close attention to green energy resource and biological environment.Ultracapacitor claims again electrochemical capacitor, is a kind of novel energy-storing device between traditional capacitor and battery.Compared with traditional storage battery, ultracapacitor has higher energy density, power density and long circulation life etc., as clean, the efficient novel energy-storing device of one, receive more and more researchers' concern, the development core of ultracapacitor technology is electrode material.Definition according to internal authority professor B.E.Conway of ultracapacitor research field to ultracapacitor, can be divided into two classes: a class is double electric layer capacitor, represents that material is porous carbon materials (active carbon, carbon fiber, carbon nano-tube etc.); Another kind of is fake capacitance device, represents that material is metal oxide (RuO
2, IrO
2deng) and conducting polymer (polyaniline, polypyrrole, polythiophene and derivative thereof).
The advantages such as ultracapacitor prepared by conducting polymer has that cost is low, capacity is high, the time that discharges and recharges is short, environmental friendliness and fail safe height, therefore conducting polymer has caused people's interest widely as the research of electrode material.Conducting polymer thin film is mainly with method and the compound electrode of super capacitor of preparing of inorganic material of electrochemical polymerization at present.Wherein, the patent application relating to has a kind of preparation method's (document number: CN102020845A) of conductive polyaniline polypyrrole composite membrane; A kind of preparation method's (document number: CN101979438A) of electric polypyrrole; Three-dimensional structure polypyrrole microelectrode and manufacture method thereof (document number: CN101950685A).More than the conducting polymer thin film of preparation is for modified electrode, and specific capacity is high, and device performance is good, but electrochemical process complexity, a little less than controllability.Also rarely have report and prepare conducting polymer thin film electrode for direct oxidation polymerization at present, not only function admirable of the film that the method is prepared, and method is simple, and easy to operate.
Microelectromechanical systems (MEMS) has mobility, automatic control, the feature such as integrated, is one of most important technological innovation in recent years.In the time that a subsystem can be integrated on chip piece, power supply also must complete the revolution of miniaturization, microminiaturization.MEMS micro-energy resource system is based on MEMS technology, be the micro-system that micron order, apparent size are Centimeter Level by an integrated one or more electric energy feedwaies characteristic size, can realize long-time, high-effect, multi-mode power supply, be specially adapted to some particular surroundings that conventional power source is unable to supply.Miniaturization of electronic products, microminiaturization, integrated be the main trend of world today's technical development, the main trend of power supply microminiaturization, integrability Ye Shi world today's technical development.
Summary of the invention
The present invention is directed to the technical problem that method is single, process is complicated existing in existing micro super capacitor electrode preparation method, a kind of conducting polymer modified micro super capacitor and preparation method thereof is provided.Conducting polymer modified micro super capacitor provided by the invention is formed by several button capacitor structure series and parallels, each button capacitor structure adopt MEMS fabrication techniques in same silicon substrate material, surface of metal electrode depositing electrically conductive thin polymer film, there is the large and high feature of integrated level of specific capacity.
Technical solution of the present invention is as follows:
A conducting polymer modified ultracapacitor, comprises silicon chip and is arranged at several button capacitors in silicon chip.
All button capacitors have identical structure; Each button capacitor comprises a pair of micro-recesses being arranged in silicon chip, has an insulated column between two micro-recesses, and the height of described insulated column is lower than the degree of depth of micro-recesses; The cell wall of two micro-recesses deposits metal electrode layer, and metal electrode layer surface deposition has conducting polymer thin film; Two micro-recesses that deposited metal electrode layer and conducting polymer thin film are respectively as negative electrode and the anode of button capacitor; Hermetically sealed in silicon chip inside after two the inner perfusion of micro-recesses electrolyte.
All button capacitors are parallel with one another, form ultracapacitor; Or first mutually connected by the button capacitor of equal number, form a series arm; Parallel with one another by several series arms again, form ultracapacitor.
Above-mentioned conducting polymer modified ultracapacitor, wherein said metal electrode layer material is metallic nickel, aluminium, platinum or titanium etc.; Described conducting polymer thin film is polyaniline film, film of poly pyrrole or polythiophene film; Described electrolyte is H
2sO
4, H
3pO
4, NaNO
3or the aqueous solution of KOH.Wherein H
2sO
4the concentration of the aqueous solution between 0.5～1mol/L, H
3pO
4the concentration of the aqueous solution between 0.5～1mol/L, NaNO
3the concentration of the aqueous solution is between 1 ~ 3mol/L, and the concentration of the KOH aqueous solution is between 0.5～1mol/L.
It should be noted that, in the button capacitor structure forming every pair of micro-recesses, the effect of the insulated column between two micro-recesses is to prevent the short circuit of button capacitor the two poles of the earth; The height of insulated column will be lower than the degree of depth of micro-recesses, to guarantee that electrolyte can flow between the two poles of the earth simultaneously.
A preparation method for conducting polymer modified ultracapacitor, comprises the following steps:
Step 1: adopt the silicon chip that two plate shapes are identical with size, region etching identical on every silicon chip is some to micro-recesses, has identical insulated column between every pair of micro-recesses;
Step 2: the micro-recesses of two silicon chips is aimed at Face to face, and bonding, obtain some to being closed in the micro-recesses in silicon materials;
Step 3: every pair of additional this of micro-recesses is etched away the silicon materials above the corresponding overall region of the insulated column between micro-recesses, make the height of the insulated column between every pair of micro-recesses lower than the degree of depth of micro-recesses;
Step 4: at all micro-recesses inwall deposit metal electrodes layers, and draw with plain conductor;
Step 5: at step 4 gained metal electrode layer surface deposition conducting polymer thin film;
Step 6: in micro-recesses, pour into electrolyte, then hermetically sealed; Every a pair of micro-recesses after hermetically sealed forms a button capacitor;
Step 7: all button capacitors are parallel with one another, forms ultracapacitor; Or first mutually connected by the button capacitor of equal number, form a series arm; Parallel with one another by several series arms again, form ultracapacitor.
In the preparation method of above-mentioned conducting polymer modified ultracapacitor, described metal electrode layer material is metallic nickel, aluminium, platinum or titanium etc.; Described conducting polymer thin film is polyaniline film, film of poly pyrrole or polythiophene film; Described electrolyte is the H of 0.5～1mol/L
2sO
4, 0.5 ~ 1mol/L H
3pO
4, 1 ~ 3mol/L NaNO
3or the KOH aqueous solution of 0.5～1mol/L.
Conducting polymer modified ultracapacitor provided by the invention, is made up of the multiple button capacitor series and parallels that are made in single piece of silicon backing material; Each button capacitor adopts MEMS fabrication techniques, comprise a pair of micro-recesses and the insulated column between two micro-recesses (insulated column height is lower than the degree of depth for type groove), micro-recesses inwall is deposit metal electrodes layer and conducting polymer thin film successively, deposited in the micro-recesses of metal electrode layer and conducting polymer thin film perfusion point and separated hermetically sealed formation micro capacitance after liquid, multiple micro capacitances adopt series and parallel technology finally to form ultracapacitor.Conducting polymer modified ultracapacitor provided by the invention has the advantages that specific capacity is large, integrated level is high, can be used as various power supplys or energy storage device and uses.
Brief description of the drawings
Fig. 1 plates silicon nitride layer schematic diagram on silicon chip, 1 is silicon nitride, and 2 is silicon base.
Fig. 2 is the micro-recesses structural representation on single piece of silicon substrate.
Fig. 3 is that silicon-silicon bond closes schematic diagram.
Fig. 4 is micro-recesses structural representation on silicon chip after bonding, etching.
Fig. 5 is micro-recesses inwall deposit metal electrodes layer schematic diagram, and 3 is metal electrode layer.
Fig. 6 is metal electrode layer surface deposition conducting polymer thin film schematic diagram, and 4 is conducting polymer thin film.
Fig. 7 is multiple micro capacitances structural representations that form super capacitor in parallel.
Embodiment
Below in conjunction with execution mode, the present invention is made and being further illustrated.
A preparation method for conducting polymer modified ultracapacitor, comprises the following steps:
Step 1: get the clean silicon chip that two plate shapes are identical with size, adopt pecvd process at its plated surface one deck silicon nitride (as shown in Figure 1), then adopt photoetching process identical region etching on every silicon chip some to micro-recesses, between every pair of micro-recesses, there is identical insulated column (as shown in Figure 2).
Step 2: the micro-recesses of two silicon chips is aimed at Face to face, and bonding, obtain some to being closed in the micro-recesses (as shown in Figure 3) in silicon materials.
Step 3: every pair of additional this of micro-recesses is etched away the silicon materials above the corresponding overall region of the insulated column between micro-recesses, make the height of the insulated column between every pair of micro-recesses lower than the degree of depth of micro-recesses (as shown in Figure 4).
Step 4: at all micro-recesses inwall deposit metal electrodes layers, and draw (as shown in Figure 5) with plain conductor; The deposition process of metal electrode layer can adopt vacuum vapour deposition, and electrode material can be the metals such as nickel, aluminium, platinum, titanium.
Step 5: at step 4 gained metal electrode layer surface deposition conducting polymer thin film; Concrete grammar is, first ferric trichloride or p-methyl benzenesulfonic acid ferroxidant, stearic acid secondary film formers, chloroform solvent mixed in the ratio of 2: 1: 10, then with micro syringe, mixed liquor spread in parfacies (deionized water); Then adopt czochralski process, obtain the oxidant film of one deck tens to hundreds of nanometer thickness on metal electrode layer surface; Finally oxidant film is immersed in aniline monomer, pyrrole monomer or thiophene monomer, after 30 minutes, takes out and dry, and clean with alcohol flushing, just on metal electrode, obtain one deck conducting polymer thin film (as shown in Figure 6).
Step 6: in micro-recesses, pour into electrolyte, then hermetically sealed; Every a pair of micro-recesses after hermetically sealed forms a button capacitor; Electrolyte can adopt acidity or alkaline electrolyte, as 0.5ml/L ~ 1mol/L sulfuric acid (H
2sO
4), 0.5mol/L ~ 1mol/L phosphoric acid (H
3pO
4), 1mol/L ~ 3mol/L sodium nitrate (NaNO
3), 0.5mol/L ~ 1mol/L potassium hydroxide (KOH) etc.
Step 7: all button capacitors are parallel with one another, forms ultracapacitor; Or first mutually connected by the button capacitor of equal number, form a series arm; Parallel with one another by several series arms again, form ultracapacitor.
The present invention utilizes MEMS technology that multiple button capacitors are integrated in single silicon chip, between multiple button capacitors, forms ultracapacitor by (or in parallel again after series connection) in parallel mode.In button capacitor manufacturing process, on the metal electrode of evaporation, with simple and effective direct chemical polymerization conducting polymer thin film, improve microelectrode specific capacity in order to modify electrode for capacitors, reduce equivalent series resistance (ESR) etc.Conducting polymer modified ultracapacitor provided by the invention has the advantages that specific capacity is large, integrated level is high, can be used as various power supplys or energy storage device and uses.
Claims (9)
1. a conducting polymer modified ultracapacitor, comprises silicon chip and is arranged at several button capacitors in silicon chip;
It is characterized in that:
All button capacitors have identical structure; Each button capacitor comprises a pair of micro-recesses being arranged in silicon chip, has an insulated column between two micro-recesses, and the height of described insulated column is lower than the degree of depth of micro-recesses; The cell wall of two micro-recesses deposits metal electrode layer, and metal electrode layer surface deposition has conducting polymer thin film; Two micro-recesses that deposited metal electrode layer and conducting polymer thin film are respectively as negative electrode and the anode of button capacitor; Hermetically sealed in silicon chip inside after two the inner perfusion of micro-recesses electrolyte;
All button capacitors are parallel with one another, form ultracapacitor; Or first mutually connected by the button capacitor of equal number, form a series arm; Parallel with one another by several series arms again, form ultracapacitor.
2. conducting polymer modified ultracapacitor according to claim 1, is characterized in that, described metal electrode layer material is metallic nickel, aluminium, platinum or titanium.
3. conducting polymer modified ultracapacitor according to claim 1, is characterized in that, described conducting polymer thin film is polyaniline film, film of poly pyrrole or polythiophene film.
4. conducting polymer modified ultracapacitor according to claim 1, is characterized in that, the H that described electrolyte is 0.5～1mol/L
2sO
4, 0.5～1mol/L H
3pO
4, 1～3mol/L NaNO
3or the KOH aqueous solution of 0.5～1mol/L.
5. a preparation method for conducting polymer modified ultracapacitor, comprises the following steps:
Step 1: adopt the silicon chip that two plate shapes are identical with size, region etching identical on every silicon chip is some to micro-recesses, has identical insulated column between every pair of micro-recesses;
Step 2: the micro-recesses of two silicon chips is aimed at Face to face, and bonding, obtain some to being closed in the micro-recesses in silicon materials;
Step 3: every pair of additional this of micro-recesses is etched away the silicon materials above the corresponding overall region of the insulated column between micro-recesses, make the height of the insulated column between every pair of micro-recesses lower than the degree of depth of micro-recesses;
Step 4: at all micro-recesses inwall deposit metal electrodes layers, and draw with plain conductor;
Step 5: at step 4 gained metal electrode layer surface deposition conducting polymer thin film;
Step 6: in micro-recesses, pour into electrolyte, then hermetically sealed; Every a pair of micro-recesses after hermetically sealed forms a button capacitor;
Step 7: all button capacitors are parallel with one another, forms ultracapacitor; Or first mutually connected by the button capacitor of equal number, form a series arm; Parallel with one another by several series arms again, form ultracapacitor.
6. the preparation method of conducting polymer modified ultracapacitor according to claim 5, is characterized in that, described metal electrode layer material is metallic nickel, aluminium, platinum or titanium.
7. the preparation method of conducting polymer modified ultracapacitor according to claim 5, is characterized in that, described conducting polymer thin film is polyaniline film, film of poly pyrrole or polythiophene film.
8. the preparation method of conducting polymer modified ultracapacitor according to claim 5, is characterized in that, the H that described electrolyte is 0.5～1mol/L
2sO
4, 0.5～1mol/L H
3pO
4, 1～3mol/L NaNO
3or the KOH aqueous solution of 0.5～1mol/L.
9. the preparation method of conducting polymer modified ultracapacitor according to claim 5, it is characterized in that, step 5 at the concrete grammar of metal electrode layer surface deposition conducting polymer thin film is: first ferric trichloride or p-methyl benzenesulfonic acid ferroxidant, stearic acid secondary film formers, chloroform solvent are mixed in the ratio of 2:1:10, then with micro syringe, mixed liquor is spread in parfacies (deionized water); Then adopt czochralski process, obtain the oxidant film of one deck tens to hundreds of nanometer thickness on metal electrode layer surface; Finally oxidant film is immersed in aniline monomer, pyrrole monomer or thiophene monomer, after 30 minutes, takes out and dry, and clean with alcohol flushing, just on metal electrode, obtain one deck conducting polymer thin film.
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| WO2009057010A1 (en) * | 2007-11-02 | 2009-05-07 | Nxp B.V. | Multilayer structure and method of producing the same |
| CN101916663B (en) * | 2010-08-03 | 2012-12-26 | 清华大学 | Hybrid micro super capacitor and manufacturing method thereof |
| CN101950685B (en) * | 2010-08-23 | 2012-05-23 | 清华大学 | Polypyrrole microelectrode with three-dimensional structure and preparation method thereof |
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