CN102709071A - 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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- CN102709071A CN102709071A CN2012101799101A CN201210179910A CN102709071A CN 102709071 A CN102709071 A CN 102709071A CN 2012101799101 A CN2012101799101 A CN 2012101799101A CN 201210179910 A CN201210179910 A CN 201210179910A CN 102709071 A CN102709071 A CN 102709071A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- 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 the ultracapacitor technical field, particularly conducting polymer modified ultracapacitor and preparation method thereof.
Background technology
Along with The development in society and economy, people more and more pay close attention to green energy resource and biological environment.Ultracapacitor is claimed electrochemical capacitor again, is a kind of novel energy-storing device between traditional capacitor and battery.Compare with traditional storage battery; Ultracapacitor has high energy density, power density and long circulation life etc.; As a kind of cleaning, novel energy-storing device efficiently, receive more and more researchers' concern, the development core of ultracapacitor technology is an electrode material.According to internal authority professor B.E.Conway of the ultracapacitor research field definition to ultracapacitor, can it be divided into two types: one type is double electric layer capacitor, and representing material is porous carbon materials (active carbon, carbon fiber, CNT etc.); Another kind of is the fake capacitance device, and representing material is metal oxide (RuO
2, IrO
2Deng) and conducting polymer (polyaniline, polypyrrole, polythiophene and derivative thereof).
Advantages such as the ultracapacitor of conducting polymer preparation has that cost is low, capacity is high, the time that discharges and recharges is short, environmental friendliness and fail safe height, so conducting polymer has caused people's extensive interest as the research of electrode material.Present conducting polymer thin film many method and the compound preparation electrode of super capacitor of inorganic material with electrochemical polymerization.Wherein, the patent application that relates to has a kind of preparation method's (document number: CN102020845A) of electrically conductive polyaniline composite polypyrrole film; A kind of preparation method's (document number: CN101979438A) of electric polypyrrole; Three-dimensional structure polypyrrole microelectrode and manufacturing approach (document number: CN101950685A) thereof.More than the conducting polymer thin film of preparation is used for modified electrode, and specific capacity is high, and device performance is good, but electrochemical process is complicated, a little less than the controllability.Also rarely have report and prepare the conducting polymer thin film electrode for the direct oxidation polymerization at present, the film that this method is prepared is function admirable not only, and method is simple, and is easy to operate.
Microelectromechanical systems (MEMS) has mobility, automatic control property, characteristics such as integrated, is one of most important technological innovation in recent years.When a sub-systems can be integrated on the chip piece, power supply also must be accomplished the revolution of miniaturization, microminiaturization.The MEMS micro-energy resource system is based on the MEMS technology; With the integrated characteristic size of one or more electric energy feedwaies is that micron order, apparent size are the micro-system of Centimeter Level; 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, power supply is microminiaturized, integrability also is the main trend of world today's technical development.
Summary of the invention
The present invention is directed to single, the process complicated technology problem of method that exists in the 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, have the big and high characteristics of integrated level of specific capacity.
Technical scheme of the present invention is following:
A kind of conducting polymer modified ultracapacitor comprises silicon chip and is arranged at several button capacitors in the silicon chip.
All button capacitors have identical structure; Each button capacitor comprises a pair of micro-recesses that is arranged in the silicon chip, has an insulated column between two micro-recesses, and the height of said insulated column is lower than the degree of depth of micro-recesses; The cell wall of two micro-recesses deposits metal electrode layer, and the 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 the negative electrode and the anode of button capacitor; Sealed package is inner in silicon chip behind two the inner perfusion of micro-recesses electrolyte.
All button capacitors are parallel with one another, form ultracapacitor; Perhaps connect each other by the button capacitor of equal number earlier, 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.; Said conducting polymer thin film is polyaniline film, film of poly pyrrole or polythiophene film; Said electrolyte is H
2SO
4, H
3PO
4, NaNO
3Or the aqueous solution of KOH.H wherein
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.
Need to prove that in the button capacitor structure that the every pair of micro-recesses constitutes, 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 simultaneously, can between the two poles of the earth, flow to guarantee electrolyte.
A kind of preparation method of conducting polymer modified ultracapacitor may further comprise the steps:
Step 1: adopt the two plate shapes silicon chip identical with size, regional 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 the silicon materials;
Step 3: every pair of micro-recesses is added these silicon materials to the pairing overall region of the insulated column between micro-recesses top etch away, make the height of the insulated column between every pair of micro-recesses be lower than the degree of depth of micro-recesses;
Step 4:, and draw with plain conductor at all micro-recesses inwall deposit metal electrodes layers;
Step 5: at step 4 gained metal electrode layer surface deposition conducting polymer thin film;
Step 6: in micro-recesses, pour into electrolyte, then sealed package; After the sealed package each forms a button capacitor to micro-recesses;
Step 7: all button capacitors are parallel with one another, form ultracapacitor; Perhaps connect each other by the button capacitor of equal number earlier, form a series arm; Parallel with one another by several series arms again, form ultracapacitor.
Among the preparation method of above-mentioned conducting polymer modified ultracapacitor, said metal electrode layer material is metallic nickel, aluminium, platinum or titanium etc.; Said conducting polymer thin film is polyaniline film, film of poly pyrrole or polythiophene film; Said 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 a plurality of button capacitor series and parallels that are made in the single piece of silicon backing material; Each button capacitor adopts the MEMS fabrication techniques; Comprise a pair of micro-recesses and be in two insulated columns (the insulated column height is lower than the degree of depth for the type groove) between the micro-recesses; The micro-recesses inwall is deposit metal electrodes layer and conducting polymer thin film successively; Deposited that sealed package forms micro capacitance after the perfusion point is separated liquid in the micro-recesses of metal electrode layer and conducting polymer thin film, a plurality of micro capacitances adopt the final ultracapacitor that forms of series and parallels technology.Conducting polymer modified ultracapacitor provided by the invention has the advantages that specific capacity is big, integrated level is high, can be used as various power supplys or energy storage device and uses.
Description of drawings
Fig. 1 is a plating silicon nitride layer sketch map on the silicon chip, and 1 is silicon nitride, and 2 is silicon base.
Fig. 2 is the micro-recesses structural representation on the single piece of silicon substrate.
Fig. 3 closes sketch map for silicon-silicon bond.
Fig. 4 is a micro-recesses structural representation on the silicon chip after bonding, the etching.
Fig. 5 is a micro-recesses inwall deposit metal electrodes layer sketch map, and 3 is metal electrode layer.
Fig. 6 is a metal electrode layer surface deposition conducting polymer thin film sketch map, and 4 is conducting polymer thin film.
Fig. 7 is the structural representation that a plurality of micro capacitance parallel connections form super capacitor.
Embodiment
Below in conjunction with execution mode the present invention is made and to further specify.
A kind of preparation method of conducting polymer modified ultracapacitor may further comprise the steps:
Step 1: the silicon chip of getting the cleaning identical of two plate shapes with size; Adopt pecvd process at its surface plating one deck silicon nitride (as shown in Figure 1); Adopt photoetching process identical regional etching on every silicon chip some then, have identical insulated column (as shown in Figure 2) between every pair of micro-recesses 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 (as shown in Figure 3) in the silicon materials.
Step 3: every pair of micro-recesses is added these silicon materials to the pairing overall region of the insulated column between micro-recesses top etch away, make the height of the insulated column between every pair of micro-recesses be lower than the degree of depth of micro-recesses (as shown in Figure 4).
Step 4:, and draw (as shown in Figure 5) with plain conductor at all micro-recesses inwall deposit metal electrodes layers; The deposition process of metal electrode layer can adopt vacuum vapour deposition, and electrode material can be 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, and is at first that ferric trichloride or p-methyl benzenesulfonic acid ferroxidant, stearic acid secondary film formers, chloroform solvent is even by 2: 1: 10 mixed, with micro syringe mixed liquor sprawled on parfacies (deionized water) then; Adopt czochralski process then, obtain the oxidant film of one deck tens to the hundreds of nanometer thickness at the metal electrode laminar surface; At last the oxidant film is immersed in aniline monomer, pyrrole monomer or the thiophene monomer, takes out oven dry after 30 minutes, 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 sealed package; After the sealed package each forms a button capacitor to micro-recesses; Electrolyte can adopt acidity or alkaline electrolyte, like 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, form ultracapacitor; Perhaps connect each other by the button capacitor of equal number earlier, form a series arm; Parallel with one another by several series arms again, form ultracapacitor.
The present invention utilizes the MEMS technology that a plurality of button capacitors are integrated in the single silicon chip, forms ultracapacitor through parallel connection (or parallel connection again after the series connection) mode between a plurality of button capacitors.In button capacitor manufacturing process, on the metal electrode of vapor deposition,, improve the microelectrode specific capacity in order to modify electrode for capacitors with simple and effective direct chemical polymerization conducting polymer thin film, reduce equivalent series resistance (ESR) etc.Conducting polymer modified ultracapacitor provided by the invention has the advantages that specific capacity is big, 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 the silicon chip;
All button capacitors have identical structure; Each button capacitor comprises a pair of micro-recesses that is arranged in the silicon chip, has an insulated column between two micro-recesses, and the height of said insulated column is lower than the degree of depth of micro-recesses; The cell wall of two micro-recesses deposits metal electrode layer, and the 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 the negative electrode and the anode of button capacitor; Sealed package is inner in silicon chip behind two the inner perfusion of micro-recesses electrolyte;
All button capacitors are parallel with one another, form ultracapacitor; Perhaps connect each other by the button capacitor of equal number earlier, 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, said metal electrode layer material is metallic nickel, aluminium, platinum or titanium.
3. conducting polymer modified ultracapacitor according to claim 1 is characterized in that, said 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, said 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.
5. the preparation method of a conducting polymer modified ultracapacitor may further comprise the steps:
Step 1: adopt the two plate shapes silicon chip identical with size, regional 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 the silicon materials;
Step 3: every pair of micro-recesses is added these silicon materials to the pairing overall region of the insulated column between micro-recesses top etch away, make the height of the insulated column between every pair of micro-recesses be lower than the degree of depth of micro-recesses;
Step 4:, and draw with plain conductor at all micro-recesses inwall deposit metal electrodes layers;
Step 5: at step 4 gained metal electrode layer surface deposition conducting polymer thin film;
Step 6: in micro-recesses, pour into electrolyte, then sealed package; After the sealed package each forms a button capacitor to micro-recesses;
Step 7: all button capacitors are parallel with one another, form ultracapacitor; Perhaps connect each other by the button capacitor of equal number earlier, 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 said 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 said 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 said 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.
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: at first that ferric trichloride or p-methyl benzenesulfonic acid ferroxidant, stearic acid secondary film formers, chloroform solvent is even by 2: 1: 10 mixed, with micro syringe mixed liquor is sprawled on parfacies (deionized water) then; Adopt czochralski process then, obtain the oxidant film of one deck tens to the hundreds of nanometer thickness at the metal electrode laminar surface; At last the oxidant film is immersed in aniline monomer, pyrrole monomer or the thiophene monomer, takes out oven dry after 30 minutes, and clean with alcohol flushing, just on metal electrode, obtain one deck conducting polymer thin film.
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| WO2019081970A1 (en) * | 2017-10-27 | 2019-05-02 | International Business Machines Corporation | Vertical superconducting capacitors for transmon qubits |
| CN111223678A (en) * | 2020-01-08 | 2020-06-02 | 重庆电子工程职业学院 | Method for preparing PPy flexible capacitor film conductor with porous structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019081970A1 (en) * | 2017-10-27 | 2019-05-02 | International Business Machines Corporation | Vertical superconducting capacitors for transmon qubits |
| US10445651B2 (en) | 2017-10-27 | 2019-10-15 | International Business Machines Corporation | Vertical superconducting capacitors for transmon qubits |
| CN111201622A (en) * | 2017-10-27 | 2020-05-26 | 国际商业机器公司 | Vertical superconducting capacitor for transmitting qubits |
| GB2581053A (en) * | 2017-10-27 | 2020-08-05 | Ibm | Vertical superconducting capacitors for transmon qubits |
| JP2021500739A (en) * | 2017-10-27 | 2021-01-07 | インターナショナル・ビジネス・マシーンズ・コーポレーションＩｎｔｅｒｎａｔｉｏｎａｌ Ｂｕｓｉｎｅｓｓ Ｍａｃｈｉｎｅｓ Ｃｏｒｐｏｒａｔｉｏｎ | Vertical superconducting capacitors for transmon cubits |
| GB2581053B (en) * | 2017-10-27 | 2021-11-03 | Ibm | Vertical superconducting capacitors for transmon qubits |
| JP7064180B2 (en) | 2017-10-27 | 2022-05-10 | インターナショナル・ビジネス・マシーンズ・コーポレーション | Vertical superconducting capacitors for transmon qubits |
| CN111201622B (en) * | 2017-10-27 | 2023-04-04 | 国际商业机器公司 | Vertical superconducting capacitor for transmitting qubits |
| CN111223678A (en) * | 2020-01-08 | 2020-06-02 | 重庆电子工程职业学院 | Method for preparing PPy flexible capacitor film conductor with porous structure |
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