CN101916663B - Hybrid micro super capacitor and manufacturing method thereof - Google Patents
Hybrid micro super capacitor and manufacturing method thereof Download PDFInfo
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- CN101916663B CN101916663B CN 201010243602 CN201010243602A CN101916663B CN 101916663 B CN101916663 B CN 101916663B CN 201010243602 CN201010243602 CN 201010243602 CN 201010243602 A CN201010243602 A CN 201010243602A CN 101916663 B CN101916663 B CN 101916663B
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- super capacitor
- negative pole
- micro super
- positive pole
- energy storage
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Abstract
The invention discloses a hybrid micro super capacitor and a manufacturing method thereof, which belong to the technical field of micro electro mechanical systems (MEMS). Two polyimide substrates are vertically arranged between two nickel sealing covers; a unit is formed by arranging an anode, an isolator and a cathode from top to bottom vertically between two polyimide substrates; a plurality of units are connected with one another and wound to form a cylinder; a nickel sealing cover is covered at two ends of the cylinder respectively; alkaline electrolyte is impregnated among the anode, the cathode and the isolator; and the anode and the cathode are led out from the two ends and play a role of a current collector as electrode terminals. Due to large-area contact between the metal nickel sealing cover and electrodes, the resistance of the micro super capacitor can be effectively reduced and the working voltage of micro super capacitor units is increased, so that the effect of improving the energy storing characteristics of the micro super capacitor is achieved.
Description
Technical field
The invention belongs to the MEMS technical scope, particularly a kind of hybrid micro super capacitor and manufacturing approach thereof.
Background technology
Miniaturization of electronic products, microminiaturization, integrated be the trend of the times of world today's technical development.Microelectromechanical systems (Micro Electro Mechanical Systems is called for short 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 meant the technology based on MEMS; It is that micron order, overall dimension are the micro-system of Centimeter Level that one or more electric energy feedwaies are integrated into a characteristic size; Can realize long-time, high-effect, multi-mode power supply, be specially adapted to some particular surroundings that conventional power source can't be used.The miniature energy of excellent performance is to the development of MEMS system and improve and just have special meaning.At present the patent in external this field mainly concentrates on fields such as miniature lithium ion battery, micro zinc-nickel battery, like the patent (US.6610440BS) of the relevant micro zinc-nickel battery of the patent (US.5567210) of the relevant miniature lithium ion battery of U.S. oak ridge National Laboratory and U.S. Bipolar technologies company.Preparation method in the involved little energy device of above-mentioned related patent U.S. Patent No. technology is through the small electrode of prepared in various methods yardstick; Receive the restriction of factors such as electrode area is limited; Indexs such as the internal resistance of prepared miniature energy device, capacity can not satisfy device requirement, have seriously restricted the application of miniature energy device.Compare with minicell, micro super capacitor requires to have lower internal resistance to satisfy its instantaneous high power discharge ability.And up to the present,, effective solution is not proposed as yet to the internal resistance that how effectively to reduce micro super capacitor.In addition, be no more than 1V based on the micro super capacitor cell operation voltage of alkaline electrolyte and same structure activated carbon positive and negative electrode, up to the present, the cell operation voltage to how improving micro super capacitor does not propose effective solution yet.
Summary of the invention
The objective of the invention is to micro super capacitor internal resistance in the correlation technique higherly, cell operation voltage is confined to 1V, can't satisfy device energy storage requirement and proposes a kind of hybrid micro super capacitor structure and manufacturing approach thereof.
A kind of hybrid micro super capacitor; It is characterized in that two polyimide matrixes 1 vertically are placed between the nickel capping 5 of two horizontal positioned, between two polyimide matrixes 1 relatively; Arrange positive pole 2, slider 4 and negative pole 3 from top to bottom by vertical direction, form a unit; A plurality of unit interconnect and are wound into cylinder; Nickel capping 5 is covered respectively at the cylinder two ends; Flooded alkaline electrolyte in above-mentioned anodal 2, negative pole 3 and the slider 4; Positive pole 2, negative pole 3 are drawn from two ends respectively, play the effect of collector simultaneously as electrode terminal, and the nickel capping contacts with the large tracts of land of electrode can effectively reduce micro super capacitor resistance.
Said anodal energy storage material is a hickelous nydroxide, and electric conducting material is an acetylene black, and adhesive is a polytetrafluoroethylene.The negative pole energy storage material is an activated carbon, and electric conducting material is an acetylene black, and adhesive is a polytetrafluoroethylene.Anodal and negative pole adopts different materials to form composite super capacitor can be increased to 1.4V with cell voltage.
Said slider is a loose structure, and its composition is a polytetrafluoroethylene.
Flooded alkaline electrolyte in said positive pole, negative pole and the slider, electrolyte solute composition is a potassium hydroxide, and solvent composition is a water, concentration range 4-6.5mol/L.
A kind of manufacturing approach of hybrid micro super capacitor is characterized in that, at first the slurry of positive pole and negative pole energy storage material adopts silk screen print method to be prepared in polyimide-based surface; Form positive pole and negative pole array, between positive pole and negative pole, coat slider, the dipping alkaline electrolyte; With a slice polyimide matrix surface that is incumbent on; Adopt the method that cuts that said structure is partitioned into unit one by one then, positive pole and negative pole are divided into equal two parts respectively in the cutting process, and belong to different units respectively; Be formed between another sheet polyimide matrix; Arrange by positive pole, slider and negative pole, each unit connects and reels by equidirectional becomes the coin structure, and coin shape structure both sides plated metal nickel capsule is to accomplish capacitor package.
The said anodal hickelous nydroxide that adopts is made energy storage material, comprises the anodal spherical hickelous nydroxide that is adopted of traditional nickel hydrogen battery and nickel-cadmium cell, and the preparation method is as follows: with the nickelous sulfate NiSO of 1.7mol/L
4, 0.048mol/L cobaltous sulfate CoSO
4, 0.086mol/L zinc sulfate ZnSO
4, 9mol/L the ammoniacal liquor of NaOH NaOH and 13mol/L mix, stream adds in the reactor, keeps 45-65 ℃ with pH value 9-11, and powerful simultaneously the stirring synthesized the green precipitate thing, after ageing, washing, dry Powdered hickelous nydroxide.
Said negative pole is an energy storage material with the activated carbon, and the activated carbon with characteristics such as high-specific surface area and low impurity contents can be elected to be negative material, and its specific area should be greater than 1500m
2/ g, carbon content in the material (mass ratio) is more than 98%.
The preparation of the slurry of said positive pole and negative pole energy storage material, admixture partially conductive material and adhesive and add deionized water and fully stir the slurry that the back forms good fluidity in positive pole and negative pole energy storage material.Conductive material is an acetylene black, and adhesive is a polytetrafluoroethylene, and the anode sizing agent composition is hickelous nydroxide, acetylene black, polytetrafluoroethylene, water, and its mass ratio is 7:2:1:30; The cathode size composition is activated carbon, acetylene black, polytetrafluoroethylene, water, and its mass ratio is 8:1:1:30; Acetylene black is the key factor of restriction electrode performance, and acetylene black is very few in the slurry, and then prepared electrode internal resistance is big and active relatively poor, and acetylene black is too much in the slurry, and then prepared pole strength is relatively poor.
The preparation of said slider: polytetrafluoroethylene is dissolved in the acetone fully dissolving, adopts then and get rid of the method that is coated with and be coated with and be formed between positive pole and the negative pole, and oven dry.
The invention has the beneficial effects as follows and adopt the hybrid micro super capacitor of the present invention's preparation to reduce the ultracapacitor internal resistance, improve micro super capacitor cell operation voltage, and then reach the effect of improving the micro super capacitor energy storage characteristic.
Description of drawings
Fig. 1 forms structural representation according to hybrid micro super capacitor of the present invention.
Fig. 2 is according to hybrid micro super capacitor schematic diagram of fabrication technology of the present invention.
Embodiment
The present invention proposes a kind of hybrid micro super capacitor structure and manufacturing approach thereof.Below with reference to accompanying drawing and combine embodiment to specify the present invention.
Fig. 1 forms sketch map according to the micro super capacitor structure of the embodiment of the invention.Among the figure, two polyimide matrixes 1 vertically are placed between the nickel capping 5 of two horizontal positioned relatively, between two polyimide matrixes 1, arrange positive pole 2, slider 4 and negative pole 3 from top to bottom by vertical direction, form a unit; A plurality of unit interconnect and are wound into cylinder; Nickel capping 5 is covered respectively at the cylinder two ends; Flooded alkaline electrolyte in above-mentioned anodal 2, negative pole 3 and the slider 4; Positive pole 2, negative pole 3 are drawn from two ends respectively, play the effect of collector simultaneously as electrode terminal, and the nickel capping contacts with the large tracts of land of electrode can effectively reduce micro super capacitor resistance.
In said structure; Through contacting with anodal 2 and the effective of negative pole 3 in large-area nickel capping 5; Thereby reduced the micro super capacitor internal resistance; Adopt different energy storage materials through anodal 2 respectively with negative pole 3, thereby improved the cell operation voltage of micro super capacitor, and then improved energy storage characteristic based on the said structure micro super capacitor.
Fig. 2 is the electrode manufacturing process sketch map according to the embodiment of the invention.The electrode manufacturing process of instance according to the present invention, it mainly is included in the anodal covering with coating of exsomatizing of negative pole array, electrode gap, another sheet polyimide matrix of the lip-deep silk screen print method preparation of a slice polyimide matrix 1.Exsomatize and another sheet polyimide film is formed by a slice polyimide matrix, positive pole, negative pole array, electrode gap; And slitting becomes unit 11; Comprised polyimide matrix 1 in the unit 11 this moment, comprised polyimide matrix 1, positive pole 2, negative pole 3 and slider 4 this moment in the unit 11.A plurality of unit interconnect to reel becomes coin structure 12.Coin structure both sides nickel deposited capping 5.The encapsulation of completion micro super capacitor.
The preparation of the silk screen print method of polyimide matrix surface electrode array comprises the choosing of positive pole and negative pole energy storage material, the preparation of electrode slurry and the silk screen print method preparation of electrod-array.
The both positive and negative polarity energy storage material is an activated carbon, and the activated carbon with characteristics such as high-specific surface area and low impurity contents can be elected to be negative material, and its specific area should be greater than 1500m
2/ g, carbon content in the material (mass ratio) should be higher than 98%.Choosing hickelous nydroxide is anodal energy storage material, and its preparation method is following: with the nickelous sulfate NiSO of 1.7mol/L
4(the cobaltous sulfate CoSO that contains 0.048mol/L
4, the zinc sulfate ZnSO of 0.086mol/L
4); The NaOH NaOH of 9mol/L and the ammoniacal liquor of 13mol/L add in the reactor with less flow velocity and stream, keep 55 ℃ of preference temperatures and pH value 10 and powerful simultaneously the stirring; Synthetic green precipitate thing, after ageing, washing, dry Powdered hickelous nydroxide.
The slurry that the back forms good fluidity is fully stirred in being prepared in admixture partially conductive material and adhesive in above-mentioned positive pole and the negative pole energy storage material and adding deionized water of electrode slurry.Conductive material is an acetylene black.Adhesive is a polytetrafluoroethylene.The anode sizing agent composition is hickelous nydroxide, acetylene black, polytetrafluoroethylene, water, and its best in quality ratio is 7:2:1:30.The cathode size composition is activated carbon, acetylene black, polytetrafluoroethylene, water, and its optimal proportion is 8:1:1:30.Acetylene black is the key factor of restriction electrode performance, and acetylene black is very few in the slurry, and then prepared electrode internal resistance is big and active relatively poor, and acetylene black is too much in the slurry, and then prepared pole strength is relatively poor.
The preparation method of electrod-array is based on above-mentioned electrode slurry, adopts method for printing screen, prints positive pole and negative pole array at large tracts of land polyimide matrix 1, like Fig. 2 (a).Anodal measure-alike with negative pole.500 microns-3000 microns of electrode widths, preferred 2000 microns.500 microns-1000 microns of electrode spacings, preferred 500 microns.200 microns-2000 microns of thickness of electrode, preferred 1000 microns.With additive method, method for printing screen can prepare thickness on matrix higher, the trickle clearly figure of figure.
The electrode gap process of coating that exsomatizes is: polytetrafluoroethylene is dissolved in fully dissolving in the acetone, adopts then and get rid of the method that is coated with and be coated with and be formed between the electrod-array, like Fig. 2 (b).Concrete grammar is that a slice polyimide matrix is fixed on the photoresist spinner platform; On this a slice polyimide matrix, drip an amount of above-mentioned polytetrafluoroethylene acetone soln; This a slice polyimide matrix rotating speed is evenly accelerated to necessarily than the slow-speed of revolution from static; Range of speeds 800-1200 rev/min, preferred 1000 rev/mins, and kept 10 seconds; Evenly accelerate to higher rotation speed then, range of speeds 1500-2000 rev/min, preferred 1800 change, and keep 25 seconds, evenly are decelerated to static then.The substrate of brush accomplishing horizontal positioned 30 minutes in 25 ℃ of room temperature environments is so that polymer oneself leveling and slowly discharge acetone solvent.Place it in thoroughly oven dry in 40 ℃ of vacuum drying ovens then.Acetone thoroughly removes the back polytetrafluoroethylene and forms vesicular texture.
The polytetrafluoroethylene slider gets rid of and is coated with the dipping that need carry out alkaline electrolyte after the completion, to be full of electrolyte in the pore space structure of guaranteeing electrode and slider.The electrolyte that the present invention adopted is potassium hydroxide aqueous solution, concentration 6mol/L.The electrolyte dipping process fully floods for the structure that will accomplish the preparation of electrode printing and slider is placed in the alkaline electrolyte, takes out the back and dries to remove unnecessary electrolyte.
After accomplishing, the electrolyte dipping above electrod-array, places a slice and identical another sheet polyimide matrix of above-mentioned a slice polyimide matrix again, shown in Fig. 2 (c).
The method that employing cuts is partitioned into some junior units with said structure, and positive pole and negative pole are divided into two parts and belong to different units respectively shown in Fig. 2 (d) in the cutting process;
This moment, unit 11 comprised polyimide matrix 1, positive pole 2, negative pole 3, slider 4; Be impregnated with electrolyte in positive pole 2, negative pole 3 and the slider 4; Unit 11 coilings are got up both to have formed the coin structure, like Fig. 2 (e).This moment anodal 2 and negative pole 3 lay respectively at the both sides up and down of coin structure and expose.
The magnetron sputtering technique process of nickel capping is included in coin structure both side surface and prepares nickel metal layer completion encapsulation with magnetically controlled sputter method, like Fig. 2 (e).Nickel metal layer is also born the function of electrode outside terminal when the performance sealing role is realized the micro super capacitor sealing, electric charge passes through nickel capping 5 inflows or flows out electrode in the charge and discharge process.Magnetron sputtering nickel capping technology can realize that electrode contacts with large tracts of land between the electrode terminal, has realized effective reduction of contact resistance between electrode and the nickel capping, and then has reduced condenser resistance, improves the heavy-current discharge characteristic of capacitor.Magnetron sputtering technique can also be guaranteed effective sealing of micro super capacitor, has avoided ultracapacitor failure phenomenon in the course of the work.The magnetron sputtering technique process of nickel capping does; Simultaneously upwards be fixed on the coin structure on the specimen holder of magnetron sputtering apparatus; Adopt nickel (99.99%) as target; Under high-purity argon gas atmosphere, carry out sputtering technology, preparation nickel metal layer thickness is greater than 10 microns, through prolonging the nickel metal layer that the sputter reaction time can prepare higher thickness.The coin structure simultaneously deposits after the completion its upset, the deposition another side.Thickness is crossed to hang down and is prone to cause the electrode covering imperfect, is prone to cause electrolyte to reveal, and the too high processing cost that then causes of thickness is too high.
Can adopt plating or chemical plating method that capsule is further thickeied after deposition is accomplished, compare with magnetically controlled sputter method, magnetron sputtering combines processing cost much lower with plating or chemical plating method.
The present invention proposes a kind of hybrid micro super capacitor structure and manufacturing approach thereof; Can improve the capacitor unit operating voltage; Can reduce the capacitor internal resistance; And then improve the energy storage characteristic of micro super capacitor, be widely used in fields such as sensor network nodes power supply, fuze power supplies based on micro super capacitor described in the invention.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. hybrid micro super capacitor; It is characterized in that; Two polyimide matrixes (1) vertically are placed between the nickel capping (5) of two horizontal positioned relatively; Between two polyimide matrixes (1), arrange positive pole (2), slider (4) and negative pole (3) from top to bottom by vertical direction, form a unit (11); A plurality of unit interconnect and are wound into cylinder; Nickel capping (5) is covered respectively at the cylinder two ends; Flooded alkaline electrolyte in above-mentioned positive pole (2), negative pole (3) and the slider (4); Anodal (2), negative pole (3) are drawn from two ends respectively, and the function of also bearing the electrode outside terminal when sealing role is realized the micro super capacitor sealing is being brought into play in nickel capping (5), and electric charge flows into through nickel capping (5) or the outflow electrode in the charge and discharge process; Play the effect of collector simultaneously as electrode terminal; The nickel capping contacts with the large tracts of land of electrode can effectively reduce micro super capacitor resistance, improves micro super capacitor cell operation voltage, and then reaches the effect of improving the micro super capacitor energy storage characteristic.
2. according to the said hybrid micro super capacitor of claim 1, it is characterized in that the energy storage material of said positive pole is a hickelous nydroxide, electric conducting material is an acetylene black, and adhesive is a polytetrafluoroethylene; The energy storage material of negative pole is an activated carbon, and electric conducting material is an acetylene black, and adhesive is a polytetrafluoroethylene, and anodal and negative pole adopts different materials to form composite super capacitor, and cell voltage is increased to 1.4V.
3. according to the said hybrid micro super capacitor of claim 1, it is characterized in that said slider is a loose structure, its composition is a polytetrafluoroethylene.
4. according to the said hybrid micro super capacitor of claim 1, it is characterized in that, flooded alkaline electrolyte in said positive pole, negative pole and the slider, electrolyte solute composition is a potassium hydroxide, and solvent composition is a water, concentration range 4-6.5mol/L.
5. the manufacturing approach of a hybrid micro super capacitor is characterized in that, at first the slurry with positive pole and negative pole energy storage material adopts silk screen print method to be prepared in the polyimide-based surface of a slice; Form positive pole and negative pole array, between positive pole and negative pole, coat slider, the dipping alkaline electrolyte; With another sheet polyimide matrix surface that is incumbent on; Adopt the method that cuts that said structure is partitioned into unit one by one then, positive pole and negative pole are divided into equal two parts respectively in the cutting process, and belong to different units respectively; Be formed between two polyimide matrixes; Arrange by positive pole, slider and negative pole, each unit connects and reels by equidirectional becomes the coin structure, and coin shape structure both sides plated metal nickel capsule is to accomplish capacitor package.
6. according to the manufacturing approach of the said hybrid micro super capacitor of claim 5, it is characterized in that the said anodal hickelous nydroxide that adopts is made energy storage material, the preparation method is as follows: with the nickelous sulfate NiSO of 1.7mol/L
4, 0.048mol/L cobaltous sulfate CoSO
4, 0.086mol/L zinc sulfate ZnSO
4, 9mol/L the ammoniacal liquor of NaOH NaOH and 13mol/L mix, stream adds in the reactor, keeps 45-65 ℃ with pH value 9-11, and powerful simultaneously the stirring synthesized the green precipitate thing, after ageing, washing, dry Powdered hickelous nydroxide.
7. according to the manufacturing approach of the said hybrid micro super capacitor of claim 5; It is characterized in that; Said negative pole is an energy storage material with the activated carbon, and the activated carbon with high-specific surface area and low impurity content characteristic is elected to be negative material, and its specific area should be greater than 1500m
2/ g, the quality of carbon is more than 98% than content in the material.
8. according to the manufacturing approach of the said hybrid micro super capacitor of claim 5; It is characterized in that; The preparation of the slurry of positive pole and negative pole energy storage material, admixture partially conductive material and adhesive and add deionized water and fully stir the slurry that the back forms good fluidity in positive pole and negative pole energy storage material; Conductive material is an acetylene black, and adhesive is a polytetrafluoroethylene, and the anode sizing agent composition is hickelous nydroxide, acetylene black, polytetrafluoroethylene and water, and its ratio of quality and the number of copies is 7:2:1:30; The cathode size composition is activated carbon, acetylene black, polytetrafluoroethylene and water, and its ratio of quality and the number of copies is 8:1:1:30.
9. according to the manufacturing approach of the said hybrid micro super capacitor of claim 5, it is characterized in that the preparation of said slider: polytetrafluoroethylene is dissolved in the acetone fully dissolving, adopts then and get rid of the method that is coated with and be coated with and be formed between positive pole and the negative pole, and oven dry.
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| CN102157271A (en) * | 2011-01-10 | 2011-08-17 | 复旦大学 | Super capacitor |
| CN102420310B (en) * | 2011-10-27 | 2013-12-11 | 武汉孚安特科技有限公司 | Preparation method of porous carbon electrode |
| CN102709071B (en) * | 2012-06-04 | 2014-10-15 | 电子科技大学 | Conducting polymer modified super capacitor and manufacturing method thereof |
| CN106098927B (en) * | 2016-08-09 | 2019-11-15 | 江苏艾伦摩尔微电子科技有限公司 | A kind of sandwich style flexible capacitance type pressure sensor and preparation method thereof |
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| CN1522453A (en) * | 2001-06-29 | 2004-08-18 | ������������ʽ���� | Organic electrolyte capacitor |
| CN101165828A (en) * | 2007-08-29 | 2008-04-23 | 李青海 | Buckle type electrochemical capacitor and its manufacture method |
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| US7061749B2 (en) * | 2002-07-01 | 2006-06-13 | Georgia Tech Research Corporation | Supercapacitor having electrode material comprising single-wall carbon nanotubes and process for making the same |
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| CN1522453A (en) * | 2001-06-29 | 2004-08-18 | ������������ʽ���� | Organic electrolyte capacitor |
| CN101165828A (en) * | 2007-08-29 | 2008-04-23 | 李青海 | Buckle type electrochemical capacitor and its manufacture method |
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