CN102800493A - Micro-capacitor with asymmetric 3D structure and producing method thereof - Google Patents
Micro-capacitor with asymmetric 3D structure and producing method thereof Download PDFInfo
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- CN102800493A CN102800493A CN2012102940949A CN201210294094A CN102800493A CN 102800493 A CN102800493 A CN 102800493A CN 2012102940949 A CN2012102940949 A CN 2012102940949A CN 201210294094 A CN201210294094 A CN 201210294094A CN 102800493 A CN102800493 A CN 102800493A
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- 238000000034 method Methods 0.000 title claims description 28
- 239000003990 capacitor Substances 0.000 title abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000011521 glass Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 94
- 239000000377 silicon dioxide Substances 0.000 claims description 47
- 239000011245 gel electrolyte Substances 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000000576 coating method Methods 0.000 claims description 37
- 239000010408 film Substances 0.000 claims description 26
- 239000010409 thin film Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001259 photo etching Methods 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000010412 perfusion Effects 0.000 claims description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 abstract description 9
- 239000011218 binary composite Substances 0.000 abstract 1
- 238000001020 plasma etching Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明涉及电容器及其制造技术，具体是一种非对称三维结构微电容及其制造方法。本发明解决了现有混合型超级电容器储能密度有限、容量低、抗过载能力弱、以及体积大的问题。非对称三维结构微电容包括阳极、阴极、以及玻璃基底；所述阳极包括阳极集流体、以及聚吡咯/氧化石墨烯二元复合功能薄膜；所述阳极集流体包括键合于玻璃基底上表面的阳极三维硅微结构、以及溅射于阳极三维硅微结构表面的阳极镍层；所述阴极包括阴极集流体、以及聚吡咯功能薄膜；所述阴极集流体包括键合于玻璃基底上表面的阴极三维硅微结构、以及溅射于阴极三维硅微结构表面的阴极镍层；阳极和阴极非对称设于玻璃基底上表面。本发明适用于节点电源、驱动电源等领域。
The invention relates to a capacitor and its manufacturing technology, in particular to an asymmetric three-dimensional structure micro capacitor and its manufacturing method. The invention solves the problems of limited energy storage density, low capacity, weak anti-overload ability and large volume of the existing hybrid supercapacitor. The asymmetric three-dimensional microcapacitor includes an anode, a cathode, and a glass substrate; the anode includes an anode current collector and a polypyrrole/graphene oxide binary composite functional film; the anode current collector includes a The three-dimensional silicon microstructure of the anode, and the anode nickel layer sputtered on the surface of the three-dimensional silicon microstructure of the anode; the cathode includes a cathode current collector and a polypyrrole functional film; the cathode current collector includes a cathode bonded to the upper surface of a glass substrate The three-dimensional silicon microstructure and the cathode nickel layer sputtered on the surface of the cathode three-dimensional silicon microstructure; the anode and the cathode are asymmetrically arranged on the upper surface of the glass substrate. The invention is applicable to the fields of node power supply, drive power supply and the like.
Description
Technical field
The present invention relates to capacitor and manufacturing technology thereof, specifically is little electric capacity of a kind of asymmetric three-dimensional structure and manufacturing approach thereof.
Background technology
Button capacitor is a kind of novel energy-storing device between traditional capacitor and storage battery, and it has advantages such as power density is big, the time that discharges and recharges lacks, have extended cycle life, cryogenic property is good, thereby receives science researcher's extensive attention in recent years.Hybrid super capacitor is a kind of of button capacitor, and it combines the anode of electrolytic capacitor and the negative electrode of electrochemical capacitor, has had the common advantage of electrolytic capacitor and electrochemical capacitor.In charge and discharge process, hybrid super capacitor can keep the two poles of the earth characteristics separately.When charging, active matter mass-energy genetic method draws pseudo-capacitance in the anode, and negative electrode then forms electric double layer capacitance on electrode/solution interface.In when discharge, active material produces back reaction in the anode, and solion also leaves cathode surface and gets back in the electrolyte.Therefore, hybrid super capacitor can improve energy storage density from improving its operating voltage in essence, demonstrates fabulous development prospect.Operation principle according to hybrid super capacitor can know that the total capacitance of hybrid super capacitor can regard anode capacitance as and cathode capacitance is composed in series through electrolyte, so have only when anode capacitance equals cathode capacitance, total capacitance could be maximum.Therefore, the key issue of design hybrid super capacitor just is how to select the material at its negative and positive the two poles of the earth, and optimizes the capacity ratio at its negative and positive the two poles of the earth.
At present, hybrid super capacitor mainly adopts the symmetrical structure design.Particularly, negative and positive the two poles of the earth material of existing hybrid super capacitor is normally identical, and the structure at its negative and positive the two poles of the earth and physical dimension are symmetrical.Yet practice shows that the hybrid super capacitor ubiquity energy storage density that adopts symmetrical structure to design is limited, capacity is low, anti-overload ability is weak and bulky problem.Be necessary to invent a kind of brand-new hybrid super capacitor, existing hybrid super capacitor energy storage density is limited, capacity is low to solve, a little less than the anti-overload ability and bulky problem for this reason.
Summary of the invention
Existing hybrid super capacitor energy storage density is limited, capacity is low in order to solve in the present invention, a little less than the anti-overload ability and bulky problem, little electric capacity of a kind of asymmetric three-dimensional structure and manufacturing approach thereof are provided.
The present invention adopts following technical scheme to realize: the little electric capacity of asymmetric three-dimensional structure comprises anode, negative electrode and substrate of glass; Said anode comprises anode collector and polypyrrole/graphene oxide binary complex function thin film; Said anode collector comprises anode three-dimensional silica micro-structural that is bonded to the substrate of glass upper surface and the anode nickel dam that is sputtered in anode three-dimensional silica micro-structure surface; Polypyrrole/graphene oxide binary complex function thin film is deposited on the anode nickel laminar surface; Said negative electrode comprises cathode current collector and polypyrrole function film; Said cathode current collector comprises negative electrode three-dimensional silica micro-structural that is bonded to the substrate of glass upper surface and the negative electrode nickel dam that is sputtered in negative electrode three-dimensional silica micro-structure surface; The polypyrrole function film is deposited on the cathode nickel laminar surface; The substrate of glass upper surface is coated with gel electrolyte layer; The gel electrolyte layer upper surface is coated with the BCB deielectric-coating; Anode and negative electrode are asymmetric is located at the substrate of glass upper surface, and anode and negative electrode all are embedded in the gel electrolyte layer.
The number of anode is two; The number of negative electrode is one; Two anodes are symmetrically set in the negative electrode both sides.
The degree of depth of the degree of depth of anode three-dimensional silica micro-structural, negative electrode three-dimensional silica micro-structural is 200 μ m.
The cross section of anode is a T section; The cross section of negative electrode is the S tee section.
Anode length is 120 μ m, and anode width is 20 μ m; The negative electrode internal diameter is 100 μ m.
The manufacturing approach of the little electric capacity of asymmetric three-dimensional structure (this method is used to make the little electric capacity of asymmetric three-dimensional structure of the present invention), this method are to adopt following steps to realize: a. selects substrate of glass; B. go out anode three-dimensional silica micro-structural and negative electrode three-dimensional silica micro-structural in the silicon chip surface etch at substrate of glass upper surface bonded silica substrate, and through MEMS (MEMS) photoetching process; C. at anode three-dimensional silica micro-structure surface sputter anode nickel dam, anode three-dimensional silica micro-structural and anode nickel dam constitute anode collector jointly; At negative electrode three-dimensional silica micro-structure surface sputter cathode nickel dam, negative electrode three-dimensional silica micro-structural and negative electrode nickel dam constitute cathode current collector jointly; D. at anode nickel laminar surface deposition polypyrrole/graphene oxide binary complex function thin film, anode collector and polypyrrole/graphene oxide binary complex function thin film constitutes anode jointly; At cathode nickel laminar surface deposition polypyrrole function film, cathode current collector and polypyrrole function film constitute negative electrode jointly; E. cover gel electrolyte layer at the substrate of glass upper surface, and guarantee that anode and negative electrode all are embedded in the gel electrolyte layer; F. cover the BCB deielectric-coating at the gel electrolyte layer upper surface.
Among the said step b, the MEMS photoetching process comprises the steps: at first, at silicon chip surface-coated one deck photoresist; Then, through whirl coating, preceding baking, exposure, back baking, development, rinsing, hard baking, form asymmetrical anode current collector volume graphic and cathode collector volume graphic successively on the silicon chip surface; At last, according to anode current collector volume graphic and cathode collector volume graphic, adopt RIE (reactive ion etching) technology to go out anode three-dimensional silica micro-structural and negative electrode three-dimensional silica micro-structural in the silicon chip surface etch.
In the said steps d, comprise the steps: at first, adopt pyrroles, surfactant, graphene oxide preparation to form electrolyte at anode nickel laminar surface deposition polypyrrole/graphene oxide binary complex function thin film; Then, anode collector as the work anode, is chosen the platinum plate as the work negative electrode, choose saturated calomel electrode as reference electrode; At last, the anode of will working, work negative electrode, reference electrode place this electrolyte, deposit polypyrrole/graphene oxide binary complex function thin film through the anodic oxidation polymerization at the anode nickel laminar surface; Comprise the steps: at first at cathode nickel laminar surface deposition polypyrrole function film, adopt pyrroles, surfactant preparation to form electrolyte; Then, cathode current collector as the work anode, is chosen the platinum plate as the work negative electrode, choose saturated calomel electrode as reference electrode; At last, the anode of will working, work negative electrode, reference electrode place this electrolyte, deposit the polypyrrole function film through the anodic oxidation polymerization at the cathode nickel laminar surface.
Among the said step e; Cover gel electrolyte layer at the substrate of glass upper surface and comprise the steps: at first, 1g polyvinyl alcohol and 1g potassium hydroxide are added in a certain amount of distilled water, stir 4h down at 70 ℃ and form homogeneous solution; After treating that polyvinyl alcohol and potassium hydroxide dissolve fully; In homogeneous solution, add the 0.3g potassium rhodanide, continue to stir 2h down, obtain gel electrolyte at 70 ℃; Then, at this gel electrolyte of substrate of glass upper surface perfusion, form gel electrolyte layer thus.
Among the said step f, covering the BCB deielectric-coating at the gel electrolyte layer upper surface and comprise the steps: at first, gel electrolyte is placed on the pallet, is 60r/min with the speed setting of pallet, and rotary-tray; Then,, and drip to gel electrolyte layer upper surface center and to be coated with the BCB medium at gel electrolyte layer upper surface spin coating one deck tackifier, until the BCB medium fully covered with the gel electrolyte layer upper surface; Subsequently, the rotating speed of pallet is increased to 400 r/min, treat pallet rotation 20s after; Rotating speed with pallet is increased to 2000 r/min again, treat pallet rotation 30s after, the speed drop of pallet is low to moderate 800r/min; After treating pallet rotation 30s, the BCB medium is spared film, form the BCB deielectric-coating thus; Subsequently; To dry by the fire the sheet temperature and be set at 80 ℃, the BCB deielectric-coating will be dried by the fire sheet 3min, make the partial solvent volatilization in the BCB deielectric-coating; Reduce BCB deielectric-coating flowing in moving process with this; Improve the uniformity of BCB deielectric-coating after curing, and in the baking sheet, feed nitrogen protection, prevent in baking sheet process BCB medium film strength to be exerted an influence because of oxygen and silicon chip react with this; At last, adopt the stepped temperature-raising method baking sheet temperature that raises, the BCB deielectric-coating dried by the fire sheet, and in the baking sheet, feed nitrogen protection, wait to dry by the fire after the sheet temperature is increased to 280 ℃, to the BCB deielectric-coating heat successively, with the stove cooling, solidify the BCB deielectric-coating thus.
Compare with existing hybrid super capacitor; Little electric capacity of asymmetric three-dimensional structure of the present invention and manufacturing approach thereof have the following advantages: one, two kinds of dissimilar electrodes are adopted at its negative and positive the two poles of the earth respectively; And the structure at negative and positive the two poles of the earth and physical dimension adopt the unsymmetric structure design, have effectively promoted the energy storage density and the capacity of electric capacity thus.Two, it has adopted the MEMS photoetching process in manufacture process, has effectively strengthened the anti-overload ability of electric capacity thus, has effectively reduced the volume of electric capacity.In sum, little electric capacity of asymmetric three-dimensional structure of the present invention and manufacturing approach thereof be based on brand-new structure and principle, efficiently solves that existing hybrid super capacitor energy storage density is limited, capacity is low, anti-overload ability is weak and bulky problem.
The present invention efficiently solves that existing hybrid super capacitor energy storage density is limited, capacity is low, anti-overload ability is weak and bulky problem; It has series of advantages such as energy storage density height, capacity is big, anti-overload ability is strong, volume is little, is applicable to fields such as node power, driving power.
Description of drawings
Fig. 1 is the structural representation of the little electric capacity of asymmetric three-dimensional structure of the present invention.
Fig. 2 is the A-A cutaway view of Fig. 1.
Among the figure: 1-anode, 2-negative electrode, 3-substrate of glass, 4-anode three-dimensional silica micro-structural; 5-anode nickel dam, 6-polypyrrole/graphene oxide binary complex function thin film, 7-negative electrode three-dimensional silica micro-structural; 8-negative electrode nickel dam, 9-polypyrrole function film, 10-gel electrolyte layer.
Embodiment
The little electric capacity of asymmetric three-dimensional structure comprises anode 1, negative electrode 2 and substrate of glass 3;
Said anode 1 comprises anode collector and polypyrrole/graphene oxide binary complex function thin film 6; The anode nickel dam 5 that said anode collector comprises the anode three-dimensional silica micro-structural 4 that is bonded to substrate of glass 3 upper surfaces and is sputtered in anode three-dimensional silica micro-structural 4 surfaces; Polypyrrole/graphene oxide binary complex function thin film 6 is deposited on anode nickel dam 5 surfaces;
Said negative electrode 2 comprises cathode current collector and polypyrrole function film 9; The negative electrode nickel dam 8 that said cathode current collector comprises the negative electrode three-dimensional silica micro-structural 7 that is bonded to substrate of glass 3 upper surfaces and is sputtered in negative electrode three-dimensional silica micro-structural 7 surfaces; Polypyrrole function film 9 is deposited on negative electrode nickel dam 8 surfaces;
Substrate of glass 3 upper surfaces are coated with gel electrolyte layer 10; Gel electrolyte layer 10 upper surfaces are coated with the BCB deielectric-coating; Anode 1 and negative electrode 2 are asymmetric is located at substrate of glass 3 upper surfaces, and anode 1 all is embedded in the gel electrolyte layer 10 with negative electrode 2;
The number of anode 1 is two; The number of negative electrode 2 is one; Two anodes 1 are symmetrically set in negative electrode 2 both sides;
The degree of depth of the degree of depth of anode three-dimensional silica micro-structural 4, negative electrode three-dimensional silica micro-structural 7 is 200 μ m;
The cross section of anode 1 is a T section; The cross section of negative electrode 2 is the S tee section;
Anode 1 length is 120 μ m, and anode 1 width is 20 μ m; Negative electrode 2 internal diameters are 100 μ m.
The manufacturing approach of the little electric capacity of asymmetric three-dimensional structure (this method is used to make the little electric capacity of asymmetric three-dimensional structure of the present invention), this method are to adopt following steps to realize:
A. select substrate of glass 3;
B. go out anode three-dimensional silica micro-structural 4 and negative electrode three-dimensional silica micro-structural 7 in the silicon chip surface etch at substrate of glass 3 upper surface bonded silica substrates, and through the MEMS photoetching process;
C. at anode three-dimensional silica micro-structural 4 surface sputtering anode nickel dams 5, anode three-dimensional silica micro-structural 4 constitutes anode collector jointly with anode nickel dam 5; At negative electrode three-dimensional silica micro-structural 7 surface sputtering negative electrode nickel dams 8, negative electrode three-dimensional silica micro-structural 7 and negative electrode nickel dam 8 common formation cathode current collectors;
D. at anode nickel dam 5 surface depositions polypyrrole/graphene oxide binary complex function thin film 6, anode collector and polypyrrole/graphene oxide binary complex function thin film 6 constitutes anodes 1 jointly; At negative electrode nickel dam 8 surface deposition polypyrrole function films 9, cathode current collector and polypyrrole function film 9 common formation negative electrodes 2;
E. cover gel electrolyte layer 10 at substrate of glass 3 upper surfaces, and guarantee that anode 1 and negative electrode 2 all are embedded in the gel electrolyte layer 10;
F. cover the BCB deielectric-coating at gel electrolyte layer 10 upper surfaces;
Among the said step b, the MEMS photoetching process comprises the steps: at first, at silicon chip surface-coated one deck photoresist; Then, through whirl coating, preceding baking, exposure, back baking, development, rinsing, hard baking, form asymmetrical anode current collector volume graphic and cathode collector volume graphic successively on the silicon chip surface; At last, according to anode current collector volume graphic and cathode collector volume graphic, adopt RIE technology to go out anode three-dimensional silica micro-structural 4 and negative electrode three-dimensional silica micro-structural 7 in the silicon chip surface etch;
In the said steps d, comprise the steps: at first, adopt pyrroles, surfactant, graphene oxide preparation to form electrolyte at anode nickel dam 5 surface depositions polypyrrole/graphene oxide binary complex function thin film 6; Then, anode collector as the work anode, is chosen the platinum plate as the work negative electrode, choose saturated calomel electrode as reference electrode; At last, the anode of will working, work negative electrode, reference electrode place this electrolyte, through the anodic oxidation polymerization at anode nickel dam 5 surface depositions polypyrrole/graphene oxide binary complex function thin film 6; Comprise the steps: at first at negative electrode nickel dam 8 surface deposition polypyrrole function films 9, adopt pyrroles, surfactant preparation to form electrolyte; Then, cathode current collector as the work anode, is chosen the platinum plate as the work negative electrode, choose saturated calomel electrode as reference electrode; At last, the anode of will working, work negative electrode, reference electrode place this electrolyte, through the anodic oxidation polymerization at negative electrode nickel dam 8 surface deposition polypyrrole function films 9;
Among the said step e; Cover gel electrolyte layer 10 at substrate of glass 3 upper surfaces and comprise the steps: at first, 1g polyvinyl alcohol and 1g potassium hydroxide are added in a certain amount of distilled water, stir 4h down at 70 ℃ and form homogeneous solution; After treating that polyvinyl alcohol and potassium hydroxide dissolve fully; In homogeneous solution, add the 0.3g potassium rhodanide, continue to stir 2h down, obtain gel electrolyte at 70 ℃; Then, at this gel electrolyte of substrate of glass 3 upper surfaces perfusion, form gel electrolyte layer 10 thus;
Among the said step f, covering the BCB deielectric-coating at gel electrolyte layer 10 upper surfaces and comprise the steps: at first, gel electrolyte layer 10 is placed on the pallet, is 60r/min with the speed setting of pallet, and rotary-tray; Then,, and drip to gel electrolyte layer 10 upper surface centers and to be coated with the BCB medium at gel electrolyte layer 10 upper surface spin coating one deck tackifier, until the BCB medium fully covered with gel electrolyte layer 10 upper surfaces; Subsequently, the rotating speed of pallet is increased to 400 r/min, treat pallet rotation 20s after; Rotating speed with pallet is increased to 2000 r/min again, treat pallet rotation 30s after, the speed drop of pallet is low to moderate 800r/min; After treating pallet rotation 30s, the BCB medium is spared film, form the BCB deielectric-coating thus; Subsequently; To dry by the fire the sheet temperature and be set at 80 ℃, the BCB deielectric-coating will be dried by the fire sheet 3min, make the partial solvent volatilization in the BCB deielectric-coating; Reduce BCB deielectric-coating flowing in moving process with this; Improve the uniformity of BCB deielectric-coating after curing, and in the baking sheet, feed nitrogen protection, prevent in baking sheet process BCB medium film strength to be exerted an influence because of oxygen and silicon chip react with this; At last, adopt the stepped temperature-raising method baking sheet temperature that raises, the BCB deielectric-coating dried by the fire sheet, and in the baking sheet, feed nitrogen protection, wait to dry by the fire after the sheet temperature is increased to 280 ℃, to the BCB deielectric-coating heat successively, with the stove cooling, solidify the BCB deielectric-coating thus.
During practical implementation, substrate of glass 3 adopts the LAS devitrified glass to process.The thickness of substrate of glass 3 is 0.5 mm.The area of substrate of glass 3 is 15mm * 15mm.The thickness of silicon chip is 0.2mm.The area of silicon chip is 12 * 12 mm.The thickness of photoresist is 10 ~ 30 μ m.The thickness of the thickness of anode nickel dam 5 and negative electrode nickel dam 8 is 0.2 ~ 0.3 μ m.Polypyrrole/the thickness of graphene oxide binary complex function thin film 6 and the thickness of polypyrrole function film 9 are 2 ~ 5 μ m.The thickness of BCB deielectric-coating is 30 μ m ~ 50 μ m.Silicon chip adopts the naked silicon chip of P type of single-sided polishing to process.
Claims (10)
1. the little electric capacity of asymmetric three-dimensional structure is characterized in that: comprise anode (1), negative electrode (2) and substrate of glass (3);
Said anode (1) comprises anode collector and polypyrrole/graphene oxide binary complex function thin film (6); The anode nickel dam (5) that said anode collector comprises the anode three-dimensional silica micro-structural (4) that is bonded to substrate of glass (3) upper surface and is sputtered in anode three-dimensional silica micro-structural (4) surface; Polypyrrole/graphene oxide binary complex function thin film (6) is deposited on anode nickel dam (5) surface;
Said negative electrode (2) comprises cathode current collector and polypyrrole function film (9); The negative electrode nickel dam (8) that said cathode current collector comprises the negative electrode three-dimensional silica micro-structural (7) that is bonded to substrate of glass (3) upper surface and is sputtered in negative electrode three-dimensional silica micro-structural (7) surface; Polypyrrole function film (9) is deposited on negative electrode nickel dam (8) surface;
Substrate of glass (3) upper surface is coated with gel electrolyte layer (10); Gel electrolyte layer (10) upper surface is coated with the BCB deielectric-coating; Anode (1) and negative electrode (2) are asymmetric is located at substrate of glass (3) upper surface, and anode (1) and negative electrode (2) all are embedded in the gel electrolyte layer (10).
2. the little electric capacity of asymmetric three-dimensional structure according to claim 1 is characterized in that: the number of anode (1) is two; The number of negative electrode (2) is one; Two anodes (1) are symmetrically set in negative electrode (2) both sides.
3. the little electric capacity of asymmetric three-dimensional structure according to claim 1 is characterized in that: the degree of depth of the degree of depth of anode three-dimensional silica micro-structural (4), negative electrode three-dimensional silica micro-structural (7) is 200 μ m.
4. the little electric capacity of asymmetric three-dimensional structure according to claim 1 is characterized in that: the cross section of anode (1) is a T section; The cross section of negative electrode (2) is the S tee section.
5. the little electric capacity of asymmetric three-dimensional structure according to claim 4 is characterized in that: anode (1) length is 120 μ m, and anode (1) width is 20 μ m; Negative electrode (2) internal diameter is 100 μ m.
6. the manufacturing approach of the little electric capacity of asymmetric three-dimensional structure, this method is used to make the little electric capacity of a kind of asymmetric three-dimensional structure as claimed in claim 1, it is characterized in that: this method is to adopt following steps to realize:
A. select substrate of glass (3);
B. go out anode three-dimensional silica micro-structural (4) and negative electrode three-dimensional silica micro-structural (7) in the silicon chip surface etch at substrate of glass (3) upper surface bonded silica substrate, and through the MEMS photoetching process;
C. at anode three-dimensional silica micro-structural (4) surface sputtering anode nickel dam (5), anode three-dimensional silica micro-structural (4) and anode nickel dam (5) constitute anode collector jointly; At negative electrode three-dimensional silica micro-structural (7) surface sputtering negative electrode nickel dam (8), negative electrode three-dimensional silica micro-structural (7) and negative electrode nickel dam (8) constitute cathode current collector jointly;
D. at anode nickel dam (5) surface deposition polypyrrole/graphene oxide binary complex function thin film (6), anode collector and polypyrrole/graphene oxide binary complex function thin film (6) constitutes anode (1) jointly; At negative electrode nickel dam (8) surface deposition polypyrrole function film (9), cathode current collector and polypyrrole function film (9) constitute negative electrode (2) jointly;
E. cover gel electrolyte layer (10) at substrate of glass (3) upper surface, and guarantee that anode (1) and negative electrode (2) all are embedded in the gel electrolyte layer (10);
F. cover the BCB deielectric-coating at gel electrolyte layer (10) upper surface.
7. the manufacturing approach of the little electric capacity of asymmetric three-dimensional structure according to claim 6 is characterized in that: among the said step b, the MEMS photoetching process comprises the steps: at first, at silicon chip surface-coated one deck photoresist; Then, through whirl coating, preceding baking, exposure, back baking, development, rinsing, hard baking, form asymmetrical anode current collector volume graphic and cathode collector volume graphic successively on the silicon chip surface; At last, according to anode current collector volume graphic and cathode collector volume graphic, adopt RIE technology to go out anode three-dimensional silica micro-structural (4) and negative electrode three-dimensional silica micro-structural (7) in the silicon chip surface etch.
8. the manufacturing approach of the little electric capacity of asymmetric three-dimensional structure according to claim 6; It is characterized in that: in the said steps d; Comprise the steps: at first at anode nickel dam (5) surface deposition polypyrrole/graphene oxide binary complex function thin film (6), adopt pyrroles, surfactant, graphene oxide preparation to form electrolyte; Then, anode collector as the work anode, is chosen the platinum plate as the work negative electrode, choose saturated calomel electrode as reference electrode; At last, the anode of will working, work negative electrode, reference electrode place this electrolyte, through the anodic oxidation polymerization at anode nickel dam (5) surface deposition polypyrrole/graphene oxide binary complex function thin film (6); Comprise the steps: at first at negative electrode nickel dam (8) surface deposition polypyrrole function film (9), adopt pyrroles, surfactant preparation to form electrolyte; Then, cathode current collector as the work anode, is chosen the platinum plate as the work negative electrode, choose saturated calomel electrode as reference electrode; At last, the anode of will working, work negative electrode, reference electrode place this electrolyte, through the anodic oxidation polymerization at negative electrode nickel dam (8) surface deposition polypyrrole function film (9).
9. the manufacturing approach of the little electric capacity of asymmetric three-dimensional structure according to claim 6; It is characterized in that: among the said step e; Cover gel electrolyte layer (10) at substrate of glass (3) upper surface and comprise the steps: at first, 1g polyvinyl alcohol and 1g potassium hydroxide are added in a certain amount of distilled water, stir 4h down at 70 ℃ and form homogeneous solution; After treating that polyvinyl alcohol and potassium hydroxide dissolve fully; In homogeneous solution, add the 0.3g potassium rhodanide, continue to stir 2h down, obtain gel electrolyte at 70 ℃; Then, at this gel electrolyte of substrate of glass (3) upper surface perfusion, form gel electrolyte layer (10) thus.
10. the manufacturing approach of the little electric capacity of asymmetric three-dimensional structure according to claim 6; It is characterized in that: among the said step f; Covering the BCB deielectric-coating at gel electrolyte layer (10) upper surface comprises the steps: at first; Gel electrolyte layer (10) is placed on the pallet, is 60r/min with the speed setting of pallet, and rotary-tray; Then,, and drip to gel electrolyte layer (10) upper surface center and to be coated with the BCB medium at gel electrolyte layer (10) upper surface spin coating one deck tackifier, until the BCB medium fully covered with gel electrolyte layer (10) upper surface; Subsequently, the rotating speed of pallet is increased to 400 r/min, treat pallet rotation 20s after; Rotating speed with pallet is increased to 2000 r/min again, treat pallet rotation 30s after, the speed drop of pallet is low to moderate 800r/min; After treating pallet rotation 30s, the BCB medium is spared film, form the BCB deielectric-coating thus; Subsequently; To dry by the fire the sheet temperature and be set at 80 ℃, the BCB deielectric-coating will be dried by the fire sheet 3min, make the partial solvent volatilization in the BCB deielectric-coating; Reduce BCB deielectric-coating flowing in moving process with this; Improve the uniformity of BCB deielectric-coating after curing, and in the baking sheet, feed nitrogen protection, prevent in baking sheet process BCB medium film strength to be exerted an influence because of oxygen and silicon chip react with this; At last, adopt the stepped temperature-raising method baking sheet temperature that raises, the BCB deielectric-coating dried by the fire sheet, and in the baking sheet, feed nitrogen protection, wait to dry by the fire after the sheet temperature is increased to 280 ℃, to the BCB deielectric-coating heat successively, with the stove cooling, solidify the BCB deielectric-coating thus.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080158778A1 (en) * | 1999-06-11 | 2008-07-03 | Lipka Stephen M | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN101325130A (en) * | 2008-05-22 | 2008-12-17 | 清华大学 | Polypyrrole micro-supercapacitor based on MEMS technology and manufacturing method thereof |
| CN101916667A (en) * | 2010-09-19 | 2010-12-15 | 西安交通大学 | Asymmetric supercapacitors based on MnO2 and PPy/F-CNTs composite materials |
| CN101989499A (en) * | 2009-07-29 | 2011-03-23 | 美国纳米股份有限公司 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN102496470A (en) * | 2011-11-14 | 2012-06-13 | 清华大学 | Asymmetric miniature ultracapacitor based on MEMS technology and manufacturing method thereof |
| CN102568848A (en) * | 2011-12-21 | 2012-07-11 | 天津大学 | Preparation method of polyaniline/graphene oxide composite electrode material |
-
2012
- 2012-08-18 CN CN201210294094.9A patent/CN102800493B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080158778A1 (en) * | 1999-06-11 | 2008-07-03 | Lipka Stephen M | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN101325130A (en) * | 2008-05-22 | 2008-12-17 | 清华大学 | Polypyrrole micro-supercapacitor based on MEMS technology and manufacturing method thereof |
| CN101989499A (en) * | 2009-07-29 | 2011-03-23 | 美国纳米股份有限公司 | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| CN101916667A (en) * | 2010-09-19 | 2010-12-15 | 西安交通大学 | Asymmetric supercapacitors based on MnO2 and PPy/F-CNTs composite materials |
| CN102496470A (en) * | 2011-11-14 | 2012-06-13 | 清华大学 | Asymmetric miniature ultracapacitor based on MEMS technology and manufacturing method thereof |
| CN102568848A (en) * | 2011-12-21 | 2012-07-11 | 天津大学 | Preparation method of polyaniline/graphene oxide composite electrode material |
Non-Patent Citations (1)
| Title |
|---|
| HONGCAI GAO ET.AL: "High-Performance Asymmetric Supercapacitor Based on Graphene Hydrogel and Nanostructured MnO2", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 4, 30 April 2012 (2012-04-30), pages 2801 - 2810 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10319528B2 (en) | 2017-10-24 | 2019-06-11 | Industrial Technology Research Institute | Magnetic capacitor element |
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