CN104701030A - All-solid-state symmetrical three-dimensional micro super capacitor and preparation method thereof - Google Patents
All-solid-state symmetrical three-dimensional micro super capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 23
- 239000011149 active material Substances 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000012530 fluid Substances 0.000 claims description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 238000010894 electron beam technology Methods 0.000 claims description 12
- 230000003628 erosive effect Effects 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000010422 painting Methods 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 238000000609 electron-beam lithography Methods 0.000 claims description 7
- 238000011056 performance test Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000003292 glue Substances 0.000 description 20
- 238000004140 cleaning Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 239000004926 polymethyl methacrylate Substances 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 206010037660 Pyrexia Diseases 0.000 description 5
- 229940075397 calomel Drugs 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 5
- 239000008236 heating water Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- -1 soaks 30s Chemical compound 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021094 Co(NO3)2-6H2O Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 101100049043 Arabidopsis thaliana PVA12 gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to an all-solid-state symmetrical three-dimensional micro super capacitor for on-chip drive and a preparation method of the super capacitor. The all-solid-state symmetrical three-dimensional micro super capacitor comprises a silicon wafer with an oxide layer as a substrate, an active material and a solid electrolyte; the all-solid-state symmetrical three-dimensional micro super capacitor is characterized in that a spiral current collector of a symmetrical structure is arranged on the substrate, and three-dimensional array columns made of a photoresist are arranged on the spiral current collector. The all-solid-state symmetrical three-dimensional micro super capacitor has the beneficial effect that another idea of increasing the energy density of the super capacitor is provided, in other words, the three-dimensional conductive column array is constructed to realize the increase of the energy density under a rapid charge/discharge condition. Meanwhile, due to the peculiarity of spiral design, the integration and serial-parallel connection coupling of the electrodes are realized conveniently and easily.
Description
Technical field
The present invention relates to ultracapacitor, particularly relate to a kind of all solid state symmetric three-dimensional spiral micro super capacitor driven on chip and preparation method thereof.
Background technology
Along with the development of science and technology, energy storage units under micron/nano size has become wearable moving electronic components limiting factor, therefore, the micro chip of a given area realizes the high-power stored energy of high-energy and builds integrated for device, microminiaturized and multifunction has great importance.
Recently, the energy supply that the micro super capacitor on chip is used as microelectronic device has caused great concern.At present, button capacitor, according to whether there is surface or nearly surface oxidation reduction reaction in stored energy process, is divided into electric double layer micro capacitance and fake capacitance micro capacitance.The former studied main material is the material with carbon element of various height than specific surface, and latter relates generally to transition metal oxide and conducting polymer and some nitride and sulfide.Improving the area ratio capacity of button capacitor and an effective means of volume and capacity ratio is development fake capacitance capacitor, and it sweeps low the storage being realized electrochemical energy under speed by reversible redox reaction.But the electrical conductivity that microelectrode materials is low is difficult to work in one fast charge and discharge process, imply a low power density.And the energy that they are high and power density are in the news in a ultra-thin electrode, and this cannot continue along with the increase of thickness of electrode to keep.Therefore, developing a fake capacitance under micron height with high-energy and power density for the driving of microdevice is a problem with great challenge and significance.
Summary of the invention
The present invention proposes a kind of all solid state symmetric three-dimensional spiral micro super capacitor and preparation method thereof, be three-dimensional controlled integrated and series parallel structure, improve electronics and ion mobility by design three-dimensional conductive array pillar and spiral-shaped structure, and then improve energy and the power density of capacitor.
To achieve these goals, technical scheme of the present invention is: all solid state symmetric three-dimensional spiral micro super capacitor, include silicon chip with oxide layer as substrate, active material and solid electrolyte, it is characterized in that spiral gathering fluid substrate with symmetrical structure, spiral gathering fluid is furnished with the cubical array post be made up of photoresist.
By such scheme, described photoresist is: SU8 2002 or SU8 2000.5.
By such scheme, described cubical array post is the photoresist cubical array post of the coated carbonization of the photoresist cubical array post of carbonization or conducting metal.
By such scheme, the shape of described spiral gathering fluid is: circular single-screw, circular double helix or square single-screw.
By such scheme, the coupled modes between described spiral gathering fluid are: serial or parallel connection.
By such scheme, described active material is: Co (OH)
2or MnO
2.
By such scheme, the electrode width of described spiral gathering fluid is 30um, and adjacent electrode spacing is 15 ~ 30um.
By such scheme, consisting of of described solid electrolyte: deionized water, polyvinyl alcohol and KOH.
The preparation method of described all solid state symmetric three-dimensional spiral micro super capacitor, is characterized in that having following steps:
1) photoresist is coated with sol evenning machine at the bottom of with the silicon wafer-based of oxide layer;
2) in step 1) basis on, utilize electron beam lithography to prepare photoresist cubical array post;
3) in step 2) basis on, use sol evenning machine painting erosion resistant agent;
4) in step 3) basis on, utilize electron beam secondary technique of alignment to etch spiral gathering fluid slot at photoresist cubical array post periphery;
5) in step 4) basis on, utilize physical gas phase deposition technology to prepare two electrodes of the spiral gathering fluid of capacitor;
6) in step 5) basis on, by lift-off technology, resist is dissolved;
7) in step 6) basis on, with silver slurry two electrodes of capacitor are linked up;
8) in step 7) basis on, on spiral gathering fluid, deposit active material with electrodeposition process;
9) in step 8) basis on, silver slurry is scratched, drips upper solid electrolyte, then carry out performance test.
The invention has the beneficial effects as follows: for improving the low density problem of capacitor energy, now common thinking has two aspects, and one is: by changing the dimensional structure of material, increase material and electrolytical contact area.As scantling nanometer, or prepare the structure of porous; Two are: by the compound with other materials, chemically composition improve its energy-storage property, as MnO
2with the compound of Graphene.And in the present invention, propose the thinking that another improves super capacitor energy density, the raising of the energy density under fast charging and discharging condition is namely achieved by constructing three-dimensional conductive pillar array.Meanwhile, due to the uniqueness of helical design, achieve the integrated of electrode and connection in series-parallel coupling easily.
Accompanying drawing explanation
Fig. 1 is the flow chart constructing three-dimensional spiral button capacitor device of embodiment 1;
Fig. 2 is mechanism figure and the electronic scanner microscope figure of the device of embodiment 1;
Fig. 3 is cyclic voltammogram and the capacity distribution map of embodiment 1;
Fig. 4 is the different integration mode of embodiment 1 and the cyclic voltammetry curve of connection in series-parallel coupling schematic diagram and correspondence.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
All solid state symmetric three-dimensional spiral micro super capacitor, include silicon chip with oxide layer as substrate, active material and solid electrolyte, substrate has the spiral gathering fluid of symmetrical structure, spiral gathering fluid is furnished with the cubical array post be made up of photoresist.
Embodiment 1:
The preparation method of all solid state symmetric three-dimensional spiral micro super capacitor, it comprises the steps, as shown in Figure 1:
1) with sol evenning machine coating photoresist SU8 2002 at the bottom of with the silicon wafer-based of oxide layer, rotating speed is 1000rpm, and spin-coating time is 40s, uses the roasting glue 5min of electric hot plate 65 DEG C subsequently, and 95 DEG C of roasting glue 5min, repeat above step 4 time;
2) utilize electron beam lithography to prepare cubical array pillar, the diameter of pillar is 2um, and tangentially bearing circle is in the heart apart from being 10um for pillar, and in axial direction spacing is 5um, and etching voltage is 30kv, and electric current is 15pA, and exposure dose is 3 μ C/cm
2;
3) develop: the substrate after electron beam exposure is soaked 1min in developer solution SU8-developer, then in isopropyl alcohol, soaks 30s, nitrogen dries up;
4) on the substrate having cubical array pillar, use sol evenning machine painting erosion resistant agent MMA, rotating speed is 4000rpm, and spin-coating time is 40s, use the roasting glue 5min of electric hot plate 180 DEG C subsequently, then painting erosion resistant agent PMMA, rotating speed is 4000rpm, time is 40s, uses the roasting glue 5min of electric hot plate 180 DEG C subsequently;
5) electron beam secondary technique of alignment is utilized to etch spiral gathering fluid slot at photoresist cubical array post periphery, the electrode width of guarantee collector is 30um, and adjacent electrode spacing is 15um, and etching voltage is 30kv, electric current is 2000pA, and exposure dose is 280 μ C/cm
2;
6) Plasma cleaning: use O
2plasma cleaning silicon chip, power is 50W, cleaning 5min, O
2flow 30-60mL/min;
7) metal fever evaporation (PVD): utilize physical gas phase deposition technology to prepare two electrodes of the spiral gathering fluid of capacitor, Cr/Au (5nm/50nm);
8) metal-stripping: had by evaporation the substrate of metal to put and leave standstill 12h in acetone, MMA/PMMA is all peeled off, and then use acetone and isopropyl alcohol rinse substrate, nitrogen dries up;
9) with silver slurry, two collectors of capacitor are linked up;
10) active material Co (OH) is prepared on a current collector with the electro-deposition of three-electrode method constant voltage
2, as shown in Fig. 2 (b) and Fig. 2 (e) He Fig. 2 (f), reference electrode made by calomel electrode, and platinum electrode is done electrode, and collector makes work electrode, and electrolyte is 0.025MCo (NO
3)
2-6H
2o, electro-deposition parameter is that constant voltage-1.2V deposits 100s;
11) configure solid electrolyte solution, be dissolved in by 4g KOH in 40ml secondary deionized water, then add 4g middle-molecular-weihydroxyethyl polyvinyl alcohol (PVA12 ~ 150,000), heating water bath in 80-90 DEG C, until PVA dissolves completely;
12) scratched by silver slurry, drip upper solid electrolyte, its structure, as shown in Fig. 2 (a) He Fig. 2 (d), then carries out performance test.
As can be seen from Fig. 2 (c), in charge and discharge cycles process, as participating in the material of electrochemical reaction, electronics and the diffusion of ion in electrode and electrolyte play a decisive role for the capacity of ultracapacitor.By constructing three-dimensional conductive array pillar, the diffusion of electronics and ion can be promoted greatly, and then improve capacity.
With Co (OH)
2for active material, SEM (as Fig. 2 (f)) shows that gained material is about 5nm ultrathin nanometer sheet, middle-molecular-weihydroxyethyl PVA 10% KOH solid electrolyte in test, circular single-screw device, test voltage interval is 0-0.8V, Fig. 3 (a), 3 (b), 3 (c) is the cyclic voltammetry curve under different scanning speed, Fig. 3 (d) is for volume and capacity ratio and area ratio capacity are with the change curve of sweep speed, and Fig. 3 (f) is for volume energy density and volumetric power density are with the change curve of sweep speed.From Fig. 3 (d) and 3 (f), when 0.01V/s, volume and capacity ratio is about 390F/cm
3, when 200V/s, volumetric power density is about 190W/cm
3.As shown in Fig. 3 (e), by constructing SU-8 conductive array pillar, when 50V/s, energy density improves more than 20%, and device cycle 50000 still has the capability retention of 98% after enclosing.
On the integrated of device and connection in series-parallel coupled modes, for single square spiral collector, as shown in Fig. 4 (a) He 4 (d), test voltage interval is 0-0.8V, and cyclic voltammetry curve is as shown in Fig. 4 (g); During circular double helix collector series connection, as shown in Fig. 4 (b) He 4 (e), be 0-1.6V between test section, cyclic voltammetry curve is as shown in Fig. 4 (h); When circular double helix collector is in parallel, as shown in Fig. 4 (c) and 4 (f), be 0-0.8V between test section, cyclic voltammetry curve is as Fig. 4 (i).Comparison loop volt-ampere curve Fig. 4 (g), 4 (h), 4 (i) is known, relative to square single-screw collector, circular double helix collector parallel-current is improved, and the voltage of circular double helix collector series connection is improved.
Embodiment 2:
The preparation method of all solid state symmetric three-dimensional spiral micro super capacitor, it comprises the steps:
1) with sol evenning machine coating photoresist SU8 2002 at the bottom of with the silicon wafer-based of oxide layer, rotating speed is 1000rpm, and spin-coating time is 40s, uses the roasting glue 5min of electric hot plate 65 DEG C subsequently, and 95 DEG C of roasting glue 5min, repeat above step 4 time;
2) utilize electron beam lithography to prepare cubical array pillar, the diameter of pillar is 2um, and tangentially bearing circle is in the heart apart from being 10um for pillar, and in axial direction spacing is 5um, and etching voltage is 30kv, and electric current is 15pA, and exposure dose is 3 μ C/cm
2;
3) develop: the substrate after electron beam exposure is soaked 1min in developer solution SU8-developer, then in isopropyl alcohol, soaks 30s, nitrogen dries up;
4) on the substrate having cubical array pillar, use sol evenning machine painting erosion resistant agent MMA, rotating speed is 4000rpm, and spin-coating time is 40s, use the roasting glue 5min of electric hot plate 180 DEG C subsequently, then painting erosion resistant agent PMMA, rotating speed is 4000rpm, time is 40s, uses the roasting glue 5min of electric hot plate 180 DEG C subsequently;
5) electron beam secondary technique of alignment is utilized to etch spiral gathering fluid slot at photoresist cubical array post periphery, the electrode width of guarantee collector is 30um, and adjacent electrode spacing is 15um, and etching voltage is 30kv, electric current is 2000pA, and exposure dose is 280 μ C/cm
2;
6) Plasma cleaning: use O
2plasma cleaning silicon chip, power is 50W, cleaning 5min, O
2flow 30-60mL/min;
7) metal fever evaporation (PVD): utilize physical gas phase deposition technology to prepare two electrodes of the spiral gathering fluid of capacitor, Cr/Au (5nm/50nm);
8) metal-stripping: had by evaporation the substrate of metal to put and leave standstill 12h in acetone, MMA/PMMA is all peeled off, and then use acetone and isopropyl alcohol rinse substrate, nitrogen dries up;
9) with silver slurry, two collectors of capacitor are linked up;
10) active material Co (OH) is prepared on a current collector with the electro-deposition of three-electrode method constant voltage
2, reference electrode made by calomel electrode, and platinum electrode is done electrode, and collector makes work electrode, and electrolyte is 0.025M Co (NO
3)
2-6H
2o, electro-deposition parameter is that constant voltage-1.2V deposits 100s;
11) configure solid electrolyte solution, 4g KOH is dissolved in 40ml secondary deionized water, then adds 4g high molecular weight polyvinyl alcohol (PVA), heating water bath in 80-90 DEG C, until PVA dissolves completely;
12) silver slurry is scratched, drip upper solid electrolyte, then carry out performance test.
With Co (OH)
2for active material, when testing with the KOH solid electrolyte of the PVA containing 10% HMW (17 ~ 220,000), be 0-0.8V between the cyclic voltammetry test section of circular single-screw collector, when 0.01V/s, capacity comparatively containing the electrolytical circular single-screw collector of middle-molecular-weihydroxyethyl PVA have an appointment 5% raising.
Embodiment 3:
The preparation method of all solid state symmetric three-dimensional spiral micro super capacitor, it comprises the steps:
1) with sol evenning machine coating photoresist SU8 2000.5 at the bottom of with the silicon wafer-based of oxide layer, rotating speed is 1000rpm, and spin-coating time is 40s, uses the roasting glue 5min of electric hot plate 65 DEG C subsequently, and 95 DEG C of roasting glue 5min, repeat above step 4 time;
2) utilize electron beam lithography to prepare cubical array pillar, the diameter of pillar is 2um, and tangentially bearing circle is in the heart apart from being 10um for pillar, and in axial direction spacing is 5um, and etching voltage is 30kv, and electric current is 15pA, and exposure dose is 3 μ C/cm
2;
3) develop: the substrate after electron beam exposure is soaked 1min in developer solution SU8-developer, then in isopropyl alcohol, soaks 30s, nitrogen dries up;
4) on the substrate having cubical array pillar, use sol evenning machine painting erosion resistant agent MMA, rotating speed is 4000rpm, and spin-coating time is 40s, use the roasting glue 5min of electric hot plate 180 DEG C subsequently, then painting erosion resistant agent PMMA, rotating speed is 4000rpm, time is 40s, uses the roasting glue 5min of electric hot plate 180 DEG C subsequently;
5) electron beam secondary technique of alignment is utilized to etch spiral gathering fluid slot at photoresist cubical array post periphery, the electrode width of guarantee collector is 30um, and adjacent electrode spacing is 20um, and etching voltage is 30kv, electric current is 2000pA, and exposure dose is 280 μ C/cm
2;
6) Plasma cleaning: use O
2plasma cleaning silicon chip, power is 50W, cleaning 5min, O2 flow 30-60mL/min;
7) metal fever evaporation (PVD): utilize physical gas phase deposition technology to prepare two electrodes of the spiral gathering fluid of capacitor, Cr/Au (5nm/50nm);
8) metal-stripping: had by evaporation the substrate of metal to put and leave standstill 12h in acetone, MMA/PMMA is all peeled off, and then use acetone and isopropyl alcohol rinse substrate, nitrogen dries up;
9) with silver slurry, two collectors of capacitor are linked up;
10) active material Co (OH) is prepared on a current collector with the electro-deposition of three-electrode method constant voltage
2, reference electrode made by calomel electrode, and platinum electrode is done electrode, and collector makes work electrode, and electrolyte is 0.025M Co (NO
3)
2-6H
2o, electro-deposition parameter is that constant voltage-1.2V deposits 100s;
11) configure solid electrolyte solution, 4g KOH is dissolved in 40ml secondary deionized water, then adds 4g high molecular weight polyvinyl alcohol (PVA), heating water bath in 80-90 DEG C, until PVA dissolves completely;
12) silver slurry is scratched, drip upper solid electrolyte, then carry out performance test.
With Co (OH)
2for active material, the ratio of collector electrode width and spacing is 30/30, pillar material is photoresist SU82000.5, when testing with the KOH solid electrolyte of the PVA containing 10% HMW, be 0-0.8V between the cyclic voltammetry test section of circular single-screw collector, when sweep speed is 0.01V/s, volume energy density is about 350F/cm
3.
Embodiment 4:
The preparation method of all solid state symmetric three-dimensional spiral micro super capacitor, it comprises the steps:
1) with sol evenning machine coating photoresist SU8 2002 at the bottom of with the silicon wafer-based of oxide layer, rotating speed is 1000rpm, and spin-coating time is 40s, uses the roasting glue 5min of electric hot plate 65 DEG C subsequently, and 95 DEG C of roasting glue 5min, repeat above step 4 time;
2) utilize electron beam lithography to prepare cubical array pillar, the diameter of pillar is 2um, and tangentially bearing circle is in the heart apart from being 10um for pillar, and in axial direction spacing is 5um, and etching voltage is 30kv, and electric current is 15pA, and exposure dose is 3 μ C/cm
2;
3) develop: the substrate after electron beam exposure is soaked 1min in developer solution SU8-developer, then in isopropyl alcohol, soaks 30s, nitrogen dries up;
4) on the substrate having cubical array pillar, use sol evenning machine painting erosion resistant agent MMA, rotating speed is 4000rpm, and spin-coating time is 40s, use the roasting glue 5min of electric hot plate 180 DEG C subsequently, then painting erosion resistant agent PMMA, rotating speed is 4000rpm, time is 40s, uses the roasting glue 5min of electric hot plate 180 DEG C subsequently;
5) electron beam secondary technique of alignment is utilized to etch spiral gathering fluid slot at photoresist cubical array post periphery, the electrode width of guarantee collector is 30um, and adjacent electrode spacing is 15um, and etching voltage is 30kv, electric current is 2000pA, and exposure dose is 280 μ C/cm
2;
6) Plasma cleaning: use O
2plasma cleaning silicon chip, power is 50W, cleaning 5min, O2 flow 30-60mL/min;
7) metal fever evaporation (PVD): utilize physical gas phase deposition technology to prepare two electrodes of the spiral gathering fluid of capacitor, Cr/Au (5nm/50nm);
8) metal-stripping: had by evaporation the substrate of metal to put and leave standstill 12h in acetone, MMA/PMMA is all peeled off, and then use acetone and isopropyl alcohol rinse substrate, nitrogen dries up;
9) with silver slurry, two collectors of capacitor are linked up;
10) active material MnO is prepared on a current collector with the electro-deposition of three-electrode method constant current
2, reference electrode made by calomel electrode, and platinum electrode is done electrode, and collector makes work electrode, and electrolyte is 0.0025M manganese acetate and 0.1M SAS, and electro-deposition parameter is constant current 0.00001A, sedimentation time 1200s;
11) configure solid electrolyte solution, 4g KOH is dissolved in 40ml secondary deionized water, then adds 4g middle-molecular-weihydroxyethyl polyvinyl alcohol (PVA), heating water bath in 80-90 DEG C, until PVA dissolves completely;
12) silver slurry is scratched, drip upper solid electrolyte, then carry out performance test.
With MnO
2for active material, the ratio of collector electrode width and spacing is 30/15, pillar material is photoresist SU82002, when testing with the KOH solid electrolyte of the PVA containing 10% middle-molecular-weihydroxyethyl, be 0-0.8V between the cyclic voltammetry test section of circular single-screw collector, when sweep speed is 0.01V/s, volume energy density is about 325F/cm
3.
Embodiment 5:
The preparation method of all solid state symmetric three-dimensional spiral micro super capacitor, it comprises the steps:
1) with sol evenning machine coating photoresist SU8 2002 at the bottom of with the silicon wafer-based of oxide layer, rotating speed is 1000rpm, and spin-coating time is 40s, uses the roasting glue 5min of electric hot plate 65 DEG C subsequently, and 95 DEG C of roasting glue 5min, repeat above step 4 time;
2) utilize electron beam lithography to prepare cubical array pillar, the diameter of pillar is 2um, and tangentially bearing circle is in the heart apart from being 10um for pillar, and in axial direction spacing is 5um, and etching voltage is 30kv, and electric current is 15pA, and exposure dose is 3 μ C/cm
2;
3) develop: the substrate after electron beam exposure is soaked 1min in developer solution SU8-developer, then in isopropyl alcohol, soaks 30s, nitrogen dries up;
4) carbonization: be placed on by silicon chip in 400 DEG C of carbonizations 4 hours in tube furnace, heating rate is 5 DEG C/min;
5) on the substrate having cubical array pillar, use sol evenning machine painting erosion resistant agent MMA, rotating speed is 4000rpm, and spin-coating time is 40s, use the roasting glue 5min of electric hot plate 180 DEG C subsequently, then painting erosion resistant agent PMMA, rotating speed is 4000rpm, time is 40s, uses the roasting glue 5min of electric hot plate 180 DEG C subsequently;
6) electron beam secondary technique of alignment is utilized to etch spiral gathering fluid slot at photoresist cubical array post periphery, the electrode width of guarantee collector is 30um, and adjacent electrode spacing is 20um, and etching voltage is 30kv, electric current is 2000pA, and exposure dose is 280 μ C/cm
2;
7) Plasma cleaning: use O
2plasma cleaning silicon chip, power is 50W, cleaning 5min, O2 flow 30-60mL/min;
8) metal fever evaporation (PVD): utilize physical gas phase deposition technology to prepare two electrodes of the spiral gathering fluid of capacitor, Cr/Au (5nm/50nm);
9) metal-stripping: had by evaporation the substrate of metal to put and leave standstill 12h in acetone, MMA/PMMA is all peeled off, and then use acetone and isopropyl alcohol rinse substrate, nitrogen dries up;
10) with silver slurry, two collectors of capacitor are linked up;
11) active material MnO is prepared on a current collector with the electro-deposition of three-electrode method constant current
2, reference electrode made by calomel electrode, and platinum electrode is done electrode, and collector makes work electrode, and electrolyte is 0.0025M manganese acetate and 0.1M SAS, and electro-deposition parameter is constant current 0.00001A, sedimentation time 1200s;
12) prepare solid electrolyte solution, 4g KOH is dissolved in 40ml secondary deionized water, then adds 4g middle-molecular-weihydroxyethyl polyvinyl alcohol (PVA), heating water bath in 80-90 DEG C, until PVA dissolves completely;
13) silver slurry is scratched, drip upper solid electrolyte, then carry out performance test.
With MnO
2for active material, pillar carbonization treatment, the ratio of collector electrode width and spacing is 30/20, pillar material is photoresist SU82002, when testing with the KOH solid electrolyte of the PVA containing 10% middle-molecular-weihydroxyethyl, be 0-0.8V between the cyclic voltammetry test section of circular single-screw collector, when sweep speed is 0.01V/s, volume energy density is about 280F/cm
3.
Claims (10)
1. all solid state symmetric three-dimensional spiral micro super capacitor, include silicon chip with oxide layer as substrate, active material and solid electrolyte, is characterized in that spiral gathering fluid substrate with symmetrical structure, spiral gathering fluid is furnished with the cubical array post be made up of photoresist.
2. all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 1, is characterized in that described photoresist is: SU82002 or SU82000.5.
3. all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 1, is characterized in that described cubical array post is the photoresist cubical array post of the coated carbonization of the photoresist cubical array post of carbonization or conducting metal.
4. all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 1, is characterized in that the shape of described spiral gathering fluid is: circular single-screw, circular double helix or square single-screw.
5. all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 1, is characterized in that the coupled modes between described spiral gathering fluid are: serial or parallel connection.
6. all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 1, is characterized in that described active material is: Co (OH)
2or MnO
2.
7. all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 1, it is characterized in that the electrode width of spiral gathering fluid is 30um, adjacent electrode spacing is 15 ~ 30um.
8. all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 1, is characterized in that consisting of of solid electrolyte: deionized water, polyvinyl alcohol and KOH.
9. the preparation method of all solid state symmetric three-dimensional spiral micro super capacitor according to claim 1, is characterized in that having following steps:
1) photoresist is coated with sol evenning machine at the bottom of with the silicon wafer-based of oxide layer;
2) in step 1) basis on, utilize electron beam lithography to prepare photoresist cubical array post;
3) in step 2) basis on, use sol evenning machine painting erosion resistant agent;
4) in step 3) basis on, utilize electron beam secondary technique of alignment to etch spiral gathering fluid slot at photoresist cubical array post periphery;
5) in step 4) basis on, utilize physical gas phase deposition technology to prepare two electrodes of the spiral gathering fluid of capacitor;
6) in step 5) basis on, by lift-off technology, resist is dissolved;
7) in step 6) basis on, with silver slurry two electrodes of capacitor are linked up;
8) in step 7) basis on, on spiral gathering fluid, deposit active material with electrodeposition process;
9) in step 8) basis on, silver slurry is scratched, drips upper solid electrolyte, then carry out performance test.
10. the preparation method of all solid state symmetric three-dimensional spiral micro super capacitor as claimed in claim 9, is characterized in that the shape of described spiral gathering fluid is: circular single-screw, circular double helix or square single-screw; Coupled modes between described spiral gathering fluid are: serial or parallel connection.
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| CN107610937A (en) * | 2017-08-01 | 2018-01-19 | 全普光电科技(上海)有限公司 | Electrode structure and preparation method thereof, graphene ultracapacitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308927A (en) * | 2007-07-09 | 2008-11-19 | 松下电器产业株式会社 | Current collector, electrode, non-aqueous electrolyte secondary battery |
| CN101325130A (en) * | 2008-05-22 | 2008-12-17 | 清华大学 | Poly-pyrrole minisize super capacitor based on MEMS technique and method for manufacturing the same |
| CN101504889A (en) * | 2009-03-16 | 2009-08-12 | 清华大学 | Micro super capacitor applied for micro system and production process thereof |
| CN102751104A (en) * | 2012-07-06 | 2012-10-24 | 海博瑞恩电子科技无锡有限公司 | Thick glue photoetching electroforming technology-based manufacture method of three-dimensional MEMS (micro-electromechanical systems) supercapacitor |
-
2015
- 2015-03-24 CN CN201510130642.8A patent/CN104701030B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308927A (en) * | 2007-07-09 | 2008-11-19 | 松下电器产业株式会社 | Current collector, electrode, non-aqueous electrolyte secondary battery |
| CN101325130A (en) * | 2008-05-22 | 2008-12-17 | 清华大学 | Poly-pyrrole minisize super capacitor based on MEMS technique and method for manufacturing the same |
| CN101504889A (en) * | 2009-03-16 | 2009-08-12 | 清华大学 | Micro super capacitor applied for micro system and production process thereof |
| CN102751104A (en) * | 2012-07-06 | 2012-10-24 | 海博瑞恩电子科技无锡有限公司 | Thick glue photoetching electroforming technology-based manufacture method of three-dimensional MEMS (micro-electromechanical systems) supercapacitor |
Non-Patent Citations (1)
| Title |
|---|
| WEI SUN等: ""Symmetric redox supercapacitor based on micro-fabrication with three-dimensional polypyrrole electrodes"", 《JOURNAL OF POWER SOURCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107610937A (en) * | 2017-08-01 | 2018-01-19 | 全普光电科技(上海)有限公司 | Electrode structure and preparation method thereof, graphene ultracapacitor and preparation method thereof |
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