CN108922791B - Interdigital electrode with nano-texture surface and preparation method and application thereof - Google Patents
Interdigital electrode with nano-texture surface and preparation method and application thereof Download PDFInfo
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- CN108922791B CN108922791B CN201810558621.XA CN201810558621A CN108922791B CN 108922791 B CN108922791 B CN 108922791B CN 201810558621 A CN201810558621 A CN 201810558621A CN 108922791 B CN108922791 B CN 108922791B
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- 238000009713 electroplating Methods 0.000 claims description 15
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 5
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 230000005540 biological transmission Effects 0.000 description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
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- 239000012691 Cu precursor Substances 0.000 description 2
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- 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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The invention relates to an interdigital electrode with a nano-texture surface, a preparation method and application thereof, wherein the interdigital electrode is a metal film with a comb-shaped periodic pattern and at least one surface of which is provided with a nano-sized microstructure, and the nano-sized microstructure is at least one of a nano cone, a nano sheet and a nano wall; preferably, the root mean square roughness of the surface of the metal film on the side with the nano-sized microstructure is 8-200 nm, and more preferably 10-100 nm.
Description
Technical Field
The invention relates to an interdigital electrode with a nano-texture surface, a preparation method and application thereof, and belongs to the technical field of engineering.
Background
The interdigital electrode is an electrode with a comb-shaped periodic pattern in a plane, and can be used as a current collector of devices such as a super capacitor, a lithium battery, a friction nano generator, a sensor and the like.
On one hand, the traditional preparation methods of the interdigital electrode comprise photoetching, ink-jet printing, laser writing, mask assisted vacuum sputtering and the like, and the methods have the defects of complex steps and high cost, so that the large-scale, efficient and low-cost preparation of the interdigital electrode is limited. On the other hand, the surface of the interdigital electrode prepared by the traditional method is compact and flat, so that the charge transmission between the interdigital electrode and an electrode material is limited, and the performance of a device is low.
Disclosure of Invention
In view of the above problems, the present invention aims to provide an interdigital electrode with a nano-textured surface, and a preparation method and an application thereof.
In one aspect, the invention provides an interdigital electrode with a nano-textured surface, wherein the interdigital electrode is a metal thin film with a comb-shaped periodic pattern and at least one surface of the metal thin film is provided with a nano-sized microstructure, and the nano-sized microstructure is at least one of a nano cone, a nano sheet and a nano wall; preferably, the root mean square roughness of the surface of the metal film on the side with the nano-sized microstructure is 8-200 nm, and more preferably 10-100 nm.
In the invention, the interdigital electrode with the nano-texture surface is attached to the flexible substrate, is composed of a metal film, is in a comb-shaped periodic pattern in the plane, and at least one surface of the interdigital electrode is provided with a nano-sized microstructure (such as a nano cone, a nano sheet, a nano wall and the like), so that the contact area between the interdigital electrode and an electrode material can be increased, the charge transmission efficiency is obviously improved, and the performances of devices such as a super capacitor, a lithium battery, a friction nano generator, a sensor and the like are improved. The charge transmission efficiency of the super capacitor is improved to a greater extent along with the increase of the surface roughness of the metal film, so that the performance of the super capacitor is better.
Preferably, the thickness of the interdigital electrode is 50 nm-100 μm.
Preferably, the material of the interdigital electrode is at least one of Ni, Cu and Zn.
Preferably, the interdigital electrode is attached to the surface of the flexible substrate, and at least one surface of the interdigital electrode, which is far away from the flexible substrate, is provided with a nano-sized microstructure. The flexible base material is one of paper, cloth and soft plastics.
In another aspect, the invention further provides a preparation method of the interdigital electrode with the nano-textured surface, which includes:
dipping a seal engraved with an interdigital electrode comb-shaped periodic pattern in ink, and then impressing the ink pattern of the comb-shaped periodic pattern on the surface of a conductive substrate, wherein the conductive substrate is FTO conductive glass or a metal sheet, the root-mean-square roughness of the surface is 8-200 nm, and the optimal roughness is 10-100 nm;
and placing the conductive substrate printed with the ink pattern in the interdigital electrode shape in a metal precursor solution for electroplating, removing the ink pattern, and transferring the ink pattern to the surface of a flexible substrate to obtain the interdigital electrode with the nano-texture surface.
In the invention, after the seal engraved with the comb-shaped periodic pattern of the interdigital electrode is dipped with ink, the ink pattern of the comb-shaped periodic pattern is stamped on the surface of a conductive substrate (FTO conductive glass or metal sheet, the root-mean-square roughness of the surface is 8-200 nm). And placing the conductive substrate printed with the ink pattern in the shape of the interdigital electrode in a metal precursor solution for electroplating to form the interdigital electrode. Because the surface of the conductive substrate is provided with the nano-sized microstructure, the nano-sized microstructure is formed on one surface of the interdigital electrode close to the conductive substrate formed by electroplating. And finally, transferring the interdigital electrode to the surface of the flexible substrate, and enabling one surface of the microstructure with the nanometer size to be far away from the flexible substrate. The method comprises the main steps of printing ink patterns, electroplating nickel, removing ink, transferring electrodes and the like, all the operations are carried out in solution, and the method is simple to operate, stable and reliable in process, low in cost and beneficial to popularization.
Preferably, the ink is an insulating, oleophilic, viscous liquid, and comprises the ingredients of alcohol, pigment, and resin.
Preferably, the metal precursor solution is one of a Ni precursor solution, a Cu precursor solution and a Zn precursor solution; preferably, the metal precursor solution is a mixed aqueous solution of a metal salt and a plating assistant, and the metal salt is NiSO4、Ni(NO3)2、CuSO4、Cu(NO3)2、ZnSO4And Zn (NO)3)2At least one of, the plating assistant is NH4Cl and H3BO3At least one of (1).
Further, it is preferable that the concentration of the metal salt is 0.1 to 1.0 mol/L and the concentration of the plating assistant is 0.05 to 5 mol/L.
Preferably, between-0.5 and-2.0 mA cm-2And (4) carrying out electroplating at constant current for 3-60 minutes.
Preferably, the ink pattern is removed using an organic agent, which is at least one of ethanol, methanol, isopropanol, acetone, and toluene.
Preferably, the surface of the flexible substrate is treated by using the transferable glue, then one surface of the flexible substrate with the transferable glue is covered on the surface of the conductive substrate after the ink is removed and is tightly attached, and then the interdigital electrode is transferred to the surface of the flexible substrate after separation.
In a fourth aspect, the present invention provides a supercapacitor comprising the above interdigitated electrode.
Compared with the prior art, the invention has the following beneficial effects:
compared with the dense and flat interdigital electrode prepared by the traditional method, the interdigital electrode provided by the invention has the nano texture on the surface, and the contact area between the interdigital electrode and an electrode material can be increased, so that the charge transmission efficiency is obviously improved, and the performances of devices such as a super capacitor, a lithium battery, a friction nano generator, a sensor and the like are improved;
according to the preparation method of the interdigital electrode with the nano-texture surface, all operations are carried out in solution. Compared with the traditional methods such as photoetching, ink-jet printing, laser writing, mask assisted vacuum sputtering and the like, the method has the advantages of stable and reliable process, simple operation, low cost, easy realization and convenient popularization and application.
Drawings
FIG. 1 is a flow chart of a method for preparing an interdigital electrode with a nano-textured surface according to the present invention;
FIG. 2 is a comb-like periodic pattern provided by the present invention;
FIG. 3 is a photograph of a stamp provided by the present invention;
FIG. 4 is a photograph of FTO conductive glass according to the present invention;
FIG. 5 is an atomic force microscope photograph of an FTO conductive glass in accordance with the present invention;
FIG. 6 is a photograph of FTO conductive glass provided by the present invention with an ink pattern;
FIG. 7 is a photograph of FTO conductive glass provided by the present invention after nickel electroplating;
FIG. 8 is a photograph of FTO conductive glass provided by the present invention after ink removal;
FIG. 9 is a photograph of FTO conductive glass covered with a polyimide plastic film provided by the present invention;
FIG. 10 is an interdigitated electrode attached to the surface of a polyimide plastic film in accordance with the present invention;
FIG. 11 is a surface scanning electron microscope image of an interdigital electrode having a nano-textured surface provided by the present invention;
FIG. 12 is a scanning electron microscope image of a cross section of an interdigital electrode having a nano-textured surface provided by the present invention;
FIG. 13 is a high resolution surface scanning electron microscope image of an interdigital electrode with a nano-textured surface provided by the present invention;
fig. 14 is an atomic force microscope picture of an interdigital electrode having a nano-textured surface provided by the present invention;
FIG. 15 is an X-ray diffraction pattern of an interdigital electrode having a nanotextured surface according to the present invention;
FIG. 16 is an X-ray photoelectron spectrum of an interdigital electrode having a nanotextured surface according to the present invention;
FIG. 17 shows electrodeposited MnO provided by the present invention2The picture of the interdigital electrode;
FIG. 18 is a photograph of an ultracapacitor provided by the present invention;
FIG. 19 is a high resolution surface scanning electron microscope image of an interdigital electrode without surface nanotexture provided by the present invention;
fig. 20 is an atomic force microscope picture of an interdigital electrode without surface nanotexture provided by the present invention;
FIG. 21 is a cyclic voltammogram of a supercapacitor provided by the present invention: 1-supercapacitors based on interdigitated electrodes with surface nanotexturing; 2-supercapacitors based on interdigitated electrodes without surface nanotexturing.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the invention, the interdigital electrode with the nano-texture surface is a metal film with a comb-shaped periodic pattern and at least one surface of the metal film is provided with a nano-sized microstructure, wherein the nano-sized microstructure can be at least one of a nano cone, a nano sheet and a nano wall. In an alternative embodiment, the material of the interdigital electrode may be at least one of Ni, Cu, and Zn. In an alternative embodiment, the interdigitated electrodes have a thickness of 50nm to 100 μm. In an alternative embodiment, the interdigital electrodes are attached to the surface of the flexible substrate such that at least the side of the interdigital electrodes facing away from the flexible substrate has a nano-sized microstructure. Wherein, the flexible substrate can be one of paper, cloth and soft plastics. Wherein, the surface root mean square roughness of the surface of the metal film with the nano-sized microstructure is 8-200 nm, and more preferably 10-100 nm.
The preparation method of the interdigital electrode with the nano-textured surface comprises the main steps of printing ink patterns, electroplating nickel, removing ink, transferring the electrode and the like, has the characteristics of stable and reliable process, simple operation and low cost, and is easy to popularize and apply. Wherein the interdigital electrodes typically have a thickness of 50nm to 100 μm. As shown in fig. 1, a method for manufacturing an interdigital electrode having a nano-textured surface is exemplarily described below.
And (5) processing the seal. The comb-shaped periodic pattern is formed on the surface of the stamp by adopting a molding technology, wherein the molding technology comprises but is not limited to laser engraving, machining, 3D printing and the like. The stamp can be made of rubber, wood, plastic, stone and other materials capable of being engraved, and the surface of the stamp is provided with an engraved comb-shaped periodic pattern.
And cleaning the conductive substrate. And (3) placing the conductive base material in acetone, ethanol and deionized water in sequence, ultrasonically cleaning for 15 minutes, and then placing the conductive base material in an oven at the temperature of 60-120 ℃ for drying for 0.5-6 hours. The conductive substrate includes but is not limited to conductive glass, metal sheets and the like, and the surface root mean square roughness is 8-200 nm, preferably 10-100 nm.
The ink pattern is embossed. And dipping the printing ink by using a stamp, and stamping an ink pattern on the surface of the conductive substrate. The ink is an insulating, oleophilic and viscous liquid, and is preferably Sipa SK-6 sign pen ink.
And preparing a metal precursor solution. Wherein the metal precursor solution is one of a Ni precursor solution, a Cu precursor solution and a Zn precursor solution. The metal precursor solution is a mixed aqueous solution of metal salt and an electroplating auxiliary agent. Wherein the metal salt can be NiSO4、Ni(NO3)2、CuSO4、Cu(NO3)2、ZnSO4And Zn (NO)3)2At least one of (1). The plating assistant may be NH4Cl and H3BO3In an alternative embodiment, the concentration of the metal salt may be 0.1-1.0 mol/L, and the concentration of the plating assistant may be 0.05-5 mol/L, taking Ni precursor solution as an example, weighing a certain amount of nickel salt (including but not limited to NiSO)4、Ni(NO3)2Etc.) and plating aids (including but not limited to NH4Cl、H3BO3Etc.) are dissolved in deionized water to form mixed aqueous solution with the concentration of 0.1-1.0 mol/L and 0.05-0.5 mol/L respectively.
And (4) electroplating metal. Using electroplated nickel as an example: the conductive substrate printed with the ink pattern is used as a working electrode, an Ag/AgCl or saturated calomel electrode is used as a reference electrode, and a platinum sheet is used as a counter electrode. Applying-0.5 to-2.0 mAcm by adopting a constant current method-2And (5) continuously electroplating for 3-60 minutes in the nickel precursor at constant current. Then, the conductive substrate is taken out, washed by deionized water and dried for 0.5 to 6 hours at the temperature of 60 to 120 ℃.
And removing the ink pattern. The ink is washed clean by rinsing with organic agents including, but not limited to, ethanol, acetone, toluene. Then washing with deionized water, and drying at 60-120 ℃ for 0.5-6 hours.
And (4) transferring the electrode. The flexible substrate is treated with a transferable glue to impart tackiness thereto. Covering the flexible substrate with viscosity on the surface of the conductive substrate to enable the conductive substrate to be tightly attached, then tearing off the conductive substrate, and transferring the interdigital electrode attached to the surface of the conductive substrate to the surface of the flexible substrate. The transferable glue is preferably 3M Super-75. Wherein, the flexible base material specifically refers to paper, cloth, soft plastic base material and the like, and is characterized by being capable of being bent and folded.
MnO is electrodeposited on the interdigital electrode2And then coating the gel electrolyte to obtain the super capacitor. In which MnO is electrodeposited2The method comprises the following steps: placing the interdigital electrode in MnO2In the precursor solution, performing electrodeposition for 0.5-30 minutes under the constant voltage of + 0.2- +1.2V to obtain MnO2Thin film (thickness 20-1000 nm). Wherein, MnO2The precursor solution is Mn (CH)3COO)2And Na2SO4The mixed aqueous solution of (1). Mn (CH)3COO)2The concentration of (b) can be 0.01-2.0 mol/L. Na2SO4The concentration of (b) is 0.005-0.5 mol/L.
In the invention, the interdigital electrode can also be applied to a super capacitor, a lithium battery, a friction nano generator, a sensor and the like, so that the performance of each device is greatly improved.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The basic steps are shown in figure 1:
(1) processing a seal: the invention adopts a laser etching method to form a comb-shaped periodic pattern on the surface of the stamp. The comb-shaped periodic pattern is shown in fig. 2, and the stamp is shown in fig. 3;
(2) cleaning the conductive substrate: the conductive substrate is conductive glass (the surface root mean square roughness is 13.303nm), in particular FTO conductive glass. The FTO conductive glass is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 15 minutes and then placed in an oven at 60 ℃ for drying for 2 hours. The cleaned FTO conductive glass is shown in fig. 4, and its atomic force microscope picture is shown in fig. 5;
(3) and (3) printing ink patterns: and (3) dipping the seal in the step (1) with ink (ink of a Sipa SK-6 sign pen), and stamping an ink pattern on the surface of the FTO conductive glass. FTO conductive glass with ink pattern attached, as shown in fig. 6;
(4) preparing a nickel precursor: weighing a certain amount of NiSO4And NH4Dissolving Cl in deionized water to form mixed aqueous solutions with the concentrations of 0.1 mol/L and 0.05 mol/L respectively;
(5) electroplating nickel: and (4) taking the FTO conductive glass attached with the ink pattern in the step (3) as a working electrode, taking an Ag/AgCl electrode as a reference electrode and taking a platinum sheet as a counter electrode. Applying-1.5 mA cm by constant current method-2Constant current, continuously electroplating for 10 minutes in the nickel precursor in the step 4. Then, the conductive substrate was taken out, washed with deionized water, and dried at 60 ℃ for 1 hour. The FTO conductive glass after nickel electroplating is shown in figure 7;
(6) removing the ink pattern: the ink was washed with ethanol and washed. Then washed with deionized water and dried at 60 ℃ for 1 hour. The FTO conductive glass after removing the ink pattern is shown in fig. 8;
(7) electrode transfer: the polyimide plastic film was treated with 3M Super-75 type transferable glue to render it tacky. Covering the surface of the FTO conductive glass obtained in the step 6 with an adhesive polyimide plastic film to enable the FTO conductive glass to be tightly attached (as shown in figure 9), then tearing off the FTO conductive glass, and transferring the interdigital electrodes attached to the surface of the FTO conductive glass to the polyimide plastic film. The interdigitated electrodes attached to the surface of the polyimide plastic film are shown in fig. 10. FIGS. 11 and 12 are the interdigital electrodes observed under a scanning electron microscope, respectively, and the interdigital electrodes have an electrode width of 1.4mm, a pitch of 300 μm, and a thickness of 200 nm. Fig. 13 is a surface morphology observed under a scanning electron microscope, and a nano-sized microstructure exists on the surface of the interdigital electrode. FIG. 14 shows the surface topography observed under an atomic force microscope, with a root mean square roughness of 10.876 nm. Fig. 15 is an X-ray diffraction pattern of the interdigital electrode, which can confirm that the composition of the interdigital electrode is metallic nickel. FIG. 16 is an X-ray photoelectron spectrum of an interdigital electrode, illustrating the presence of nickel oxide on the surface of the interdigital electrode;
(8) configuring MnO2Precursor: weighing a certain amount of Mn (CH)3COO)2And Na2SO4Dissolving in deionized water, wherein the concentration is 0.1 mol/L;
(9) electrodeposition of MnO2: the interdigital electrode attached to the surface of the polyimide plastic film is a working electrode, the Ag/AgCl electrode is a reference electrode, and the platinum sheet is a counter electrode. Applying a constant voltage of +0.6V, MnO in step 82Electrodeposition was continued for 4 minutes in the precursor. Then, the interdigital electrode is taken out, washed by deionized water and dried for 1 hour at 60 ℃. Electrodeposition of MnO2The latter interdigital electrode is shown in FIG. 17, MnO2Uniformly covering the surface of the interdigital electrode with MnO2The thickness of the film is 200 nm;
(10) preparing a gel electrolyte: weighing 1.5g of sodium carboxymethylcellulose and 3.0g of Na2SO4Dissolving in 25m L deionized water, heating to 90 deg.C, continuously magnetically stirring for 3 hr to form clear gel-like substance, and naturally cooling to room temperature;
(11) coating a gel electrolyte: applying the gel electrolyte of step 10 to the electrodeposited MnO of step 92And forming the surface of the interdigital electrode in the step 7 and the surface of the interdigital electrode in the step 7 to form the super capacitor. The supercapacitor is shown in fig. 18.
Comparative example 1
The polyimide plastic film is treated by 3M Super-75 type transferable glue to be sticky. The polyimide plastic film with adhesiveness is covered on the polyimide plastic film surface adhered with the interdigital electrode obtained in the step (7) of example 1, and then torn off, so that the interdigital electrode has a nano-sized microstructure on one side close to the flexible substrate and has a surface without a surface nano-texture on the other side away from the flexible substrate. Fig. 19 and 20 show high-resolution surface scanning electron microscope images and atomic force microscope images of the interdigital electrode without surface nanotexture, respectively. Compared with the interdigital electrode with the surface nano-texture in the step (7), the surface of the electrode is smoother, and the root mean square roughness of the surface is only 5.005 nm. On the basis of the above, a supercapacitor was prepared, and referring to example 1, a supercapacitor without the interdigital electrode having the surface nanotexture was obtained.
Fig. 21 is a cyclic voltammogram of a supercapacitor. The capacitance value of the supercapacitor based on the interdigital electrode with the surface nano-texture provided by the invention is 4.15mF cm-2The capacitance value of the super capacitor based on the interdigital electrode without the surface nano texture is 2.96mF cm-2. Therefore, the interdigital electrode with the surface nano-texture can increase the contact area between the interdigital electrode and an electrode material, thereby obviously improving the charge transmission efficiency and improving the performance of the super capacitor.
Claims (9)
1. The preparation method of the interdigital electrode with the nano-texture surface is characterized in that the interdigital electrode is a metal film which is provided with a comb-shaped periodic pattern and at least one surface of which is provided with a nano-sized microstructure, and the nano-sized microstructure is at least one of a nano cone, a nano sheet and a nano wall; the preparation method of the interdigital electrode comprises the following steps:
dipping the seal engraved with the comb-shaped periodic pattern of the interdigital electrode in ink, and then impressing the ink pattern of the comb-shaped periodic pattern on the surface of the conductive substrate; the conductive substrate is FTO conductive glass or a metal sheet, and the root mean square roughness of the surface is 8-200 nm;
placing the conductive substrate printed with the comb-shaped periodic pattern ink pattern in a metal precursor solution for electroplating, and removing the ink pattern;
and treating the surface of the flexible substrate by adopting transferable glue, covering one surface of the flexible substrate with the transferable glue on the surface of the conductive substrate with the ink removed, tightly attaching the conductive substrate with the ink removed, and separating to transfer the interdigital electrode to the surface of the flexible substrate to obtain the interdigital electrode with the nano-texture surface.
2. The method according to claim 1, wherein the root mean square roughness of the surface of the metal thin film on the side having the nano-sized microstructure is 10 to 100 nm.
3. The method according to claim 1, wherein the interdigital electrode has a thickness of 50nm to 100 μm.
4. The method according to claim 1, wherein the interdigital electrode is made of at least one of Ni, Cu, and Zn.
5. The preparation method according to claim 1, wherein the interdigital electrodes are attached to the surface of the flexible substrate, and at least one surface of the interdigital electrodes, which is far away from the flexible substrate, is provided with a nano-sized microstructure; the flexible base material is one of paper, cloth and soft plastics.
6. The method of claim 1, wherein the ink is an insulating, oleophilic, and viscous liquid, and the components include alcohol, pigment, and resin.
7. The production method according to claim 1, wherein the metal precursor solution is a mixed aqueous solution of a metal salt and a plating assistant, and the metal salt is NiSO4、Ni(NO3)2、CuSO4、Cu(NO3)2、ZnSO4And Zn (NO)3)2At least one of, the plating assistant is NH4Cl and H3BO3At least one of (1).
8. The method according to claim 7, wherein the concentration of the metal salt is 0.1 to 1.0 mol/L, and the concentration of the plating assistant is 0.05 to 5 mol/L.
9. The method of claim 1, wherein-0.5 to-2.0 mA cm is applied-2And (4) carrying out electroplating at constant current for 3-60 minutes.
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| CN110085444A (en) * | 2019-04-23 | 2019-08-02 | 西北工业大学深圳研究院 | Flexible miniature supercapacitor and preparation method thereof based on electrochemistry increasing material manufacturing |
| CN110085445B (en) * | 2019-05-23 | 2021-04-06 | 南京邮电大学 | Flexible super capacitor and preparation method thereof |
| CN111505065B (en) * | 2020-04-20 | 2023-04-18 | 河北工业大学 | Interdigital counter electrode type flexible touch sensor based on super-capacitor sensing principle and preparation method thereof |
| CN111596135A (en) * | 2020-05-29 | 2020-08-28 | 中国科学院微电子研究所 | Method for analyzing resistance characteristics of electrodeposited gold structure |
| CN113162477B (en) * | 2021-02-05 | 2023-07-18 | 西安交通大学 | Liquid drop energy collecting device and method based on thin film interdigital electrode |
| CN116261388B (en) * | 2023-05-16 | 2023-07-25 | 北京中科飞鸿科技股份有限公司 | Method for preparing interdigital electrode for semiconductor package and semiconductor package |
| CN116347971B (en) * | 2023-05-24 | 2023-08-08 | 北京中科飞鸿科技股份有限公司 | Semiconductor package for radio frequency front end |
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