Super capacitor based on three-dimensional ZnO@MnO2 composite nano array interdigital electrode and manufacturing method thereof

A technology of supercapacitors and interdigitated electrodes, which is applied in the field of energy storage, can solve the problems that it is difficult to adapt to the development requirements of high-power and high-energy flexible transparent supercapacitors, it is difficult to apply solid-state electronic devices, and the capacitors are low, so as to meet the requirements of high-power , meet the charging and discharging needs, long life effect

Active Publication Date: 2015-03-25

THE NAT CENT FOR NANOSCI & TECH NCNST OF CHINA

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AI-Extracted Technical Summary

Problems solved by technology

Using this technology to prepare interdigitated electrodes on a flexible transparent substrate is a very effective way to process transparent electronic devices. For example, patent document CN 201210579735.5 discloses a transparent and flexible electrochemical device based on a planar comb-shaped electrode structure and its The preparation method uses an interdigitated electrode to prepare an electric double ...

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Abstract

The invention relates to a super capacitor based on a three-dimensional ZnO@MnO2 composite nano array interdigital electrode and a manufacturing method of the super capacitor. The super capacitor comprises a packaging bag and a solid electrolyte, and further comprises the ZnO@MnO2 composite nano array interdigital electrode, the solid electrolyte and the ZnO@MnO2 composite nano array interdigital electrode are arranged in the packaging bag, and the ZnO@MnO2 composite nano array interdigital electrode is smeared with the solid electrolyte. The micro-nano machining technology is adopted in the ZnO@MnO2 composite nano array interdigital electrode, a transparent interdigital collector electrode is manufactured on a flexible and transparent PET substrate, a three-dimensional ZnO bar nano array is grown on the collector electrode through a solution method, and three-dimensional ZnO bars are coated with a layer of MnO2 based on an electro-deposition technology. According to the super capacitor, the area ratio capacitance of a device is greatly improved, a nano array clearance is adopted as a channel facilitating ion transmission and exchange, and the rate capacity and circulating performance of the capacitor are improved.

Application Domain

Hybrid capacitor electrodesDouble layer capacitors +1

Technology Topic

Micro nanoIon +7

Image

Examples

Experimental program(4)

Example Embodiment

[0044] Example 1

[0045] Preparation of ZnOMnO 2 Composite nano array interdigital electrode

[0046] 1. Substrate selection: PET is selected as the substrate and treated with an oxygen plasma surface treatment machine for 2 minutes.

[0047] 2. Interdigital electrode design: Using semiconductor device micromachining technology, the interdigital electrode pattern is processed on the PET substrate. The design of the interdigital electrode pattern used as a UV lithography mask is as follows figure 1 Shown. It can be seen from the figure that the number of pairs of interdigital electrodes prepared is 8 pairs, and the distance between the interdigital electrodes and the finger width are 100 microns. The operating conditions of the photolithography process are: the photoresist model used in UV lithography is AZ4620, the thickness of the uniform glue is 3 microns, the uniform glue speed is 2000 revolutions per minute, the pre-baking temperature is 105 degrees, the exposure time is 25s, and the development time For 70 seconds, an interdigital counter electrode pattern was prepared on the PET sink.

[0048] 3. Preparation of collector electrode and ZnO seed layer: using magnetron sputtering, a 70nm Pt film and a 20nm ZnO film are deposited on the PET substrate with the interdigital electrode pattern prepared in step 2 above.

[0049] 4. Preparation of ZnO nanorod array: Put the PET substrate prepared in step 3 above into a sealable container, and add deionized water and 0.5mol/L in a ratio of 32:2:4:2:1. Zinc nitrate solution, 0.1 mol/L polyvinyl imine solution, 0.25 mol/L hexamethylene tetramine solution and 75% ammonia water. Stir thoroughly and seal, then heat in a water bath at 65°C for 10 hours to obtain a nanometer zinc oxide array of about 6 microns, such as figure 2 Shown. From figure 2 It can be seen that the ZnO nanorods are uniformly distributed on the interdigital Pt electrode film, and the ZnO nanorods are closely arranged, and their length is about 6 microns. In order to further improve the conductivity of the zinc oxide nanorods, magnetron sputtering can also be used to coat the zinc oxide nanorods with a 10nm Pt film;

[0050] 5. Three-dimensional MnO 2 Array preparation: three-electrode electrochemical deposition method is used to coat cheap and environmentally friendly MnO on the three-dimensional ZnO nanorod array 2 Materials, the operating conditions of electrochemical deposition are: the electrodeposition solution is a mixture of 0.02mol/L manganese nitrate and 0.1mol/L sodium nitrate, and the three-dimensional ZnO nanorod array interdigital electrode prepared in step 4 is used as the working electrode. The platinum sheet is the counter electrode, the calomel electrode is the reference electrode, and the current density of electrodeposition is 0.5mA/cm 2 , The deposition time is 25min, MnO is electrodeposited around the ZnO nanorods 2 Electrode material, get MnO 2 Coated ZnO nanorod array;

[0051] 6. Lift-Off process. The three-dimensional MnO obtained in step 5 2 The array is immersed in acetone for 2 hours and ultrasonicated for 10 minutes to remove excess photoresist to obtain flexible and transparent ZnOMnO 2 Composite nano-array interdigital electrodes, such as image 3 Shown. It can be seen from the figure that the MnO 2 The film is evenly coated on the three-dimensional ZnO nanorod array, MnO 2 The film thickness is about 40nm.

Example Embodiment

[0052] Example 2

[0053] Fabrication of flexible and transparent solid 3D supercapacitors

[0054] Lithium chloride and PVA were dissolved in an appropriate amount of deionized water at a mass ratio of 2:1, and stirred in a water bath at 85°C for 1 hour to obtain a solid electrolyte. Spread the solid electrolyte evenly on the prepared interdigital capacitor and encapsulate it with PMMA to obtain a flexible transparent solid super capacitor, such as Figure 4 As shown, it can be seen from the figure that the solid-state supercapacitor has a length of about 5 cm, high transparency, bendable, and good flexibility. The cyclic voltammetry curve of the prepared flexible transparent solid supercapacitor is as Figure 5 As shown, it can be seen from the figure that at different scanning speeds, the CV curve has a nearly rectangular structure, which is a typical amorphous MnO 2 Capacitance characteristics, the area capacitance of the device can reach 167mF/cm at a scanning speed of 2mV/s -2. Image 6 For the cycle performance curve of the device under cross-current charging and discharging, it can be seen that after 5000 cycles, the capacity of the device still remains at about 99%, indicating that the device has good stable performance.

Example Embodiment

[0055] Example 3

[0056] Preparation of ZnOMnO 2 Composite nano array interdigital electrode

[0057] 1. Substrate selection: PDMS is selected as the substrate and treated with an oxygen plasma surface treatment machine for 2 minutes.

[0058] 2. Interdigital electrode design: Using semiconductor device micromachining technology, the interdigital electrode pattern is processed on the PDMS substrate. The pitch and finger width of the interdigital electrodes used as the UV lithography mask are 2 microns. The operating conditions of the photolithography process are: the photoresist model used in UV lithography is AZ4620, the thickness of the gel is 4 microns, the speed of the gel is 1000 rpm, the pre-baking temperature is 80 degrees, the exposure time is 15s, and the development time For 65s, the interdigital electrode pattern was prepared on the PDMS substrate.

[0059] 3. Preparation of collector electrode and ZnO seed layer: Using magnetron sputtering, a 60nm Pt film and a 10nm ZnO film are deposited on the PDMS substrate with interdigitated electrode pattern prepared in step 2 above.

[0060] 4. Preparation of three-dimensional ZnO nanorod array: Put the PDMS substrate prepared in step 3 above into a sealable container, and add deionized water and 0.55mol/L according to the ratio of 32:2:4:2:1 Zinc nitrate solution, 0.15mol/L polyvinylimine solution, 0.3mol/L hexamethylenetetramine solution and 75% ammonia water. Stir thoroughly and seal, then heat in a water bath at 70°C for 13 hours to obtain a nanometer zinc oxide array of about 6 microns;

[0061] 5. Three-dimensional MnO 2 Array preparation: three-electrode electrochemical deposition method is used to coat cheap and environmentally friendly MnO on the three-dimensional ZnO nanorod array 2 Materials, the operating conditions of electrochemical deposition are: the electrodeposition solution is a mixture of 0.02mol/L manganese nitrate and 0.1mol/L sodium nitrate, and the three-dimensional ZnO nanorod array interdigital electrode prepared in step 4 is used as the working electrode. The platinum sheet is the counter electrode, the calomel electrode is the reference electrode, and the current density of electrodeposition is 0.6mA/cm 2 , The deposition time is 30min, MnO is electrodeposited around the ZnO nanorods 2 Electrode material, get MnO 2 Coated ZnO nanorod array;

[0062] 6. Lift-Off process. The three-dimensional MnO obtained in step 5 2 The array is immersed in acetone for 2 hours and ultrasonicated for 10 minutes to remove excess photoresist to obtain ZnOMnO 2 Composite nano-array interdigital electrode.

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PUM

Property	Measurement	Unit
Thickness	60.0 ~ 70.0	nm
Thickness	10.0 ~ 20.0	nm
Thickness	40.0	nm
tensile		MPa
Particle size		Pa
strength	10

Description & Claims & Application Information

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Classification and recommendation of technical efficacy words

Strong flexibility
High transparency

Super capacitor based on three-dimensional ZnO@MnO2 composite nano array interdigital electrode and manufacturing method thereof

AI-Extracted Technical Summary

Problems solved by technology

Abstract

Image

Examples

Example Embodiment

Example Embodiment

Example Embodiment

PUM

Description & Claims & Application Information

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