CN113539700A - Preparation method of flexible stretchable micro supercapacitor - Google Patents

Preparation method of flexible stretchable micro supercapacitor Download PDF

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CN113539700A
CN113539700A CN202110732201.0A CN202110732201A CN113539700A CN 113539700 A CN113539700 A CN 113539700A CN 202110732201 A CN202110732201 A CN 202110732201A CN 113539700 A CN113539700 A CN 113539700A
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cnt
interdigital electrode
silver
mold
bottom plate
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孙义民
陈振宇
周爱军
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Wuhan Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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

Abstract

The invention discloses a preparation method of a flexible stretchable micro supercapacitor, which comprises the following steps: 1) designing an interdigital electrode pattern by utilizing modeling software; 2) printing an interdigital electrode mold by using a 3D printer and taking a polylactic acid wire material as a raw material, wherein the interdigital electrode mold consists of a bottom plate and an outer wall, and an interdigital electrode pattern formed by protrusions is arranged on the bottom plate; 3) mixing silicone rubber withUniformly mixing the cross-linking agent, injecting the mixture into a mold, and curing and molding to obtain a silicon rubber-based interdigital electrode template, wherein the surface of the template is provided with an interdigital electrode pattern formed by grooves; 4) sequentially depositing a silver current collector and Bi in the groove by a dropping coating process2O3The method comprises the following steps of (1) carrying out a/CNT active material and a silver current collector to obtain an interdigital electrode; 5) and coating electrolyte on the interdigital part, connecting copper sheets at two ends of the electrode, and performing plastic packaging on the PET film. The method has simple process, and the obtained capacitor substrate has light weight, good bending performance and high mechanical stability, and is suitable for large-scale production.

Description

Preparation method of flexible stretchable micro supercapacitor
Technical Field
The invention belongs to the technical field of miniature super capacitors, and particularly relates to a preparation method of a flexible stretchable miniature super capacitor.
Background
In recent years, with the rapid development of microelectronic technology, a series of novel electronic products, such as wearable, miniaturized, foldable, and highly integrated, are beginning to appear, and therefore the energy storage and supply problems of these emerging electronic products become a problem to be solved urgently. The novel miniature flexible super capacitor has the advantages of being integratable, high in power density, high in charging and discharging speed, reversible in energy storage process, bendable, safe and environment-friendly and the like, and becomes a research hotspot of emerging micro energy storage equipment in recent years. The micro super capacitor is composed of a current collector, an electrode material, a substrate and an electrolyte, and the key factor determining the performance of the super capacitor is the electrode material. Therefore, the flexible micro-capacitor with high energy storage efficiency, good stability, simple production process and low manufacturing cost becomes the difficult point and the key point of the research of the super capacitor nowadays.
Since the oxide of bismuth has excellent performance in the electrode material, among them Bi2O3The crystal of the super capacitor is in a two-dimensional sheet structure, the energy storage of the super capacitor based on the two-dimensional sheet bismuth trioxide electrode material is realized through the adsorption/desorption of oxygen ions between the electrode and the electrolyte interface, but at the same time, the potential interlayer energy storage space is not completely utilized due to the aggregation and stacking of the two-dimensional material sheets, so that a longer ion transmission path is caused, the full contact between the electrolyte and the sheets is not facilitated, the electrochemical utilization rate is reduced, and therefore how to realize the effective dispersion of the bismuth trioxide nanosheets makes the bismuth trioxide nanosheets have high specific surface area and excellent conductivity become the key for preparing the micro super capacitor.
Because the electrochemical performance of a single micro supercapacitor can be improved by reducing the electrode distance, and the energy density of an electrode can be improved by increasing the carrying capacity of an electrode active substance per unit area, the method for increasing the vertical thickness of the electrode active substance under the condition of unchanged unit area is a method for enhancing the energy density of the micro capacitor.
Due to the rigid nature of conventional energy storage devices, their use in flexible electronic devices that are now emerging is greatly limited. Flexible capacitor devices have attracted much attention because of their advantages of being lightweight, flexible, durable, and conformal. However, the existing preparation process of the flexible electrode device usually involves complicated processes such as laser etching, high-pressure pressing, mask method and the like. Therefore, a simple and convenient flexible electrode preparation process is a hot spot of current research.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible stretchable micro super capacitor, which has the advantages of simple process, high manufacturing precision, low cost and capability of automatically designing an electrode pattern, and the obtained micro super capacitor has the advantages of high electrode active substance load per unit area, large bending angle, good ductility, high mechanical strength, excellent energy storage performance and good application prospect.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
1) designing an interdigital electrode pattern by utilizing modeling software;
2) printing an interdigital electrode mold by using a 3D printer and taking a polylactic acid wire material as a raw material, wherein the mold consists of a bottom plate and an outer wall, and an interdigital electrode pattern formed by protrusions is arranged on the bottom plate;
3) uniformly mixing silicon rubber and a cross-linking agent, injecting the mixture into the mold obtained in the step 2), and curing and molding to obtain a silicon rubber-based interdigital electrode template, wherein the surface of the template is provided with an interdigital electrode pattern formed by grooves;
4) dropping the silicon rubber-based finger-shaped electrode template obtained in the step 3) into the grooveSequentially depositing silver current collector and Bi2O3The method comprises the following steps of (1) carrying out a/CNT active material and a silver current collector to obtain an interdigital electrode;
5) coating electrolyte on the interdigital part of the interdigital electrode obtained in the step 4), connecting copper sheets at two ends of the electrode, and carrying out plastic packaging on a PET film to obtain the flexible stretchable micro supercapacitor.
According to the scheme, the interdigital electrode pattern is designed by utilizing modeling software in the step 1), and parameters such as the length, the width, the thickness and the like of the interdigital can be adjusted according to requirements.
According to the scheme, the interdigital electrode die in the step 2) has the same external contour dimension of the outer wall as that of the bottom plate. Preferably, the size of the bottom plate is 50-60mm in length, 40-50mm in width and 3-5mm in height; the height of the outer wall is 10-15mm, and the thickness of the outer wall is 4-6 mm.
According to the scheme, the protruding height of the interdigital electrode pattern formed by the protrusions in the step 2) is 0.2-0.8 mm.
According to the scheme, in the step 2), the line thickness of the polylactic acid wire is 1.5-2 mm.
According to the scheme, in the step 2), the 3D printing parameters are as follows: the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
According to the scheme, in the step 3), the depth of the grooves of the formed interdigital electrode pattern is 0.2-0.8 mm.
According to the scheme, in the step 3), the addition amount of the cross-linking agent is 10-12 wt% of the silicone rubber.
According to the scheme, in the step 3), the mixed silicon rubber and the cross-linking agent are injected into a mold, the mold is placed in a vacuum environment for 30-50min, after bubbles are completely removed, the mold is insulated at 75-125 ℃ for 5-8 hours for curing, and finally the cured silicon rubber is peeled off from the bottom plate to obtain the silicon rubber-based interdigital electrode template.
According to the scheme, in the step 3), the thickness of the obtained silicon rubber-based interdigital electrode template is 3-5 mm.
According to the scheme, in the step 4), the grooves are sequentially coated by a drop coating processDeposited silver Current collector, Bi2O3The specific steps of the/CNT active material and the silver current collector are as follows: dripping conductive silver paste into the bottom of the groove, drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping Bi into the groove2O3Ethanol dispersion slurry of/CNT, then drying, repeating for multiple times to Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dropwise adding conductive silver paste on the surface of the/CNT active substance, drying, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active is completely covered.
Preferably, the drying is natural airing or drying at 30-60 ℃.
Preferably, the Bi2O3In ethanol dispersion slurry of/CNT, Bi2O3And CNT at a mass ratio of 4.66:1-5, Bi2O3The concentration of the/CNT is 20-40 mg/ml.
Preferably, the conductive silver paste is a dispersion of nano silver in ethyl acetate, and the concentration is 5-20 mg/ml.
Preferably, the Bi2O3The preparation of ethanol dispersion slurry of/CNT is as follows: bismuth nitrate and carboxylated carbon nanotubes are used as raw materials, and a hydrothermal method is utilized to prepare Bi2O3Nano-sheet is loaded on carboxylated CNT, annealing treatment is carried out to obtain Bi2O3the/CNT composite is then dispersed in ethanol to obtain Bi2O3a/CNT paste.
More preferably, the hydrothermal conditions are: 100 ℃ and 200 ℃ for 3-8 h.
More preferably, the annealing conditions are: calcining at 200 ℃ and 500 ℃ for 2h, and then cooling to normal temperature.
More preferably, the carboxylated carbon nanotubes are prepared by: the volume ratio of the multi-wall carbon nano-tube is 3: 1, condensing and heating the mixture at 85-95 ℃ for reflux for 2-3h, cooling and washing the mixture to be neutral to obtain the carboxylated carbon nanotube.
More preferably, the mass ratio of the bismuth nitrate to the carboxylated carbon nanotubes is 0.97: 0.1 to 0.5.
According to the scheme, in the step 5), the electrolyte is polyvinyl alcohol/potassium hydroxide (PVA/KOH) conductive gel, wherein the concentration of PVA is 0.1-0.125g/ml, and the concentration of KOH is 1-2 mol/L.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a flexible stretchable micro supercapacitor, which comprises the steps of firstly obtaining an interdigital chip type electrode convex mould by a 3D printing technology, further obtaining a silicon rubber-based interdigital chip type electrode concave mould plate, obtaining a deeper groove depth (0.2-0.8mm), loading more electrode active substances in a unit area, and increasing the vertical thickness of the electrode active substances; the bottom of the silicon rubber-based interdigital chip type electrode concave template is closed, and the current collector and the electroactive substance are difficult to fill through the traditional filtering mode.
2. The micro super capacitor provided by the invention takes the composite material made of the bismuth trioxide carbon nano tube and the carbon nano tube as the electrode material, so that the energy storage capacity of the micro super capacitor is improved, and the mass of the micro super capacitor can be effectively reduced; in addition, the method has the advantage of good tensile strain, and the loading capacity of the electrode active substances in unit area is increased, so that higher capacitance value in unit area is obtained, and the energy density of the micro-capacitor is enhanced; the obtained micro super capacitor has large bending angle, good ductility, high mechanical strength and excellent energy storage performance, and the bending angle is 1mA/cm2The area capacitance is 275mF/cm at the current density of (3)2And has good application prospect.
3. The method adopts a simple hydrothermal method, and grows the orderly-arranged bismuth trioxide arrays on the surfaces of the carbon nanotubes through low-temperature annealing treatment, and the orderly-arranged bismuth trioxide arrays provide more active sites for ion exchange; and the carbon nano tube forms a cross-linked net structure, so that the problem of insufficient conductivity of the bismuth trioxide is effectively solved.
Drawings
FIG. 1 is a photograph of a finished micro supercapacitor made in example 1 of the present invention.
FIG. 2 is a photograph showing the bent and stretched micro-sized supercapacitor prepared in example 1 of the present invention
FIG. 3 is a schematic diagram of the main process flow in the example of the present invention.
FIG. 4 is a graph (a) showing the cyclic voltammetry characteristics and galvanostatic charge-discharge test results of the micro-supercapacitors prepared in example 1 of the present invention.
Fig. 5 is a graph of cyclic voltammetry characteristics of the micro-supercapacitor prepared in example 1 of the present invention before bending and after bending by 90 °.
Detailed Description
The technical solution of the present invention is further explained below with reference to specific examples and drawings, and the process flow in the following examples is shown in fig. 3.
Example 1
The preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
(1) a mold model and interdigital electrode patterns are constructed by using 3D modeling software, the size of the bottom plate is 50mm in length, 40mm in width and 3mm in height, and the protruding height of the electrode patterns on the bottom plate is 0.5 mm. The outer wall thickness is 4mm, and high 10mm, the external profile size is with the bottom plate.
(2) The bottom plate part and the outer wall part of the die are printed by using a 3D printing process and selecting a commercialized polylactic acid wire material with the diameter of 1.75mm, wherein the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
(3) Combining the outer wall of the mold with a bottom plate, injecting 6g of mixed Sylgard-184 silicon rubber and a cross-linking agent (the addition amount is 10 wt% of the silicon rubber) into the mold, preserving for 30min under vacuum to remove bubbles, then preserving the heat for 8h at 75 ℃, and after natural cooling, stripping the silicon rubber substrate from the bottom plate to obtain the silicon rubber-based interdigital electrode template.
(4) Commercial carbon nanotubes (tube diameter of 5-15nm and length of 0.5-2 μm)1g are mixed with 90ml concentrated sulfuric acid and 30ml concentrated nitric acid, and then the mixture is condensed and heated under reflux at 90 ℃ for 2.5 h. And cooling and washing for many times until the carbon nano tube is neutral to obtain the carboxylated carbon nano tube.
(5) 0.1g of the carboxylated carbon nanotube and 0.97g of bismuth nitrate pentahydrate were dissolved in a mixed solution of 34ml of ethanol and 17ml of ethylene glycol, and sufficiently dispersed. And (3) placing the solution in a hydrothermal reaction kettle, and keeping the temperature at 180 ℃ for 6 hours. Cooling, centrifugally separating, retaining solid-phase precipitate, and drying. The solid phase material was calcined at 300 ℃ for 2 h. Cooling to obtain Bi2O3/CNT electrode material, Bi obtained2O3CNT to 20mg/ml Bi dispersed in ethanol2O3Ethanol dispersion slurry of/CNT.
(6) The polyvinyl alcohol/potassium hydroxide conductive gel is prepared by dissolving 3g of polyvinyl alcohol in 30ml of deionized water at 85 ℃, then adding 1.68g of potassium hydroxide solid, fully stirring, mixing uniformly and then gradually cooling to room temperature.
(7) Sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based interdigital electrode template obtained in the step 3) by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: diluting commercial nano-silver solid into 15mg/ml slurry with ethyl acetate, dripping into a groove of a silicon rubber substrate by using a rubber head dropper, naturally drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping 20mg/ml Bi into the groove2O3Drying the ethanol dispersed slurry of/CNT at 50 ℃ for a plurality of times until Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dripping conductive silver paste on the surface of the CNT active substance, naturally airing, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active material is completely covered, and the grooves are completely filled, so that the interdigital electrode is obtained.
(8) 2g of polyvinyl alcohol/potassium hydroxide conductive gel with PVA concentration of 100g/L and KOH of 1mol/L is smeared on the surface of the interdigital pattern of the interdigital electrode obtained in the step (7), and is dried for 2 hours at room temperature; and connecting copper foils at two ends of the electrode substrate, and packaging by using a PET (polyethylene terephthalate) film to obtain the micro capacitor.
Fig. 1 shows a physical representation of the fabricated interdigitated supercapacitor of example 1.
Fig. 2 shows the state of the fabricated interdigitated micro supercapacitor substrate of example 1 when it is bent.
FIG. 4 is a graph (a) showing the cyclic voltammetry characteristics and galvanostatic charge-discharge test results of the interdigital micro supercapacitor prepared in example 1; the figure shows a capacitance per unit area of 278.1mF/cm, which has a larger specific capacitance than conventional micro-capacitors.
Fig. 5 is a test chart of cyclic voltammetry characteristics of the interdigital micro supercapacitor prepared in example 1 before bending and after bending by 90 °. As shown in FIG. 4, the change of the cyclic voltammetry characteristics after bending is not obvious, and the capacitance value before testing is 278.1mF/cm2After bending, the thickness is 240.2mF/cm2The retention thereof was 86.3%. Showing good capacity retention after bending.
Example 2
The preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
(1) and 3D modeling software is utilized to construct a mold model and an electrode pattern, the size of the bottom plate is 50mm in length, 40mm in width and 3mm in height, and the protruding height of the electrode pattern on the bottom plate is 0.5 mm. The outer wall thickness is 4mm, and the external profile dimension of height 10mm is with the bottom plate.
(2) The bottom plate part and the outer wall part of the die are printed by using a 3D printing process and selecting a commercialized polylactic acid wire material with the diameter of 1.75mm, wherein the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
(3) Combining the outer wall of the mold with a bottom plate, injecting 6g of mixed Sylgard-184 silicon rubber and a cross-linking agent (the addition amount is 10 wt% of the silicon rubber) into the mold, preserving for 30min under vacuum to remove bubbles, then preserving the heat for 8h at 75 ℃, and after natural cooling, stripping the silicon rubber substrate from the bottom plate to obtain the silicon rubber-based interdigital electrode template.
(4) Commercial carbon nanotubes (1 g) were mixed well with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, and condensed and heated under reflux at 90 ℃ for 2.5 hours. After cooling, washing for many times to neutrality to obtain the carboxylated carbon nanotube
(5) 0.2g of the carboxylated carbon nanotube and 0.97g of bismuth nitrate pentahydrate were dissolved in a mixed solution of 34ml of ethanol and 17ml of ethylene glycol, and the mixture was sufficiently dispersed. And (3) placing the solution in a hydrothermal reaction kettle, and keeping the temperature at 180 ℃ for 6 hours. Cooling, centrifugally separating, retaining solid-phase precipitate, and drying. The solid phase material was calcined at 300 ℃ for 2 h. Cooling to obtain Bi2O3/CNT electrode material, Bi obtained2O3CNT to 20mg/ml Bi dispersed in ethanol2O3Ethanol dispersion slurry of/CNT.
(6) The polyvinyl alcohol/potassium hydroxide conductive gel is prepared by dissolving 3g of polyvinyl alcohol in 30ml of deionized water at 85 ℃, adding 1.68g of potassium hydroxide solid, fully stirring, mixing uniformly, and gradually cooling to room temperature to obtain the polyvinyl alcohol/potassium hydroxide conductive gel
(7) Sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based interdigital electrode template obtained in the step 3) by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: diluting commercial nano-silver solid into 15mg/ml slurry by using ethyl acetate by using a dripping method, dripping the slurry into a groove of a silicon rubber substrate by using a rubber head dropper, naturally airing the slurry, repeating the process for many times until the bottom of the groove is completely covered by silver, and continuously dripping 20mg/ml Bi into the groove2O3Drying the ethanol dispersed slurry of/CNT at 50 ℃ for a plurality of times until Bi2O3the/CNT electrode material reaches the required thickness, and finally Bi2O3Continuously dripping conductive silver paste on the surface of the CNT active substance, naturally airing, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active material is completely covered, and the grooves are completely filled, so that the interdigital electrode is obtained.
(8) And (3) coating 2g of polyvinyl alcohol/potassium hydroxide conductive gel with PVA concentration of 100g/L and KOH of 1mol/L on the surface of the interdigital pattern of the interdigital electrode obtained in the step (7), and drying at room temperature for 2 hours. And connecting copper foils at two ends of the electrode substrate, and packaging by using a PET (polyethylene terephthalate) film to obtain the micro capacitor.
Example 3
The preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
(1) and 3D modeling software is utilized to construct a mold model and an electrode pattern, the size of the bottom plate is 50mm in length, 40mm in width and 3mm in height, and the protruding height of the electrode pattern on the bottom plate is 0.5 mm. The outer wall thickness is 4mm, and the external profile dimension of height 10mm is with the bottom plate.
(2) The bottom plate part and the outer wall part of the die are printed by using a 3D printing process and selecting a commercialized polylactic acid wire material with the diameter of 1.75mm, wherein the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
(3) Combining the outer wall of the mold with a bottom plate, injecting 5g of mixed Sylgard-184 silicon rubber and a cross-linking agent (the addition amount is 10 wt% of the silicon rubber) into the mold, preserving for 30min under vacuum to remove bubbles, then preserving the heat for 5h at 125 ℃, and after natural cooling, stripping the silicon rubber substrate from the bottom plate to obtain the silicon rubber-based interdigital electrode template.
(4) Commercial carbon nanotubes (1 g) were mixed well with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, and condensed and heated under reflux at 90 ℃ for 2.5 hours. After cooling, washing for many times to neutrality to obtain the carboxylated carbon nanotube
(5) 0.3g of the carboxylated carbon nanotube and 0.97g of bismuth nitrate pentahydrate were dissolved in a mixed solution of 34ml of ethanol and 17ml of ethylene glycol, and the mixture was sufficiently dispersed. And (3) placing the solution in a hydrothermal reaction kettle, and keeping the temperature at 160 ℃ for 8 h. Cooling, centrifugally separating, retaining solid-phase precipitate, and drying. The solid phase material was calcined at 300 ℃ for 2 h. Cooling to obtain Bi2O3/CNT electrode material, Bi obtained2O3CNT to 20mg/ml Bi dispersed in ethanol2O3Ethanol dispersion slurry of/CNT.
(6) The polyvinyl alcohol/potassium hydroxide conductive gel is prepared by dissolving 2-3g of polyvinyl alcohol in 20mL of deionized water at 85 ℃, adding 0.112g of potassium hydroxide solid, fully stirring, uniformly mixing, and gradually cooling to room temperature to obtain the polyvinyl alcohol/potassium hydroxide conductive gel
(7) Sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based interdigital electrode template obtained in the step 3) by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: diluting commercial nano-silver solid into 15mg/ml slurry with ethyl acetate, dripping into a groove of a silicon rubber substrate by using a rubber head dropper, naturally drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping 20mg/ml Bi into the groove2O3Drying the ethanol dispersed slurry of/CNT at 55 ℃ for a plurality of times until Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dripping conductive silver paste on the surface of the CNT active substance, naturally airing, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active material is completely covered, and the grooves are completely filled, so that the interdigital electrode is obtained.
(8) And (3) coating 2g of polyvinyl alcohol/potassium hydroxide conductive gel with PVA concentration of 100g/L and KOH of 1mol/L on the surface of the interdigital pattern of the interdigital electrode obtained in the step (7), drying at room temperature for 3h, connecting copper foils at two ends of the electrode substrate, and packaging by using a PET (polyethylene terephthalate) film to obtain the micro capacitor.
Example 4
The preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
(1) and 3D modeling software is utilized to construct a mold model and an electrode pattern, the size of the bottom plate is 50mm in length, 40mm in width and 3mm in height, and the protruding height of the electrode pattern on the bottom plate is 0.5 mm. The outer wall thickness is 4mm, and the external profile dimension of height 10mm is with the bottom plate.
(2) The bottom plate part and the outer wall part of the die are printed by using a 3D printing process and selecting a commercialized polylactic acid wire material with the diameter of 1.75mm, wherein the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
(3) Combining the outer wall of the mold with a bottom plate, injecting 6g of mixed Sylgard-184 silicon rubber and a cross-linking agent (the addition amount is 10 wt% of the silicon rubber) into the mold, preserving for 30min under vacuum to remove bubbles, then preserving the heat for 7h at 80 ℃, and stripping the silicon rubber substrate from the bottom plate after natural cooling to obtain the silicon rubber-based interdigital electrode template.
(4) Commercial carbon nanotubes (1 g) were mixed well with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, and condensed and heated under reflux at 90 ℃ for 2.5 hours. After cooling, washing for many times to neutrality to obtain the carboxylated carbon nanotube
(5) 0.4g of the carboxylated carbon nanotube and 0.97g of bismuth nitrate pentahydrate were dissolved in a mixed solution of 34ml of ethanol and 17ml of ethylene glycol, and the mixture was sufficiently dispersed. And (3) placing the solution in a hydrothermal reaction kettle, and keeping the temperature at 160 ℃ for 8 h. Cooling, centrifugally separating, retaining solid-phase precipitate, and drying. The solid phase material was calcined at 300 ℃ for 2 h. Cooling to obtain Bi2O3/CNT electrode material, Bi obtained2O3CNT to 20mg/ml Bi dispersed in ethanol2O3Ethanol dispersion slurry of/CNT.
(6) The polyvinyl alcohol/potassium hydroxide conductive gel is prepared by dissolving 2g of polyvinyl alcohol in 30ml of deionized water at 85 ℃, adding 0.112g of potassium hydroxide solid, fully stirring, mixing uniformly, and gradually cooling to room temperature to obtain the polyvinyl alcohol/potassium hydroxide conductive gel
(7) Sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based interdigital electrode template obtained in the step 3) by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: diluting commercial nano-silver solid into 15mg/ml slurry with ethyl acetate, dripping into a groove of a silicon rubber substrate by using a rubber head dropper, naturally drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping 20mg/ml Bi into the groove2O3Drying the ethanol dispersed slurry of/CNT at 45 ℃ for a plurality of times until Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dripping conductive silver paste on the surface of the CNT active substance, naturally airing, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active material is completely covered, and the grooves are completely filled, so that the interdigital electrode is obtained.
(8) And (3) coating 2g of polyvinyl alcohol/potassium hydroxide conductive gel with PVA concentration of 100g/L and KOH of 1mol/L on the surface of the interdigital pattern of the interdigital electrode obtained in the step (7), drying at room temperature for 3h, connecting copper foils at two ends of the electrode substrate, and packaging by using a PET (polyethylene terephthalate) film to obtain the micro capacitor.
Example 5
The preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
(1) and 3D modeling software is utilized to construct a mold model and an electrode pattern, the size of the bottom plate is 50mm in length, 40mm in width and 3mm in height, and the protruding height of the electrode pattern on the bottom plate is 0.5 mm. The outer wall thickness is 4mm, and the external profile dimension of height 10mm is with the bottom plate.
(2) The bottom plate part and the outer wall part of the die are printed by using a 3D printing process and selecting a commercialized polylactic acid wire material with the diameter of 1.75mm, wherein the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
(3) Combining the outer wall of the mold with a bottom plate, injecting 5g of mixed Sylgard-184 silicon rubber and a cross-linking agent (the addition amount is 10 wt% of the silicon rubber) into the mold, preserving for 50min under vacuum to remove bubbles, then preserving the heat for 5h at 125 ℃, and after natural cooling, stripping the silicon rubber substrate from the bottom plate to obtain the silicon rubber-based interdigital electrode template.
(4) Commercial carbon nanotubes (1 g) were mixed well with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, and condensed and heated under reflux at 90 ℃ for 2.5 hours. After cooling, washing for many times to neutrality to obtain the carboxylated carbon nanotube
(5) 0.5g of the carboxylated carbon nanotube and 0.97g of bismuth nitrate pentahydrate were dissolved in a mixed solution of 34ml of ethanol and 17ml of ethylene glycol, and the mixture was sufficiently dispersed. Putting the solution into a hydrothermal reaction kettle, and preserving the heat at 160 ℃ for 3-8 h. Cooling, centrifugally separating, retaining solid-phase precipitate, and drying. The solid phase material was calcined at 300 ℃ for 2 h. Cooling to obtain Bi2O3/CNT electrode material, Bi obtained2O3CNT to 20mg/ml Bi dispersed in ethanol2O3Ethanol dispersion slurry of/CNT.
(6) The polyvinyl alcohol/potassium hydroxide conductive gel is prepared by dissolving 2g of polyvinyl alcohol in 30ml of deionized water at 85 ℃, adding 1.68g of potassium hydroxide solid, fully stirring, mixing uniformly, and gradually cooling to room temperature to obtain the polyvinyl alcohol/potassium hydroxide conductive gel
(7) Sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based interdigital electrode template obtained in the step 3) by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: diluting commercial nano-silver solid into 15mg/ml slurry with ethyl acetate, dripping into a groove of a silicon rubber substrate by using a rubber head dropper, naturally drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping 20mg/ml Bi into the groove2O3Drying the alcohol dispersed slurry of/CNT at 45-55 deg.C, repeating the above steps until Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dripping conductive silver paste on the surface of the CNT active substance, naturally airing, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active material is completely covered, and the grooves are completely filled, so that the interdigital electrode is obtained.
(8) And (3) coating 2g of polyvinyl alcohol/potassium hydroxide conductive gel with PVA concentration of 100g/L and KOH of 1mol/L on the surface of the interdigital pattern of the interdigital electrode obtained in the step (7), and drying at room temperature for 5 hours. And connecting copper foils at two ends of the electrode substrate, and packaging by using a PET (polyethylene terephthalate) film to obtain the micro capacitor.
Example 7
The preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
(1) and 3D modeling software is utilized to construct a mold model and an electrode pattern, the size of the bottom plate is 50mm in length, 40mm in width and 3mm in height, and the protruding height of the electrode pattern on the bottom plate is 0.5 mm. The outer wall thickness is 4mm, and the external profile dimension of height 10mm is with the bottom plate.
(2) The bottom plate part and the outer wall part of the die are printed by using a 3D printing process and selecting a commercialized polylactic acid wire material with the diameter of 1.75mm, wherein the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
(3) Combining the outer wall of the mold with a bottom plate, injecting 5g of mixed Sylgard-184 silicon rubber and a cross-linking agent (the addition amount is 10 wt% of the silicon rubber) into the mold, preserving for 30min under vacuum to remove bubbles, then preserving the heat for 5h at 75 ℃, and after natural cooling, stripping the silicon rubber substrate from the bottom plate to obtain the silicon rubber-based interdigital electrode template.
(4) Commercial carbon nanotubes (1 g) were mixed well with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, and condensed and heated under reflux at 90 ℃ for 2.5 hours. After cooling, washing for many times to neutrality to obtain the carboxylated carbon nanotube
(5) 0.1g of the carboxylated carbon nanotube and 0.485g of bismuth nitrate pentahydrate are dissolved in a mixed solution of 34ml of ethanol and 17ml of ethylene glycol, and the mixture is fully dispersed. Putting the solution into a hydrothermal reaction kettle, and preserving the heat at 160 ℃ for 3-8 h. Cooling, centrifugally separating, retaining solid-phase precipitate, and drying. The solid phase material was calcined at 300 ℃ for 2 h. Cooling to obtain Bi2O3/CNT electrode material, Bi obtained2O3CNT to 20mg/ml Bi dispersed in ethanol2O3Ethanol dispersion slurry of/CNT.
(6) The polyvinyl alcohol/potassium hydroxide conductive gel is prepared by dissolving 2-3g of polyvinyl alcohol in 30ml of deionized water at 85 ℃, adding 1.68g of potassium hydroxide solid, fully stirring, uniformly mixing, and gradually cooling to room temperature to obtain the polyvinyl alcohol/potassium hydroxide conductive gel
(7) Sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based interdigital electrode template obtained in the step 3) by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: diluting commercial nano-silver solid into 15mg/ml slurry with ethyl acetate, dripping into a groove of a silicon rubber substrate by using a rubber head dropper, naturally drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping 20mg/ml Bi into the groove2O3Drying the ethanol dispersed slurry of/CNT at 55 ℃ for a plurality of times until Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dripping conductive silver paste on the surface of the CNT active substance, naturally airing, and repeating for multiple times until the conductive silver paste is formedCoating of silver current collector with Bi2O3the/CNT active material is completely covered, and the grooves are completely filled, so that the interdigital electrode is obtained.
(8) And (3) coating 2g of polyvinyl alcohol/potassium hydroxide conductive gel with PVA concentration of 100g/L and KOH of 1mol/L on the surface of the interdigital pattern of the interdigital electrode obtained in the step (7), drying at room temperature for 2h, connecting copper foils at two ends of the electrode substrate, and packaging by using a PET (polyethylene terephthalate) film to obtain the micro capacitor.
Example 8
The preparation method of the flexible stretchable micro supercapacitor comprises the following steps:
(1) and 3D modeling software is utilized to construct a mold model and an electrode pattern, the size of the bottom plate is 50mm in length, 40mm in width and 3mm in height, and the protruding height of the electrode pattern on the bottom plate is 0.5 mm. The outer wall thickness is 4mm, and the external profile dimension of height 10mm is with the bottom plate.
(2) The bottom plate part and the outer wall part of the die are printed by using a 3D printing process and selecting a commercialized polylactic acid wire material with the diameter of 1.75mm, wherein the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
(3) Combining the outer wall of the mold with a bottom plate, injecting 6g of mixed Sylgard-184 silicon rubber and a cross-linking agent (the addition amount is 10 wt% of the silicon rubber) into the mold, preserving for 40min under vacuum to remove bubbles, then preserving the heat for 8h at 75 ℃, and stripping the silicon rubber substrate from the bottom plate after natural cooling to obtain the silicon rubber-based interdigital electrode template.
(4) Commercial carbon nanotubes (1 g) were mixed well with 90ml of concentrated sulfuric acid and 30ml of concentrated nitric acid, and condensed and heated under reflux at 90 ℃ for 2.5 hours. After cooling, washing for many times to neutrality to obtain the carboxylated carbon nanotube
(5) 0.2g of the carboxylated carbon nanotube and 0.485g of bismuth nitrate pentahydrate are dissolved in a mixed solution of 34ml of ethanol and 17ml of ethylene glycol, and the mixture is fully dispersed. And (3) placing the solution in a hydrothermal reaction kettle, and keeping the temperature at 160 ℃ for 8 h. Cooling, centrifugally separating, retaining solid-phase precipitate, and drying. The solid phase material was calcined at 300 ℃ for 2 h. Cooling to obtain Bi2O3a/CNT electrode material, wherein the CNT electrode material,the obtained Bi2O3CNT to 20mg/ml Bi dispersed in ethanol2O3Ethanol dispersion slurry of/CNT.
(6) The polyvinyl alcohol/potassium hydroxide conductive gel is prepared by dissolving 2g of polyvinyl alcohol in 30ml of deionized water at 85 ℃, adding 1.68g of potassium hydroxide solid, fully stirring, mixing uniformly, and gradually cooling to room temperature to obtain the polyvinyl alcohol/potassium hydroxide conductive gel
(7) Sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based interdigital electrode template obtained in the step 3) by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: diluting commercial nano-silver solid into 15mg/ml slurry with ethyl acetate, dripping into a groove of a silicon rubber substrate by using a rubber head dropper, naturally drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping 20mg/ml Bi into the groove2O3Drying the ethanol dispersed slurry of/CNT at 50 ℃ for a plurality of times until Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dripping conductive silver paste on the surface of the CNT active substance, naturally airing, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active material is completely covered, and the grooves are completely filled, so that the interdigital electrode is obtained.
(8) And (3) coating 2g of polyvinyl alcohol/potassium hydroxide conductive gel with PVA concentration of 100g/L and KOH of 1mol/L on the surface of the interdigital pattern of the interdigital electrode obtained in the step (7), drying at room temperature for 5 hours, connecting copper foils at two ends of the electrode substrate, and packaging by using a PET (polyethylene terephthalate) film to obtain the micro capacitor.
The above embodiments are only used for illustrating but not limiting the technical solutions of the present invention, and although the above embodiments describe the present invention in detail, those skilled in the art should understand that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and any modifications and equivalents may fall within the scope of the claims.

Claims (10)

1. A preparation method of a flexible stretchable micro supercapacitor is characterized by comprising the following steps:
1) designing an interdigital electrode pattern by utilizing modeling software;
2) printing an interdigital electrode mold by using a 3D printer and taking a polylactic acid wire material as a raw material, wherein the mold consists of a bottom plate and an outer wall, and an interdigital electrode pattern formed by protrusions is arranged on the bottom plate;
3) uniformly mixing silicon rubber and a cross-linking agent, injecting the mixture into the mold obtained in the step 2), and curing and molding to obtain a silicon rubber-based interdigital electrode template, wherein the surface of the template is provided with an interdigital electrode pattern formed by grooves;
4) sequentially depositing a silver current collector and Bi in the groove of the silicon rubber-based finger-shaped electrode template obtained in the step 3) through a dropping coating process2O3The method comprises the following steps of (1) carrying out a/CNT active material and a silver current collector to obtain an interdigital electrode;
5) coating electrolyte on the interdigital part of the interdigital electrode obtained in the step 4), connecting copper sheets at two ends of the electrode, and carrying out plastic packaging on a PET film to obtain the flexible stretchable micro supercapacitor.
2. The method according to claim 1, wherein the protrusions in step 2) form an interdigital electrode pattern having a protrusion height of 0.2-0.8 mm.
3. The production method according to claim 1, wherein in the step 2), the thickness of the thread of the polylactic acid filament is 1.5 to 2 mm; the 3D printing parameters are as follows: the printing layer height is 0.1mm, the printing precision is 0.1mm, the filling type is a grid, the filling density is 100%, and the printing temperature is 150 ℃.
4. The preparation method according to claim 1, wherein in the step 3), the mixed silicone rubber and the crosslinking agent are injected into a mold, and placed in a vacuum environment for 30-50min, after bubbles are completely removed, the mold is cured at 75-125 ℃ for 5-8 hours, and finally the cured silicone rubber is peeled off from the bottom plate to obtain the silicone rubber-based interdigital electrode template.
5. The preparation method according to claim 1, wherein in the step 4), a silver current collector, Bi and a silver/bismuth (Bi) are sequentially deposited in the groove by a drop coating process2O3The specific steps of the/CNT active material and the silver current collector are as follows: dripping conductive silver paste into the bottom of the groove, drying, repeating for many times until the bottom of the groove is completely covered by silver, and continuously dripping Bi into the groove2O3Ethanol dispersion slurry of/CNT, then drying, repeating for multiple times to Bi2O3the/CNT active reaches the required thickness, finally in Bi2O3Continuously dropwise adding conductive silver paste on the surface of the/CNT active substance, drying, repeating for multiple times until a silver current collector covering layer is formed, and adding Bi2O3the/CNT active is completely covered.
6. The method according to claim 5, wherein the Bi is2O3In ethanol dispersion slurry of/CNT, Bi2O3And CNT at a mass ratio of 4.66:1-5, Bi2O3The concentration of the/CNT is 20-40 mg/ml; the conductive silver paste is a dispersion of nano silver in ethyl acetate, and the concentration is 5-20 mg/ml.
7. The method according to claim 5, wherein the Bi is2O3The preparation of ethanol dispersion slurry of/CNT is as follows: bismuth nitrate and carboxylated carbon nanotubes are used as raw materials, and a hydrothermal method is utilized to prepare Bi2O3Nano-sheet is loaded on carboxylated CNT, annealing treatment is carried out to obtain Bi2O3the/CNT composite is then dispersed in ethanol to obtain Bi2O3Ethanol dispersion slurry of/CNT.
8. The method of claim 7, wherein the carboxylated carbon nanotube is prepared by: the volume ratio of the multi-wall carbon nano-tube is 3: 1, condensing and heating the mixture at 85-95 ℃ for reflux for 2-3h, cooling and washing the mixture to be neutral to obtain the carboxylated carbon nanotube.
9. The method according to claim 5, wherein the drying is natural airing or oven-drying at 30-60 ℃.
10. The method according to claim 1, wherein in the step 5), the electrolyte is polyvinyl alcohol/potassium hydroxide conductive gel, wherein the concentration of PVA is 0.1-0.125g/ml, and the concentration of KOH is 1-2 mol/L.
CN202110732201.0A 2021-06-30 2021-06-30 Preparation method of flexible stretchable micro supercapacitor Pending CN113539700A (en)

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Application publication date: 20211022