KR20220144029A - Method for manufacturing micro-supercapacitor using solution process and micro-supercapacitor produced by the production method thereof - Google Patents

Abstract

The present invention relates to a manufacturing method of a micro-supercapacitor using a solution process and a micro-supercapacitor manufactured by the manufacturing method and, more specifically, to a manufacturing method of a micro-supercapacitor using a solution process for manufacturing a high-performance micro-supercapacitor by utilizing a patterning method capable of high capacity and large area and a micro-supercapacitor manufactured by the manufacturing method. The manufacturing method of a micro-supercapacitor using a solution process of the present invention comprises the steps of: a) preparing a MXene solution; b) coating a substrate with a photoresist mask; c) coating the substrate coated with the photoresist mask with the MXene solution; and d) manufacturing a micro-supercapacitor by obtaining a patterned MXene from the substrate.

Description

Method for manufacturing a micro supercapacitor using a solution process and a micro supercapacitor manufactured by the manufacturing method

The present invention relates to a method for manufacturing a micro-supercapacitor using a solution process and a micro-supercapacitor manufactured by the method, and more particularly, to a high-performance micro-supercapacitor by using a patterning method capable of high capacity and large area. It relates to a method for manufacturing a micro-supercapacitor using a solution process for the following and to a micro-supercapacitor manufactured by the method for manufacturing the same.

The rapid development of miniaturized electronic devices is increasing the demand for small on-chip energy storage devices.

Micro supercapacitors have great potential to supplement and replace conventional batteries and electrolytic capacitors due to their many advantages such as fast charging and discharging (faster rate), high power (high power), and high lifetime stability (unlimited lifetime).

However, in the conventional micro-supercapacitor manufacturing technology, it is cumbersome to construct a micro-scale electrode in terms of cost-effectiveness, and wide application of the micro-supercapacitor is impossible due to the limitation of large-area fabrication.

In recent years, the development of supercapacitors using maxine, which has high conductivity and excellent electrochemical properties, shows excellent performance in energy storage devices.

A conventional micro supercapacitor was manufactured by forming a maxine film on a glass or plastic substrate using a dip-coating method, and using a pattern using a physical scratching method on the maxine film as an electrode.

This manufacturing method is characterized in that patterning of various shapes is possible and flexible micro-supercapacitors can be manufactured using flexible substrates.

However, since the conventional manufacturing method as described above is a direct-write method in the form of automated scalpel engraving after deep coating, it is difficult to increase the area and it takes a lot of time to manufacture the micro supercapacitor.

In addition, it was dependent on the Scalpel machining technique, which resulted in low resolution. In particular, there was a problem in that the device efficiency was lowered to the level of 200 μm in the inter-electrode spacing of the manufactured micro supercapacitor.

Therefore, there is a need for a micro-supercapacitor manufacturing technology with a high capacity and a large area.

Automated Scalpel patterning of Solution Processed Thin Films for Fabrication of Transparent Mxene Microsupercapacitors. Thesis Journal: Small (2018, 1802864)

An object of the present invention to solve the above problems is a method of manufacturing a micro supercapacitor using a solution process for manufacturing a high-performance micro supercapacitor using a patterning method capable of high capacity and large area, and manufacturing method thereof It is to provide a micro-supercapacitor.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.

The configuration of the present invention for achieving the above object is a) preparing a maxin solution; b) coating a photoresist mask on the substrate; c) coating the maxin solution on the substrate coated with the photoresist mask; and d) obtaining a patterned maxine from the substrate to prepare a micro supercapacitor.

In an embodiment of the present invention, the step a) comprises: a1) obtaining a maxine; and a2) mixing the obtained maxine with distilled water to form a maxin solution.

In an embodiment of the present invention, the step a1) may be characterized in that the maxine is obtained by etching the MAX phase under LiF+HCL 6M conditions.

In an embodiment of the present invention, in step a2), the concentration of maxin may be 10-15 mg/ml.

In an embodiment of the present invention, in step b), the photoresist mask may be of a negative type.

In an embodiment of the present invention, in step b), the substrate may be a SiO ₂ substrate.

In an embodiment of the present invention, step c) may be characterized in that it is made by dip coating or spin coating.

In an embodiment of the present invention, the step d) comprises: d1) taking out the substrate from the maxin solution; d2) removing the photoresist mask from the removed substrate; and d3) manufacturing a micro-supercapacitor using the maxine patterned on the substrate.

In an embodiment of the present invention, in step d2), the photoresist mask may be removed by an acetone solvent in an ultrasonic cleaner.

The configuration of the present invention for achieving the above object is a micro supercapacitor manufactured by a method of manufacturing a micro supercapacitor using a solution process, wherein the micro supercapacitor has an electrode width and an inter-electrode spacing of 45 to 55 μm. There is provided a micro supercapacitor manufactured by a method for manufacturing a micro supercapacitor using a solution process, characterized in that it is formed.

According to the effect of the present invention according to the above configuration, it is possible to manufacture a micro supercapacitor by using an easy and simple solution process method, and mass production and large area of the micro supercapacitor are possible.

According to the present invention, high-resolution micrometer-level patterning is possible.

According to the present invention, there is no limitation on the type of substrate for the process, so it is easy to manufacture a capacitor through a flexible and continuous process.

According to the present invention, since all processes for manufacturing a capacitor are compatible with a semiconductor process, it can be used as a high-performance capacitor in an IC chip.

According to the present invention, a micro supercapacitor has an excellent volumetric capacity value, and has high energy density and high power density characteristics.

The effects of the present invention are not limited to the above effects, and it should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flowchart of a method of manufacturing a micro supercapacitor using a solution process according to an embodiment of the present invention.
2 is a process exemplary diagram of a method of manufacturing a micro supercapacitor using a solution process according to an embodiment of the present invention.
Figure 3 is a flowchart of a step of preparing a maxin solution according to an embodiment of the present invention.
Figure 4 is an exemplary view of the step of coating the maxin solution according to an embodiment of the present invention.
5 is a flowchart of steps of manufacturing a micro-supercapacitor according to an embodiment of the present invention.
6 is a photograph showing a patterned maxine formed on a wafer according to an embodiment of the present invention.
7 is an image illustrating a microcapacitor having a patterned maxine formed on a substrate according to an embodiment of the present invention.
8 is an exemplary view showing the shape of a patterned maxine according to an embodiment of the present invention.
9 is an SEM image of a micro supercapacitor according to an embodiment of the present invention.
10 is an AFM 3D image of a micro supercapacitor according to an embodiment of the present invention.
11 is a graph showing the thickness of the topography before the AFM image of the micro supercapacitor according to an embodiment of the present invention.
12 is a graph showing line profile data of a topography image of a micro supercapacitor according to an embodiment of the present invention.
13 is a graph showing characteristics of cyclic voltammetry of a micro supercapacitor according to an embodiment of the present invention.
14 is a graph showing a volumetric capacity value according to a scan speed of a micro supercapacitor according to an embodiment of the present invention.
15 is a graph showing EIS characteristics of a micro supercapacitor according to an embodiment of the present invention.
16 is a graph illustrating galvanostatic charge-discharge (GCD) characteristics of a micro supercapacitor according to an embodiment of the present invention.
17 is a graph showing characteristics of cycle stability of a micro supercapacitor according to an embodiment of the present invention.
18 is a graph showing energy density versus output density of a micro supercapacitor according to an embodiment of the present invention.
19 is a table comparing differences in electrochemical properties between a micro supercapacitor according to an embodiment of the present invention and a conventional example.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member interposed therebetween. "Including cases where In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a flowchart of a method of manufacturing a micro supercapacitor using a solution process according to an embodiment of the present invention, and FIG. 2 is a process illustration of a method of manufacturing a micro supercapacitor using a solution process according to an embodiment of the present invention to be.

1 and 2, in the method of manufacturing a micro supercapacitor using a solution process, a step (S10) of preparing a maxine solution may be performed first.

Figure 3 is a flowchart of a step of preparing a maxin solution according to an embodiment of the present invention.

Referring further to Figure 3, the step (S10) of preparing a maxine solution may first be a step (S11) of obtaining maxine.

In the step of obtaining maxine (S11), it is provided to synthesize MAX and MXene. As an example, the step of obtaining maxine (S11) may be prepared to obtain the maxine by etching the MAX phase under LiF (lithium fluoride) + HCL (hydrogen chloride) 6M (6 moles) conditions.

After the step (S11) of obtaining maxine, the step (S12) of forming a maxine solution by mixing the obtained maxine with distilled water may be performed.

In the step (S12) of mixing the obtained maxine with distilled water to form a maxine solution, the maxine solution may refer to a solution obtained by mixing the maxine with distilled water at a predetermined concentration.

For example, the concentration of the maxin in the maxin solution may be prepared to prepare the maxin solution by adding the distilled water so that 5-15 mg/ml.

After the step (S10) of preparing the maxin solution, the step of coating the photoresist mask on the substrate (S20) may be performed.

In the step of coating the photoresist mask on the substrate ( S20 ), the substrate 110 may be a SiO ₂ substrate. However, the type of the substrate is not limited thereto.

In addition, in the step of coating the photoresist mask on the substrate ( S20 ), the photoresist mask 120 may be provided in a negative shape.

More specifically, the photoresist mask 120 may have a width of 50 μm in a portion where the microelectrodes are formed, a gap between the grooves in a portion where the microelectrodes are formed to be 50 μm, and a thickness of 3.5 μm.

The above numerical values are the most preferred examples, and the numerical values thereof in the present invention are not limited to one embodiment. The present invention includes a groove having a width of 45 to 55 μm in a portion in which the microelectrodes are formed, a spacing between the grooves in a portion in which a microelectrode is formed, in a range of 45 to 55 μm, and a thickness of 3 to 5 μm. The shape of the grooved portion of the photoresist mask 120 corresponds to the shape of the patterned maxine 140 to be formed later, and a more specific shape thereof will be described later.

In the step of coating the photoresist mask on the substrate ( S20 ), the photoresist mask 120 may be coated on the substrate 110 thus prepared.

After the step of coating the photoresist mask on the substrate (S20), the step of coating the maxine solution on the substrate coated with the photoresist mask (S30) may be performed.

The step of coating the maxine solution on the photoresist mask-coated substrate (S30) may be performed by dip coating or spin coating.

During dip coating, it is prepared to perform coating at a speed of 0.95 to 1.05 μm/s, preferably at a speed of 1 μm/s, and during spin coating, coating is prepared under the conditions of 300 rpm to 1000 rpm, 100 seconds to 300 seconds. can

Figure 4 is an exemplary view of the step of coating the maxin solution according to an embodiment of the present invention.

For example, as shown in FIG. 4 , the substrate 110 coated with the photoresist mask 120 is placed in a water tank containing the maxin solution 130 and the maxine solution 130 is placed in an empty space within the photoresist mask 120 . This can be coated. Accordingly, the patterned maxine 140 corresponding to the shape of the photoresist mask 120 may be formed on the substrate 110 .

After the step (S30) of coating the maxine solution on the photoresist mask-coated substrate, a step (S40) of manufacturing a micro-supercapacitor by obtaining a patterned maxine from the substrate may be performed.

5 is a flowchart of the steps of manufacturing a micro-supercapacitor according to an embodiment of the present invention.

Referring to FIG. 5 , in the step ( S40 ) of manufacturing a micro supercapacitor by obtaining a patterned maxine from a substrate, first, a step ( S41 ) of taking out the substrate from the maxin solution may be performed.

In the step (S41) of taking out the substrate from the maxin solution, the substrate 110 coated with the maxin solution may be lifted from the maxin solution contained in the water tank and taken out.

After the step (S41) of taking out the substrate from the maxin solution, a step (S42) of removing the photoresist mask on the taken out substrate may be performed.

In the step (S42) of removing the photoresist mask from the removed substrate, the photoresist mask 120 is removed by acetone solvent while remaining in the ultrasonic cleaner for 30 seconds to 5 minutes after a baking process is performed at 120 degrees for 30 minutes. can be In this case, the baking process of the photoresist mask 120 may be performed within a range of 110 to 130 degrees and 25 to 35 minutes.

After removing the photoresist mask from the removed substrate ( S42 ), a step ( S43 ) of manufacturing a micro-supercapacitor by using the maxine patterned on the substrate may be performed.

6 is a photograph showing a patterned maxine formed on a wafer according to an embodiment of the present invention.

As shown in FIG. 6 , the patterned maxine 140 formed as described above may be formed in plurality on the wafer 150 .

7 is an image illustrating a microcapacitor having a patterned maxine formed on a substrate according to an embodiment of the present invention.

And, as shown in FIG. 7, when Dip coating or Spin coating is used using the SiO ₂ substrate patterned by photolithography, a uniform maxine film can be formed without being affected by the existing pattern, and can be microscaled. A patterned maxine 140 can be obtained.

8 is an exemplary view showing the shape of a patterned maxine according to an embodiment of the present invention.

8, the shape of the patterned maxine 140 manufactured according to the present invention will be described in detail.

The patterned maxine 140 includes a first body portion 141 , a second body portion 142 , a first extension portion 143 , a second extension portion 144 , a first electrode 145 and a second An electrode 146 may be included.

The first body part 141 and the second body part 142 may be spaced apart from both side surfaces of the substrate 110 at the same distance and may be formed to extend in a width direction of the substrate 110 .

In addition, the first body portion 141 and the second body portion 142 may be formed symmetrically with respect to the center line of the substrate 110 , and may be formed to be spaced apart from each other.

The first extension 143 may extend upwardly from the first body 141 , and the second extension 144 may extend upwardly from the second body 142 . have.

Here, the outer surfaces of the first extension part 143 and the second extension part 144 may be provided to be formed at points dividing the substrate into thirds. In addition, the first extension part 143 and the second extension part 144 may be formed to be spaced apart from each other to form a microelectrode between the first extension part 143 and the second extension part 144 . It may be provided so that a space is formed.

The first electrode 145 is formed to extend from the first extension part 143 toward the second extension part 144 , one end extending from the first extension part 143 , and the other end extending from the second extension part 143 . It may be formed to be spaced apart from the extension portion 144 .

The second electrode 146 is formed to extend from the second extension portion 144 toward the first extension portion 143 , one end extending from the second extension portion 144 , and the other end extending from the first extension portion 144 . It may be formed to be spaced apart from the extension part 143 .

The first electrode 145 and the second electrode 146 may be formed at regular intervals, and may be provided to be alternately arranged between the first extension part 143 and the second extension part 144 .

At this time, the gap between the first electrode 145 and the second electrode 146 and the width of the first electrode 145 and the second electrode 146 are 45 to 55 μm, and uniform spacing And it may be formed to have a width.

In addition, the first electrode 145 and the second electrode 146 may have a thickness of 3 to 5 μm, and may be formed to have a uniform thickness.

9 is an SEM image of a micro supercapacitor according to an embodiment of the present invention.

Referring to FIG. 9 , it can be seen that in the micro-supercapacitor prepared in this way, the spacing, width, etc. of the patterned maxine 140 are uniform.

10 is an AFM 3D image of a micro supercapacitor according to an embodiment of the present invention, and FIG. 11 is a graph showing the thickness of the topography before topography in the AFM image of the micro supercapacitor according to an embodiment of the present invention, FIG. is a graph showing line profile data of a topography image of a micro supercapacitor according to an embodiment of the present invention.

Referring to FIGS. 10 to 12 , the electrode of the patterned maxine 140 has a small area of 6 mm x 5 mm and a high aspect ratio by the width and inter-electrode spacing of the small electrodes uniformly formed on the micro scale. formation can be confirmed.

13 is a graph showing characteristics of cyclic voltammetry of a micro supercapacitor according to an embodiment of the present invention.

13, various scan rates (1, 2, 5, 10, 20, 50, 100, 200, 500, 1000, 2000, 5000, 10000 mV/s) for the micro supercapacitor manufactured by the present invention It can be seen that an ideal rectangular CV curve was shown at sruf and a relatively low scan rate (1-50 mV/s) by testing the CV characteristics.

14 is a graph showing a volumetric capacity value according to a scan speed of a micro supercapacitor according to an embodiment of the present invention.

Referring to FIG. 14, when the volumetric capacitance is calculated through the CV curve of the micro supercapacitor manufactured by the present invention, 1754.4, 1798.6, 1774.1, It showed stable volumetric capacity values of 1729.4, 1660.6, and 1519.8 F/cm ³ , and stable volumetric capacity values of 1353.4, 1101.0, 604.8 and 268.6 F/cm ³ at a fast scan speed (100~1,000 mV/s). . And, the volumetric capacity values of 101.6, 25.1, and 10.2 F/cm ³ were maintained even at very high scan rates (2,000 to 10,000 mV/s).

15 is a graph showing EIS characteristics of a micro supercapacitor according to an embodiment of the present invention.

Referring to FIG. 15 , the ESR (equivalent series resistance) of the micro supercapacitor manufactured by the present invention exhibited an internal resistance characteristic of a 279.1 Ω electrolyte. And, Rct (charge transfer resistance) means a semi-circle part, and showed resistance characteristics at the 538.8 Ω electrode/electrolyte interface. In addition, it can be seen that the low-frequency region is a part that is predominantly affected by ion diffusion, and exhibits capacitive behavior due to the influence of warburge impedance.

16 is a graph illustrating galvanostatic charge-discharge (GCD) characteristics of a micro supercapacitor according to an embodiment of the present invention.

Referring to FIG. 16 , GCD characteristics can be seen at various current densities (1.05, 2.11, 5.27, 10.5, 21.1, 52.7 A/cm ³ ). An isosceles triangle-shaped ideal GCD curve was exhibited, and there was almost no IR drop representing the resistive element. In addition, at each current density (1.05, 2.11, 5.27, 10.5, 21.1, 52.7 A/cm ³ ), it showed excellent volumetric capacity values of 1587.2, 1999.7, 1875.5, 1677.8, 1575.0, 1508.3 F/cm ³ , and fast It showed an excellent volumetric capacity value of 1508.3 F/cm ³ even at a rate of 52.7 A/cm ³ .

17 is a graph showing characteristics of cycle stability of a micro supercapacitor according to an embodiment of the present invention.

Referring to FIG. 17 , when cycle stability (GCD) was measured using a current density of 21.1A/cm ³ at a fast rate, the capacitance hardly fell even in repeated cycles of 2,000 cycles or more, and the initial It can be seen that the capacity is maintained at 72.4% or more compared to the value.

18 is a graph showing energy density versus output density of a micro supercapacitor according to an embodiment of the present invention.

Referring to FIG. 18 , compared with other Maxine micro supercapacitors, the micro supercapacitor manufactured by the present invention has a higher energy density of 38.5 mWh/cm ³ (0.62 W/cm ³ ) characteristics and a high power density of 27.3 W/ cm ³ (28.1 mWh/cm ³ ) showed characteristics.

19 is a table comparing differences in electrochemical properties between a micro supercapacitor according to an embodiment of the present invention and a conventional example.

Referring to FIG. 19 , it can be confirmed that Cv (volumetric capacitance), Ev (vol.

As such, the micro-supercapacitor manufactured according to the present invention described above can be manufactured using an easy and simple solution process method, and the micro-supercapacitor can be mass-produced and large-area.

In addition, according to the present invention, high-resolution micrometer-level patterning is possible, and there is no limitation on the type of substrate for the process, so it is easy to manufacture a capacitor through flexible and continuous processes.

And, according to the present invention, since all processes for manufacturing capacitors are compatible with semiconductor processes, they can be used as high-performance capacitors in IC chips, and micro-supercapacitors have excellent volumetric capacity values and are higher than in the prior art. It has energy density and high power density characteristics.

The foregoing description of the present invention is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and likewise components described as distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

110: substrate
120: photoresist mask
130: maxin solution
140: patterned maxine
141: first body portion
142: second body portion
143: first extension
144: second extension
145: first electrode
146: second electrode
150: wafer

Claims (10)

a) preparing a maxin solution;
b) coating a photoresist mask on the substrate;
c) coating the maxin solution on the substrate coated with the photoresist mask; and
d) obtaining a patterned maxine from the substrate to prepare a micro supercapacitor.
The method of claim 1,
Step a) is,
a1) obtaining a maxine; and
a2) mixing the obtained maxine with distilled water to form a maxine solution.
3. The method of claim 2,
Step a1) is,
A method of manufacturing a micro supercapacitor using a solution process, characterized in that the maxine is obtained by etching the MAX phase under LiF+HCL 6M conditions.
3. The method of claim 2,
In step a2),
The method of manufacturing a micro supercapacitor using a solution process, characterized in that the concentration of the maxin is 5 ~ 15 mg / ml.
The method of claim 1,
In step b),
The photoresist mask is a method of manufacturing a micro supercapacitor using a solution process, characterized in that the negative (negative) type.
The method of claim 1,
In step b),
The substrate is
A method of manufacturing a micro supercapacitor using a solution process, characterized in that it is a SiO ₂ substrate.
The method of claim 1,
Step c) is,
A method of manufacturing a micro supercapacitor using a solution process, characterized in that it is made by dip coating or spin coating.
The method of claim 1,
Step d) is,
d1) taking the substrate out of the maxin solution;
d2) removing the photoresist mask from the removed substrate; and
d3) A method of manufacturing a micro supercapacitor using a solution process, comprising the step of manufacturing a micro supercapacitor using a maxine patterned on the substrate.
9. The method of claim 8,
In step d2),
The photoresist mask is a method of manufacturing a micro supercapacitor using a solution process, characterized in that removed by an acetone solvent in an ultrasonic cleaner.
In the micro supercapacitor manufactured by the manufacturing method of the micro supercapacitor using the solution process according to claim 1,
The micro-supercapacitor is a micro-supercapacitor manufactured by a method of manufacturing a micro-supercapacitor using a solution process, characterized in that the electrode width and the inter-electrode spacing are formed to be 45 to 55 μm.

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