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WO2023038197A1 - Procédé de fabrication d'élément micro-supercondensateur flexible par transfert d'un motif d'électrode mxène à grande échelle - Google Patents

Procédé de fabrication d'élément micro-supercondensateur flexible par transfert d'un motif d'électrode mxène à grande échelle Download PDF

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Publication number
WO2023038197A1
WO2023038197A1 PCT/KR2021/016719 KR2021016719W WO2023038197A1 WO 2023038197 A1 WO2023038197 A1 WO 2023038197A1 KR 2021016719 W KR2021016719 W KR 2021016719W WO 2023038197 A1 WO2023038197 A1 WO 2023038197A1
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Prior art keywords
mxene
substrate
pattern
present
flexible
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English (en)
Korean (ko)
Inventor
이용희
송진규
김은지
안치원
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Korea Advanced Institute of Science and Technology KAIST
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Korea Advanced Institute of Science and Technology KAIST
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a method for manufacturing a flexible micro-supercapacitor device by transferring a large-area MXene electrode pattern, and more particularly, to a technique for manufacturing a high-performance micro-supercapacitor by utilizing a patterning method capable of high capacity and large area. It's about
  • Micro-supercapacitors have great potential to complement and replace conventional batteries and electrolytic capacitors due to their many advantages, such as fast charge/discharge rate, high power, and unlimited lifetime.
  • micro-supercapacitor manufacturing technology it is cumbersome to construct micro-scale electrodes in terms of cost-effectiveness, and wide application of micro-supercapacitors is impossible due to limitations in large-area fabrication. Accordingly, recently, supercapacitors using MXene showing excellent performance in energy storage devices due to high conductivity and excellent electrochemical properties have been developed.
  • a conventional micro-supercapacity was prepared by forming a MXene film on a glass or plastic substrate using a dip-coating method, and using a pattern using a physical scratching method as an electrode on the MXene film.
  • This manufacturing method is characterized in that it can be patterned in various shapes and can manufacture flexible micro-supercapacitors using flexible substrates.
  • the conventional manufacturing method as described above is a direct-write method in the form of automated scalpel engraving after dip coating, there is a problem in that it is difficult to large-area and takes a lot of time to manufacture a micro-supercapacitor.
  • it is dependent on the scalpel machining technique, resulting in low resolution.
  • the device efficiency was lowered as the interelectrode spacing of the manufactured micro-supercapacitor was about 200 ⁇ m. Therefore, there is a need for a micro-supercapacitor manufacturing technology that is easy to have a high capacity and a large area.
  • Non-Patent Document 1 Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage (Nature communications (2013, 4;1475))
  • An object of the present invention to solve the above problems is to provide a micro-supercapacitor manufacturing method 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 manufacturing method thereof. To provide a manufactured micro-supercapacitor.
  • the configuration of the present invention for achieving the above object is a first step of preparing a MXene solution; A second step of coating a photoresist mask on the substrate; a third step of coating the MXene solution on the photoresist mask; a fourth step of removing the photoresist mask from the substrate to form a MXene pattern that is patterned MXene on the substrate; a fifth step of coating a synthetic resin solution on the substrate on which the MXene pattern is formed and then heating it to form a film; and a sixth step of separating the film and the MXene pattern by removing the substrate to form a flexible element that is a combination of the film and the MXene pattern.
  • the synthetic resin solution is a polyimide solution
  • the film may be formed of polyimide
  • primary heating may be performed at a temperature of 50 to 100 degrees (° C.) on the coating layer formed by coating the polyimide solution on the substrate.
  • the coating layer is imidized by performing secondary heating at a temperature of 250 to 350 degrees (° C.) on the primary heated coating layer to imidize the film. can form.
  • the coating of the polyimide solution on the substrate may be performed by dip coating or spin coating.
  • the substrate may be a SiO 2 layer formed on a silicon wafer.
  • the substrate in the sixth step, may be removed by hydrogen fluoride (HF) etching.
  • HF hydrogen fluoride
  • the photoresist mask in the fourth step, may be removed by using an acetone solvent in an ultrasonic cleaner.
  • MAXene in the first step, may be obtained by etching the MAX phase under LiF+HCL 6M conditions.
  • the thickness of the film may be 0.1 to 5 micrometers ( ⁇ m).
  • a plurality of flexible elements may be connected in series or parallel.
  • micro-supercapacitor can be manufactured using an easy and simple solution process method, and mass-production and large-area micro-supercapacitors are possible.
  • the effect of the present invention is that it is possible to provide a microsupercapacitor that can be applied to various applications in which the shape is deformed, such as a roll-up display and a wearable device, by forming a patterned MXene on the surface of a film of a flexible material.
  • FIG. 1 is a schematic diagram of a process for forming MXene patterns according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram of a process for coating MXene solution according to an embodiment of the present invention.
  • FIG 3 is an image of a MXene pattern on a wafer according to an embodiment of the present invention.
  • FIG. 5 is an image showing the shape of a MXene pattern according to an embodiment of the present invention.
  • FIG. 6 is a SEM image of MXene patterns according to an embodiment of the present invention.
  • FIG. 7 is a schematic diagram of formation of MXene patterns on a substrate according to an embodiment of the present invention.
  • FIG. 8 is a schematic diagram of the formation of a film according to an embodiment of the present invention.
  • FIG. 9 is a schematic diagram of an etching process according to an embodiment of the present invention.
  • FIG. 10 is a schematic diagram of formation of a flexible element according to an embodiment of the present invention.
  • 11 and 12 are images of a flexible element according to an embodiment of the present invention.
  • FIG. 13 is a CV curve graph for each of a substrate having a MXene pattern and a flexible device according to an embodiment of the present invention.
  • FIG. 14 is a graph showing volumetric capacitance values according to scan speeds of a substrate having a MXene pattern and a flexible element according to an embodiment of the present invention.
  • GCD Galvanostatic charge-discharge
  • 17 is an image of bending of a flexible element according to an embodiment of the present invention.
  • 19 is a graph showing volumetric capacity values according to bending degrees of a flexible element according to an embodiment of the present invention.
  • 20 to 25 are graphs showing cyclic voltammetry characteristics according to the degree of bending of a flexible element according to an embodiment of the present invention.
  • 26 is a graph showing volumetric capacity values according to bending degrees of a flexible element according to an embodiment of the present invention.
  • FIG. 27 is a CV curve graph according to the number of bending times of a flexible element according to an embodiment of the present invention.
  • 29 is a CV curve graph according to the number of charge/discharge cycles of a flexible device according to an embodiment of the present invention.
  • FIG. 30 is a graph of a capacitance retention rate according to the number of charge/discharge cycles of a flexible device according to an embodiment of the present invention.
  • 31 is a CV curve graph according to whether flexible elements are connected in series or in parallel according to an embodiment of the present invention.
  • GCD Galvanostatic charge-discharge
  • GCD Galvanostatic charge-discharge
  • GCD 34 is a graph showing Galvanostatic charge-discharge (GCD) characteristics according to whether flexible devices are connected in series according to an embodiment of the present invention.
  • 35 is a graph of capacitance change according to the number of parallel connections of flexible elements according to an embodiment of the present invention.
  • 39 is a table summarizing materials and properties of flexible devices and other comparative devices according to an embodiment of the present invention.
  • the first step of preparing a MXene solution A second step of coating a photoresist mask on the substrate; a third step of coating the MXene solution on the photoresist mask; a fourth step of removing the photoresist mask from the substrate to form a MXene pattern that is patterned MXene on the substrate; a fifth step of coating a synthetic resin solution on the substrate on which the MXene pattern is formed and then heating it to form a film; and a sixth step of separating the film and the MXene pattern by removing the substrate to form a flexible element that is a combination of the film and the MXene pattern.
  • FIG. 1 is a schematic diagram of a process for forming MXene patterns 140 according to an embodiment of the present invention
  • FIG. 2 is a schematic diagram of a process of coating MXene solution 130 according to an embodiment of the present invention. .
  • FIG. 3 is an image of a MXene pattern 140 on a wafer 150 according to an embodiment of the present invention
  • FIG. 4 is an image of a MXene pattern 140 according to an embodiment of the present invention
  • 5 is an image showing the shape of the MXene pattern 140 according to an embodiment of the present invention
  • FIG. 6 is a SEM image of MXene pattern 140 according to an embodiment of the present invention.
  • FIG. 7 is a schematic diagram of the formation of the MXene pattern 140 on the substrate 110 according to an embodiment of the present invention
  • FIG. 8 is a schematic diagram of the formation of the film 160 according to an embodiment of the present invention.
  • 9 is a schematic diagram of an etching process according to an embodiment of the present invention.
  • Figure 10 is a schematic diagram of the formation of the flexible element 10 according to an embodiment of the present invention.
  • (a) of FIG. 6 is for a case where the resolution is 500 micrometers ( ⁇ m)
  • (b) of FIG. 6 is for a case where the resolution is 100 micrometers ( ⁇ m)
  • (c) of FIG. is for the case where the resolution is 10 micrometers ( ⁇ m).
  • FIG. 7 (a) is a plan view of the wafer 150 on which a plurality of MXene patterns 140 are formed
  • FIG. 7 (b) is a perspective view of the wafer 150 on which a plurality of MXene patterns 140 are formed.
  • FIG. 8(a) is a plan view of a wafer 150 and a film 160 assembly on which a plurality of MXene patterns 140 are formed
  • FIG. 8(b) is a wafer on which a plurality of MXene patterns 140 are formed ( 150) and the film 160 is a perspective view of the assembly.
  • FIG. 10(a) relates to the separation of the film 160 and MXene pattern 140 from the substrate 110 by removing the substrate 110, and FIG. 10(b) shows the flexible element 10 It is about the matters formed.
  • a first step of preparing MXene solution 130 may be performed.
  • the first step may include a 1-1 step of obtaining MXene and a 1-2 step of forming MXene solution 130 by mixing the obtained MXene with distilled water.
  • step 1-1 it may be prepared to synthesize MAX and MXene.
  • MAXene may be obtained by etching the MAX phase under LiF+HCL 6M conditions.
  • the obtained MXene is mixed with distilled water
  • the MXene solution 130 may refer to a solution obtained by mixing distilled water with a predetermined concentration.
  • the MXene solution 130 may be prepared by adding distilled water so that the MXene concentration in the MXene solution 130 is 5-15 mg/ml.
  • the substrate 110 may be a SiO 2 layer formed on a silicon wafer (Si wafer).
  • the type of substrate 110 is not limited thereto.
  • the SiO 2 layer may be formed by oxidizing the surface of a silicon wafer (Si wafer), and each process related to the substrate 110 below is for the SiO 2 layer on the wafer 150 and is a process using the wafer 150.
  • Si wafer silicon wafer
  • the substrate 110 SiO 2 layer
  • the photoresist mask 120 may be of a negative type. More specifically, the photoresist mask 120 has a width of 50 micrometers ( ⁇ m) at the perforated portion where the microelectrodes are formed, The thickness may be formed to be 3.5 micrometers ( ⁇ m).
  • the width of the perforated part of the part where the microelectrode is formed is 45 to 55 micrometers ( ⁇ m)
  • the interval between the perforated parts of the part where the microelectrode is formed is 45 to 55 micrometer ( ⁇ m)
  • the thickness is 3 to 5 It includes micrometers ( ⁇ m).
  • the shape of the perforated portion of the photoresist mask 120 corresponds to the shape of the MXene pattern 140 to be formed later, and its more specific shape will be described later.
  • a third step of coating the MXene solution 130 on the photoresist mask 120 may be performed.
  • dip coating or spin coating may be performed to coat the MXene solution 130 on the substrate 110 coated with the photoresist mask 120 .
  • Dip coating is provided to perform coating at a speed of 0.95 to 1.05 ⁇ m/s, preferably 1 ⁇ m/s, and during spin coating, coating is performed under conditions of 300 rpm to 1,000 rpm and 100 to 300 seconds. It can be.
  • the substrate 110 coated with the photoresist mask 120 is supported in a water tank containing the MXene solution, and the MXene solution 130 is formed in the empty space within the photoresist mask 120. can be coated. Accordingly, the MXene solution 130 may be coated on the substrate 110 in a pattern corresponding to the shape of the photoresist mask 120 .
  • a fourth step may be performed in which the photoresist mask 120 is removed from the substrate 110 to form the MXene pattern 140 , which is a patterned MXene on the substrate 110 .
  • the photoresist mask 120 may be removed by an acetone solvent while staying in an ultrasonic cleaner for 30 seconds to 5 minutes after a baking process is performed at 120 degrees for 30 minutes.
  • the baking process of the photoresist mask 120 may be performed within a range of 110 to 130 degrees and 25 to 35 minutes.
  • distilled water is evaporated from the MXene solution 130 coated in a predetermined pattern by the baking process as described above, and thus, the MXene pattern 140, which is a patterned MXene, can be formed on the substrate 110.
  • a plurality of MXene patterns 140 may be formed on the substrate 110, that is, a plurality may be manufactured using one wafer 150, and as such, a plurality of MXene patterns may be formed on a large area. Since the MXene pattern 140 can be formed, manufacturing efficiency can be remarkably increased.
  • the MXene pattern 140 includes a first body 141, a second body 142, a first extension 143, a second extension 144, a first electrode 145, and a second electrode 146. ) may be included.
  • the first body portion 141 and the second body portion 142 are spaced apart from both side surfaces of the substrate 110 at equal intervals and may extend long in the width direction of the substrate 110 .
  • 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 spaced apart from each other.
  • the first extension part 143 may extend upward from the first body part 141
  • the second extension part 144 may extend upward from the second body part 142 .
  • outer surfaces of the first extension part 143 and the second extension part 144 may be provided to be formed at a point dividing the substrate 110 into thirds.
  • the first extension 143 and the second extension 144 are spaced apart from each other to form a space in which a microelectrode can be formed between the first extension 143 and the second extension 144. can be arranged so that
  • the first electrode 145 extends from the first extension 143 toward the second extension 144, one end extending with the first extension 143, and the other end extending with the second extension 144. It can be formed spaced apart from.
  • the second electrode 146 extends from the second extension part 144 toward the first extension part 143, one end extends with the second extension part 144, and the other end extends with the first extension part 143. It can be formed spaced apart from.
  • the first electrode 145 and the second electrode 146 are formed at regular intervals, and may be arranged to cross each other between the first extension part 143 and the second extension part 144 . At this time, the interval between the first electrode 145 and the second electrode 146 and the width of the first electrode 145 and the second electrode 146 are formed to be 45 to 55 ⁇ m, but a uniform interval and width can be formed to have In addition, the first electrode 145 and the second electrode 146 may have a thickness of 3 to 5 ⁇ m and may be formed with a uniform thickness.
  • a fifth step of forming a film 160 by coating a synthetic resin solution on the substrate 110 on which the MXene pattern 140 is formed is performed, and then heated. It can be.
  • the synthetic resin solution is a polyimide solution
  • the film 160 may be formed of polyimide.
  • the material of the film 160 is formed as described above, but it is not limited thereto, and other synthetic resin materials other than polyimide may be used.
  • coating of the polyimide solution on the substrate 110 may be performed by dip coating or spin coating.
  • Dip coating is provided to perform coating at a speed of 0.95 to 1.05 ⁇ m/s, preferably 1 ⁇ m/s, and during spin coating, coating is performed under conditions of 1,500 rpm to 2,500 rpm, 20 seconds to 70 seconds It can be.
  • spin coating may be performed for coating the polyimide solution, and spin coating may be performed at a speed of 2,000 rpm for 50 seconds.
  • the polyimide solution can be uniformly coated on the substrate 110 on which the MXene pattern 140 is formed by the coating, and thus the surface of the film 160 and the MXene pattern 140 are formed. ) can be increased while the binding force is uniform.
  • the coating layer formed by coating the substrate 110 with the polyimide solution may be subjected to primary heating at a temperature of 50 to 100 degrees (°C). And, in the fifth step, by performing secondary heating at a temperature of 250 to 350 degrees (° C.) on the primary heated coating layer, the coating layer may be imidized to form a film 160 .
  • the primary heating as described above is heating performed toward the film 160 from the ambient of the film 160, and may be performed for 20 to 40 minutes (min).
  • the first heating soft-baking
  • the first heating may be performed at a temperature of 80 degrees (° C.) for 30 minutes (min).
  • the polyimide coating layer on the substrate 110 may be bonded to the substrate 110 and the MXene pattern 140 by the primary heating as described above, and the polyimide coating layer may form the shape of the film 160 by the primary heating. It is cured to form a film 160.
  • secondary heating may be performed to perform imidation annealing on the film 160, and secondary heating may be performed for 50 to 130 degrees min in the above temperature range.
  • the same secondary heating may be performed under an inert gas atmosphere such as argon (Ar) gas in a furnace.
  • the thickness of the film 160 may be 0.1 to 5 micrometers ( ⁇ m). By forming the film 160 to such a thickness, a flexible and thin film 160 having elasticity may be formed. As a result, the flexible element 10, which is the film 160 having the MXene pattern 140, can be used for roll-up displays, e-paper, smart sensors, transparent RFID, wearable devices, etc. Efficiency in large-area applications can be increased.
  • the substrate 110 is removed to separate the film 160 and the MXene pattern 140 to form the flexible element 10, which is a combination of the film 160 and the MXene pattern 140.
  • a sixth step may be performed.
  • the substrate 110 may be removed by hydrogen fluoride (HF) etching. That is, the flexible element 10, which is the film 160 having the MXene pattern 140, may be delaminated from the substrate 110.
  • HF hydrogen fluoride
  • Hydrogen fluoride (HF) etching can be performed by immersing the combination of the substrate 110 and the film 160 on which the MXene pattern 140 is formed in a water tank in which hydrogen fluoride (HF) at a concentration of 49% is stored. At this time, The etching time may be performed for 3 to 7 minutes (min), preferably, it may be performed for 5 minutes (min).
  • the MXene pattern 140 is transferred to the film 160 and is used as a flexible micro-supercapacitor.
  • Device 10 can be obtained.
  • the substrate 110 on which the MXene pattern 140 is formed can also be used as a micro-supercapacitor, but the flexible element 10 formed as described above is easily attached to a surface having elasticity due to its high flexibility and elasticity. Elastic shape deformation (bending, twisting, rolling, etc.) is possible to correspond to the deformation of the surface having a surface.
  • a plurality of flexible devices 10 may be connected in series or parallel. Even when one flexible element 10 and another flexible element 10 are connected, the same process as described above may be performed.
  • each pattern is formed on a film 160 as described above.
  • a film 160 as described above.
  • each flexible element 10 is not limited to the above method, and it is natural that each flexible element 10 can be connected using a metal nano wire or the like.
  • connection method of each flexible element 10 is not limited to the above method, and it is natural that each flexible element 10 can be connected using a metal nano wire or the like.
  • FIG. 11 and 12 are images of the flexible element 10 according to an embodiment of the present invention.
  • (a) of FIG. 11 is an image of one flexible element 10
  • (b) of FIG. 11 is an image of the flexible element 10 attached to the back of a person's hand.
  • FIG. 12 (a) is an image of the matter of deforming the flexible element 10 attached to the back of a person's hand
  • FIG. 12 (b) is an image of the rolled flexible element 10.
  • the flexible element 10 of the present invention is in the form of a thin film 160 formed of synthetic resin, and is not only free to deform, but also has an electrode pattern, that is, a MXene pattern 140 even when wound or bent. ) is prevented, and the performance is maintained even when attached to a flexible surface.
  • graph a is for the substrate 110 (including the wafer 150, the same below) on which the MXene pattern 140 is formed
  • graph b is for the flexible element 10 of the present invention.
  • both the substrate 110 on which the MXene pattern 140 is formed and the flexible device 10 show ideal rectangular CV curves at a scan rate of 10 mV/s and similar graph patterns. And, a performance improvement of about 20% was shown at a scan rate of 10 mV/s. (substrate 110 on which MXene pattern 140 is formed: 1218.2 F/cm 3 , flexible device 10: 1472.7 F/cm 3 )
  • HF hydrogen fluoride
  • volumetric capacitance values according to scan speeds of the substrate 110 having the MXene pattern 140 and the flexible device 10 according to an embodiment of the present invention.
  • the MXene pattern 140 which is a graph of square dots, shows values at each scan speed.
  • the flexibility of the present invention is generally compared to the substrate 110 on which the MXene pattern 140 is formed. It can be seen that the capacitance of the element 10 is increased.
  • FIG. 15 and 16 are graphs showing respective galvanostatic charge-discharge (GCD) characteristics of the substrate 110 having the MXene pattern 140 and the flexible device 10 according to an embodiment of the present invention.
  • a graph in FIG. 15 and a square dot graph in FIG. 16 are graphs for the substrate 110 having MXene patterns 140
  • graph b in FIG. 15 and a circular dot graph in FIG. 16 are for the flexible element 10.
  • it's a graph 15 and 16 it can be confirmed that the capacitance of the flexible device 10 of the present invention is increased compared to the substrate 110 on which the MXene pattern 140 is formed. Specifically, at a scan rate of 10 mV/s, about It showed a performance improvement of 12%.
  • substrate 110 on which MXene pattern 140 is formed 1275.7 F/cm 3
  • flexible element 10 1436.4 F/cm 3
  • FIG. 17 is an image of bending of the flexible element 10 according to an embodiment of the present invention.
  • FIG. 17 (a) is an image of a state in which the flexible element 10 is maintained in an unfolded state
  • (b) in FIG. 17 is an image in which the flexible element 10 is bent (radius: 5.27 mm). ) is an image of the items kept.
  • FIG. 18 is a CV curve graph according to a degree of bending of the flexible element 10 according to an embodiment of the present invention.
  • FIG. 19 is a graph showing the volumetric capacity value according to the degree of bending of the flexible element 10 according to an embodiment of the present invention.
  • 20 to 25 are graphs showing cyclic voltammetry characteristics according to the degree of bending of the flexible element 10 according to an embodiment of the present invention.
  • Each graph shows CV characteristics at various scan speeds (10, 20, 50, 100, 200, 500, 1000, 2000, 5000, 10000 mV/s) according to the degree of bending of the flexible element 10. This is the result.
  • FIG. 26 is a graph showing the volumetric capacity value according to the degree of bending of the flexible element 10 according to an embodiment of the present invention.
  • graphs according to the degree of bending of the flexible element 10 are classified in a dot shape of the graph.
  • FIG. 20 is a graph of the flexible element 10 in a flat state
  • FIG. 21 is a graph of the flexible element 10 bent to a radius of 3.87 mm
  • FIG. 22 is a graph of the flexible element 10 bent to a radius of 4.25 mm ( 10)
  • FIG. 23 is a graph of the flexible element 10 bent to a radius of 5.27 mm
  • 24 is a graph of the flexible element 10 bent to a radius of 5.27 mm
  • FIG. 25 is a graph of the flexible element 10 bent to a radius of 5.27 mm.
  • each graph shows a similar shape even when the shape of the flexible element 10 is deformed. Therefore, it can be confirmed that the performance of the flexible element 10 is maintained even if the flexible element 10 of the present invention is bent, and thus, damage to the MXene pattern 140 is prevented even when the shape is deformed, and the It can be confirmed that the micro-supercapacitor function is implemented.
  • FIG. 27 is a CV curve graph according to the number of times of bending of the flexible element 10 according to an embodiment of the present invention.
  • graphs for the results of testing the CV characteristics of the flexible element 10 at a scan rate of 50 mV/s are shown, and each graph is a graph according to the number of times of bending (200, 500, and 1000 times).
  • FIG. 28 is a graph of the capacitance retention rate according to the number of times of bending of the flexible element 10 according to an embodiment of the present invention.
  • the bending radius of the flexible element 10 is set to 5.27 mm.
  • 29 is a CV curve graph according to the number of charge/discharge cycles of the flexible element 10 according to an embodiment of the present invention.
  • graphs are shown for the results of testing the CV characteristics of the flexible element 10 at a scan rate of 50 mV/s, and each graph shows the number of charge/discharge cycles (1, 10, 50, 100, 5000, 1000 times).
  • 30 is a graph of the capacitance retention rate according to the number of charge/discharge cycles of the flexible element 10 according to an embodiment of the present invention.
  • the bending radius of the flexible element 10 is set to 5.27 mm.
  • 31 is a CV curve graph according to whether flexible elements 10 are connected in series or in parallel according to an embodiment of the present invention. Here, it is the result of an experiment at a scan rate of 10 mv/s for the flexible element 10 or the flexible element 10 connection body according to each connection method.
  • the single graph shows the CV curve for a single flexible element 10
  • the 4-Series (4S) graph shows the CV curve for a connection body connecting four flexible elements 10 in series.
  • 4-Parallel (4P) graph may indicate a CV curve for a connection body in which four flexible elements 10 are connected in parallel.
  • the 2-Series-2-Parallel (2S2P) graph may represent a CV curve for a connection body in which two flexible elements 10 are serially connected unit connectors connected in parallel.
  • a required voltage may be implemented using a series connection of the flexible devices 10 and a required capacitance may be implemented using a parallel connection of the flexible devices 10 .
  • the output voltage is increased four times from 0.6V to 2.4V by the 4-series connection of the flexible element 10 .
  • the 4-parallel connection of the flexible element 10 the output current is improved, and it can be confirmed that the capacity is linearly increased by about 4 times.
  • FIG. 32 is a graph showing Galvanostatic charge-discharge (GCD) characteristics according to whether flexible devices 10 are connected in series or parallel according to an embodiment of the present invention
  • FIG. 33 is a graph showing a flexible device according to an embodiment of the present invention
  • 34 is a graph showing the characteristics of Galvanostatic charge-discharge (GCD) according to whether or not (10) is connected in parallel
  • FIG. ) is a graph showing the characteristics.
  • FIG. 35 is a graph of capacitance change according to the number of parallel connections of flexible devices 10 according to an embodiment of the present invention
  • FIG. 36 is a series or parallel of flexible devices 10 according to an embodiment of the present invention. This is a CV curve graph depending on whether or not it is connected. In the experiment related to FIG. 36, the CV characteristics were tested by setting the scan rate to 10 mV/s for each connector.
  • the capacity of the flexible element 10 connected body tends to increase linearly. That is, it can be confirmed that the output current shows a linear increase along with the increase in the number of (parallel) parallel connections.
  • FIG. 37 is a CV curve graph when a plurality of flexible elements 10 are connected in parallel according to an embodiment of the present invention
  • FIG. 38 is a graph showing a plurality of flexible elements 10 connected in parallel according to an embodiment of the present invention. In this case, it is a graph showing capacitance change according to scan speed.
  • FIG. 37 and 38 are graphs of CV characteristics and capacitance in the case of forming a 12-connected body in which 12 flexible elements 10 are connected in parallel. And, in FIG. 37, each graph was tested for CV characteristics at various scan rates (10, 20, 50, 100, 200, 500, 1000, 2000, 5000, 10000 mV/s) for the above-described 12-connected body. is a result In addition, in FIG. 38, the capacitance change was measured while the scan rate was changed from 10 mV/s to 10,000 mV/s, and the capacitance change was 11.7, 11.6, 11.0, 10.1, 8.6, 5.6, 3.0, 1.3, 0.18, 0.16 mF.
  • the method of manufacturing the flexible element 10 of the present invention which is a micro-supercapacitor, by the above process does not require an additional process for producing ink, and compared to the inkjet printing and laser methods, the size is 50 ⁇ m or less. It may be possible to implement a fine pattern of
  • the transfer method using HF etching has a limitation that the target material is limited due to HF (strong acid). can be suitable as In particular, as shown above, it can be confirmed that the effect of improving the characteristics of the MXene pattern 140 (MXene thin film) after transfer is realized.
  • HF strong acid
  • the problem of mass production due to the slow process speed, which is a limitation of laser printing, and the problem of additional process/additive and line width limitation for ink production, which is a limitation of inkjet printing, are solved. can be solved at the same time.
  • the characteristics of the fabricated flexible device 10 (Mxene microsupercapacitor device) have a very excellent advantage.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Abstract

Un mode de réalisation de la présente invention est un micro-supercondensateur haute performance utilisant un procédé de formation de motifs à haute capacité et à grande échelle. Selon un mode de réalisation de la présente invention, un procédé de fabrication d'un élément micro-supercondensateur flexible par transfert d'un motif d'électrode Mxene à grande échelle comprend : une première étape de préparation d'une solution de Mxene ; une deuxième étape consistant à appliquer un masque de résine photosensible sur un substrat ; une troisième étape d'application de la solution de Mxene sur le masque de résine photosensible ; une quatrième étape consistant à retirer le masque de résine photosensible du substrat de manière à former, sur le substrat, un motif de Mxene, qui est un Mxene à motifs ; une cinquième étape consistant à appliquer une solution de résine synthétique sur le substrat ayant le motif de Mxene formé sur celui-ci, puis à chauffer celle-ci pour former un film ; et une sixième étape consistant à retirer le substrat de manière à séparer le film du motif de Mxene, formant ainsi un élément flexible, qui est une combinaison du film et du motif de Mxene.
PCT/KR2021/016719 2021-09-08 2021-11-16 Procédé de fabrication d'élément micro-supercondensateur flexible par transfert d'un motif d'électrode mxène à grande échelle Ceased WO2023038197A1 (fr)

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KR20250118571A (ko) 2024-01-30 2025-08-06 한양대학교 에리카산학협력단 마이크로슈퍼캐패시터 구조 및 제작방법

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