METAL DEPOSITION-BASED STRECHABLE ELECTRODE USING ELECTROSPUN MAT AND MANUFACTURING METHOD THEREFOR
20230043933 · 2023-02-09
Inventors
Cpc classification
D01D5/003
TEXTILES; PAPER
H01B13/0026
ELECTRICITY
D01D5/0038
TEXTILES; PAPER
H01B5/16
ELECTRICITY
H01B5/14
ELECTRICITY
D01F6/42
TEXTILES; PAPER
International classification
H01B5/14
ELECTRICITY
H01B13/00
ELECTRICITY
Abstract
A metal deposition-based stretchable electrode using an electrospun mat and a manufacturing method therefor are disclosed. The stretchable electrode is a stretchable electrode comprising a conductive mat, wherein the conductive mat comprises: nanofibers including a polymer; and a conductive layer formed on the surface of the nanofibers and including a conductor. The stretchable electrode has air/fluid permeability and may have conductivity that exhibits a stable change even in a biaxial deformation environment.
Claims
1. A stretchable electrode comprising a conductive mat, wherein the conductive mat comprises: nanofibers comprising a polymer; and a conductive layer formed on surfaces of the nanofibers and comprising a conductor.
2. The stretchable electrode of claim 1, further comprising a base mat on the conductive mat, wherein the base mat comprises nanofibers comprising a polymer.
3. The stretchable electrode of claim 1 or 2, wherein the conductive mat and the base mat each independently further comprises a polyalkyleneimine obtained by crosslinking the polymer.
4. The stretchable electrode of claim 3, wherein the crosslinking each independently comprises at least one selected from a group consisting of inter-crosslinking which crosslinks surfaces of nanofibers with each other and intra-crosslinking which crosslinks the polymer within a single nanofiber.
5. The stretchable electrode of claim 3, wherein the conductive mat and the base mat are bonded, and the bonding is by at least one selected from a group consisting of sharing of a part of the polymer of the conductive mat and a part of the polymer of the base mat, and crosslinking between the polymer of the conductive mat and the polymer of the base mat.
6. The stretchable electrode of claim 3, wherein the polyalkyleneimines are the same or different from each other, and each independently comprises at least one selected from a group consisting of linear polyalkyleneimine, comb polyalkyleneimine, branched polyalkyleneimine, and dendrimer polyalkyleneimine.
7. The stretchable electrode of claim 3, wherein the polyalkyleneimines are the same or different from each other, and each independently comprises at least one selected from a group consisting of polyethyleneimine and polypropyleneimine.
8. The stretchable electrode of claim 2, wherein the polymer is an elastic body.
9. The stretchable electrode of claim 7, wherein the polymers are the same or different from each other, and each independently comprises at least one selected from a group consisting of styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene block copolymer (SBR), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-methyl methacrylate copolymer (PSMMA), styrene-acrylonitrile copolymer (PSAN), polyurethane, silicone rubber, and butadiene rubber.
10. The stretchable electrode of claim 9, wherein the polymer further comprises an organic acid anhydride grafted to a main chain.
11. The stretchable electrode of claim 10, wherein the organic acid anhydride comprises at least one selected from a group consisting of maleic anhydride, succinic anhydride, acetic anhydride, Naphthalenetetracarboxylic dianhydride, and ethanoic anhydride.
12. The stretchable electrode of claim 1, wherein the conductor comprises at least one selected from a group consisting of gold, silver, copper, platinum palladium, nickel, indium, aluminum, iron, rhodium, ruthenium, osmium, cobalt, molybdenum, zinc, vanadium, tungsten, titanium, manganese, chromium, graphene, and carbon nano tube (CNT).
13. The stretchable electrode of claim 1, wherein a thickness of the conductive mat is 0.01 to 100 μm, and a thickness of the base mat is 0.1 to 1000 μm.
14. The stretchable electrode of claim 2, wherein each of the conductive mat and the base mat is porous.
15. A method of manufacturing a stretchable electrode, the method comprising: (a) preparing a porous mat comprising a polymer crosslinked with a polyalkyleneimine by supporting, swelling, and crosslinking a porous mat comprising nanofibers comprising a polymer in a polyalkyleneimine solution; and (b) depositing a conductor to a predetermined depth of the porous mat to form a conductive layer on surfaces of nanofibers.
16. The method of claim 15, further comprising: prior to (a), (a′) electrospinning a polymer solution comprising the polymer to prepare the porous mat comprising the nanofibers.
17. The method of claim 16, wherein the polymer solution further comprises at least one selected from a group consisting of an aprotic polar solvent and a non-polar solvent.
18. The method of claim 15, wherein the polyalkyleneimine solution further comprises a protic polar solvent.
19. The method of claim 15, wherein the predetermined depth is controlled by adjusting a deposition time.
20. A stretchable electronic device comprising the stretchable electrode of claim 1.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0032] Since the drawings are for reference in describing exemplary embodiments, the technical spirit of the present disclosure should not be construed as limited to the accompanying drawings.
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BEST MODE FOR CARRYING OUT THE INVENTION
[0057] Hereinafter, example embodiments will be described in detail with reference to the accompanying drawings for those of ordinary skill in the art to easily carry out.
[0058] However, it should be understood that these example embodiments are not construed as limited to the illustrated forms, and when it is determined that a detailed description of a related art may obscure the gist of the present disclosure in describing example embodiments, the detailed description will be omitted.
[0059] The terminology used herein is for the purpose of describing particular example embodiments only and is not to be limiting of the example embodiments. The singular forms herein include plural forms unless the context clearly dictates the singular. As used herein, it should be understood that the terms such as “comprise”, “have”, etc. are intended to indicate the presence of features, steps, operations, components, or combinations thereof, and not to exclude the possibility of the presence of features, steps, operations, components, or combinations thereof.
[0060] In addition, although terms of “first,” “second,” and the like are used to explain various components, the components are not limited to such terms. These terms are used only to distinguish one component from another component. For example, a first component may be referred to as a second component, or similarly, the second component may be referred to as the first component within the scope of the present disclosure.
[0061] In addition, when it is mentioned that one component is “formed” or “stacked” on another component, it may be understood that the one component may be formed or stacked by being directly attached to the front surface or one surface on the surface of another component, still other component may be present therebetween.
[0062] Hereinafter, a metal deposition-based stretchable electrode using the electrospinning mat and a method of manufacturing the same according to example embodiments will be described in detail. However, it should be understood that these example embodiments are not construed as limited to the illustrated forms, and the scope of the disclosure is defined by the scope of the claims below.
[0063] According to an example embodiment, there is provided a stretchable electrode including a conductive mat, wherein the conductive mat includes nanofibers including a polymer, and a conductive layer formed on surfaces of the nanofibers and including a conductor.
[0064] Further, the stretchable electrode may further include a base mat on the conductive mat, and the base mat may include nanofibers including a polymer.
[0065] Further, the conductive mat and the base mat may each independently further include a polyalkyleneimine obtained by crosslinking the polymer.
[0066] Further, the crosslinking may each independently include at least one selected form a group consisting of inter-crosslinking which crosslinks surfaces of nanofibers with each other and intra-crosslinking which crosslinks the polymer within a single nanofiber.
[0067] Further, the conductive mat and the base mat may be bonded, wherein the bonding may be by at least one selected from a group consisting of sharing of a part of the polymer of the conductive mat and a part of the polymer of the base mat, and crosslinking between the polymer of the conductive mat and the polymer of the base mat.
[0068] Further, the polyalkyleneimines may be the same or different from each other, and may each independently include at least one selected from a group consisting of linear polyalkyleneimine, comb polyalkyleneimine, branched polyalkyleneimine, and dendrimer polyalkyleneimine, and preferably include branched polyalkyleneimine.
[0069] Further, the polyalkyleneimines may be the same or different from each other, and may each independently include at least one selected from a group consisting of polyethyleneimine and polypropyleneimine, and preferably include polyethyleneimine.
[0070] Further, the polymer may be an elastic body.
[0071] Further, the polymers may be the same or different from each other, and may each independently include at least one selected from a group consisting of styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene block copolymer (SBR), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-methyl methacrylate copolymer (PSMMA), styrene-acrylonitrile copolymer (PSAN), polyurethane, silicone rubber, and butadiene rubber, and preferably include styrene-ethylene-butylene-styrene block copolymer (SEBS).
[0072] Further, the polymer may further include an organic acid anhydride grafted to a main chain.
[0073] Further, the organic acid anhydride may include at least one selected from a group consisting of maleic anhydride, succinic anhydride, acetic anhydride, Naphthalenetetracarboxylic dianhydride, and ethanoic anhydride, and preferably include maleic anhydride.
[0074] Further, the conductor may include at least one selected from a group consisting of gold, silver, copper, platinum palladium, nickel, indium, aluminum, iron, rhodium, ruthenium, osmium, cobalt, molybdenum, zinc, vanadium, tungsten, titanium, manganese, chromium, graphene, and carbon nano tube (CNT), and preferably include gold.
[0075] Meanwhile, when the surfaces of the graphene and carbon nanotubes are functionalized with NH.sub.2 functional groups, they may be coupled with the organic acid anhydride to form a stable conductive layer.
[0076] Further, a thickness of the conductive mat may be 0.01 to 100 μm, preferably 0.5 to 50 μm, and more preferably 0.7 to 10 μm. When the thickness of the conductive mat is less than 0.01 μm, this is not preferable because it is difficult to secure conductivity due to the thickness of the thin conductive layer, and when more than 100 μm, this is not preferable because the overall elasticity of the mat is inhibited by the thick thickness of the conductive layer.
[0077] Further, a thickness of the base mat may be 0.1 to 1000 μm, preferably 10 to 500 μm, and more preferably 50 to 100 μm. When the thickness of the base mat is less than 0.1 μm, this is not preferable because the fiber is damaged in a swelling process by a protic polar solvent (ethanol) and it is difficult to maintain the shape of the mat, and when more than 1,000 μm, this is not preferable because the protic polar solvent cannot permeate deep into the mat due to the excessively thick thickness and the mat cannot be sufficiently swollen.
[0078] Further, each of the conductive mat and the base mat may be porous. As each of the conductive mat and the base mat is porous, it is possible to manufacture a stretchable electrode having air/fluid permeability.
[0079] According to an example embodiment, there is provided a method of manufacturing a stretchable electrode including (a) preparing a porous mat including a polymer crosslinked with a polyalkyleneimine by supporting, swelling, and crosslinking a porous mat including nanofibers including a polymer in a polyalkyleneimine solution, and (b) depositing a conductor to a predetermined depth of the porous mat to form a conductive layer on surfaces of nanofibers.
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[0081] Further, the method of manufacturing a stretchable electrode may further include, prior to (a), (a′) electrospinning a polymer solution including the polymer to prepare the porous mat including the nanofibers.
[0082] Further, the polymer solution may further include at least one selected from a group consisting of an aprotic polar solvent and a non-polar solvent.
[0083] Further, the polyalkyleneimine solution may further include a protic polar solvent.
[0084] Further, the deposition may be performed by at least one selected from a group consisting of sputtering, thermal evaporation, e-beam evaporation, thermal chemical vapor deposition, plasma enhanced chemical vapor deposition, atmospheric pressure chemical vapor deposition, and low pressure chemical vapor deposition, preferably by using sputtering, thermal evaporation, or e-beam evaporation alone or in combination, and more preferably by sputtering.
[0085] Further, the predetermined depth may be controlled by adjusting a deposition time.
[0086] According to an example embodiment, there is provided a stretchable electronic device including the stretchable electrode.
[0087] Further, the stretchable electronic device may include a stretchable display device, a stretchable light emitting electronic device, a stretchable electronic skin, a stretchable pressure sensor, a stretchable chemical sensor, and a stretchable wearable electronic device.
[0088] Further, the stretchable electronic device may include a device attachable to the body and a device implantable in the body.
Example Embodiments
[0089] Hereinafter, preferred example embodiments will be described. However, this is for illustrative purposes, and the scope of the present disclosure is not limited thereto.
Preparation Example 1: Nanofiber Mat
[0090] Polystyrene-block-poly(ethylene butylene)-block-polystyrene grafted with maleic anhydrides (SEBS-g-MA) was dissolved in a solvent mixture of cyclohexane/tetrahydrofuran (THF)/dimethylformamide (DMF) (wt/wt/wt=7:2:1). Here, the concentration of the polymer solution was used as 10 wt %.
[0091] The polymer solution was electrospun on a silicon wafer at a fixed feed rate of 20 μL/min and a voltage of 18.0 kV. Here, the distance between the nozzle-collectors was 15 cm, and a 25 G nozzle was used. After collecting a thickness of 80 μm by electrospinning, a nanofiber mat having nanofibers with an average diameter of 4 μm was prepared by peeling off from the silicon wafer.
Preparation Example 2: Nanofiber Mat
[0092] A nanofiber mat was prepared in the same manner as in Preparation Example 1, except that the average diameter of the nanofibers was set to 750 nm by using the concentration of the polymer solution at 7 wt % instead of setting the average diameter of the nanofibers 4 μm by using the concentration of the polymer solution at 10 wt %.
Preparation Example 3: Nanofiber Mat
[0093] A nanofiber mat was prepared in the same manner as in Preparation Example 1, except that the average diameter of the nanofibers was set to 9 μm by using the concentration of the polymer solution at 10 wt % instead of setting the average diameter of the nanofibers 4 μm by using the concentration of the polymer solution at 10 wt %.
Preparation Example 4: Bulk Film
[0094] Polystyrene-block-poly(ethylene butylene)-block-polystyrene grafted with maleic anhydrides (SEBS-g-MA) was dissolved in a solvent mixture of cyclohexane/tetrahydrofuran (THF)/dimethylformamide (DMF) (wt/wt/wt=7:2:1). Here, the concentration of the polymer solution was used as 10 wt %.
[0095] The polymer solution was spin-coated on a silicon wafer at 300 rpm for 30 seconds to prepare a 500 μm-thick bulk film.
Preparation Example 5: Imidized Nanofiber Mat
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[0097] Referring to
Preparation Example 6: Imidized Nanofiber Mat
[0098] An imidized nanofiber mat was prepared in the same manner as in Preparation Example 5, except that the nanofiber mat prepared according to Preparation Example 2 was used instead of using the nanofiber mat prepared according to Preparation Example 1.
Preparation Example 7: Imidized Nanofiber Mat
[0099] An imidized nanofiber mat was prepared in the same manner as in Preparation Example 5, except that the nanofiber mat prepared according to Preparation Example 3 was used instead of using the nanofiber mat prepared according to Preparation Example 1.
Preparation 8: Imidized Bulk Film
[0100] An imidized bulk film was prepared in the same manner as in Preparation Example 5, except that the bulk film prepared according to Preparation Example 4 was used instead of using the nanofiber mat prepared according to Preparation Example 1.
[0101] Table 1 summarizes the nanofiber mats and bulk films prepared according to Preparation Examples 1 to 8.
TABLE-US-00001 TABLE 1 SEBS- Average g-MA diameter concen- of nano- Thick- tration Preparation fibers ness Imidized Class (wt %) method (μm) (μm) or not Preparation 10 Electro- 4 80 — Example 1 spinning Preparation 7 Electro- 0.75 80 — Example 2 spinning Preparation 15 Electro- 9 80 — Example 3 spinning Preparation 10 Spin — 500 — Example 4 coating Preparation 10 Electro- 4 80 0 Example 5 spinning Preparation 7 Electro- 0.75 80 0 Example 6 spinning Preparation 15 Electro- 9 80 0 Example 7 spinning Preparation 10 Spin — 500 0 Example 8 coating
Example Embodiment 1: Stretchable Electrode
[0102] The imidized nanofiber mat prepared according to Preparation Example 5 was sputtered with Au by DC magnetron sputter (Cressington, 108 Auto). The deposition conditions were 20 mA, 50 sec, and thus, a stretchable electrode in which 1 μm-thick Au was permeated into the nanofiber mat was manufactured.
Example Embodiment 2: Stretchable Electrode
[0103] A stretchable electrode in which 8 μm-thick Au was permeated into was manufactured in the same manner as in Example Embodiment 1, except that Au was deposited under the deposition conditions of 20 mA and 500 seconds instead of to depositing Au under the deposition conditions of 20 mA and 50 sec.
Example Embodiment 3: A Dog Bone Shaped Stretchable Electrode
[0104] The imidized nanofiber mat prepared according to Preparation Example 5 was sputtered with Au by DC magnetron sputter (Cressington, 108 Auto). The deposition conditions were 20 mA, 50 sec and a dog bone shaped stretchable electrode in which 1 μm-thick Au was permeated into the nanofiber mat was manufactured by using two 3 cm×3 cm high conductive pads and a dog bone shaped shadow mask deposited with a width of 1 mm and a length of 1 cm.
Example Embodiment 4: A Dog Bone Shaped Stretchable Electrode
[0105] The imidized nanofiber mat prepared according to Preparation Example 5 was sputtered with Au by DC magnetron sputter (Cressington, 108 Auto). The deposition conditions were 20 mA, 500 sec and a dog bone shaped stretchable electrode in which 8 μm-thick Au was manufactured into the nanofiber mat was prepared by using two 3 cm×3 cm high conductive pads and a dog bone shaped shadow mask deposited with a width of 0.2 mm and a length of 1 cm.
Comparative Example 1: Electrode
[0106] An electrode was manufactured in the same manner as in Example Embodiment 1, except that the nanofiber mat prepared according to Preparation Example 1 was used instead of using the imidized nanofiber mat prepared according to Preparation Example 5.
TEST EXAMPLES
Test Example 1: Average Diameter of Nanofibers in Nanofiber Mats
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[0108] Referring to
Test Example 2: Confirmation of the Reaction Between SEBS-g-MA and PEI
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[0110] Referring to
[0111] Referring to
Test Example 3: Tensile Strength Test of Nanofiber Mats
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[0114] Referring to
[0115] Referring to
[0116] Therefore, it may be confirmed that the Young's modulus (E.sub.0) is increased after the nanofiber mat is imidized.
Test Example 4: Analysis of Mechanical Behavior of Nanofiber Mats
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[0118] Referring to
[0119] On the other hand, in Preparation Example 5 which is imidized, the fibers are aligned in the tensile direction at the initial stage of tension, and the bonding part of the fibers acts as a deformation constraint which prevents alignment, and high strain is concentrated in this part. Therefore, the result shows that the strain according to the deformation is distributed high in the fiber bonding part and relatively low in the other parts.
Test Example 5: Metal Layer Fracture Behavior Upon Deformation for Metal Deposition Depending on Whether Imidized or not
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[0121] Referring to
Test Example 6: Metal Deposition Characteristics of Nanofiber Mats
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[0123] Referring to
[0124] Referring to
Test Example 7: Characteristics Due to Including Thermoplastic Polymer Film
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[0126] Referring to
[0127] Referring to
[0128] Referring to
[0129] Therefore, the scope of the disclosure is defined not by the detailed description, but by the claims and their equivalents, and all variations within the scope of the claims and their equivalents are to be construed as being included in the disclosure.