JP2013136016A - Structure producing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a structure producing method capable of easily producing a structure at low cost.SOLUTION: A structure producing method for producing a meshed structure includes a step of preparing a base having a surface, a step of disposing a mixture containing a formed article and air bubbles on a surface of the base, and a step of forming the structure comprising the formed article obtained by drying the air bubbles of the mixture.

Description

  The present invention relates to a structure manufacturing method for manufacturing a mesh-shaped structure.

  The net-like structure has properties such as high light transmittance, large specific surface area, and light weight. Therefore, it has various properties such as solar cell electrodes, secondary battery or fuel cell current collectors, and lightweight frames. It is used for various purposes. For example, when a net-like structure is used as an electrode in a solar cell, the light receiving area is increased due to high light transmittance, and energy conversion efficiency can be improved. Further, in the case of a secondary battery or a fuel cell, when a mesh-like current collector is used, since the specific surface area is large, more reactive substances and the current collector can be brought into contact with each other, and the reactivity is improved. . As examples of such a net-like structure, those described in Patent Documents 1 and 2 and Non-Patent Document 1, for example, are known.

  Patent Document 1 discloses a technique for forming a mesh-like conductive film used for a solar cell by forming grid lines on a substrate by a screen printing method.

  In Patent Document 2, an emulsion obtained by mixing a mixture containing a metal powder and a solvent is applied to a substrate, and the coating layer obtained by evaporating the solvent from the emulsion is sintered and plated. Thus, a technique for producing a network-like transparent conductive film is disclosed.

  Non-Patent Document 1 discloses a technique for producing a network-like three-dimensional structure by pouring a carbon nanotube dispersion into three-dimensionally arranged plastic spheres, drying them, and then removing the plastic spheres by chemical treatment. Has been.

Japanese Patent Application No. 2003-349359 Special table 2008-546165

Macromolecular Rapid Communications, 2010, 31, 609-615

  When grid lines are formed by a screen printing method as described in Patent Document 1, a highly transmissive conductive film can be manufactured by controlling the line width and pitch. However, a printing apparatus is required. Further, since the printing pressure is applied to the substrate and it is broken when it is brittle, the applicable substrates are limited.

  In the case of Patent Document 2 and Non-Patent Document 1, since the sintering and plating process or the process of removing the plastic sphere as a template is necessary, the process is complicated and the cost is increased.

  The present invention has been made in view of the above problems, and an object thereof is to provide a method for manufacturing a structure that can be easily manufactured at low cost.

  The production method of the present invention is a structure production method for producing a mesh-shaped structure, and a step of preparing a base having a surface, and a mixture containing a formation and bubbles on the surface of the base A step of arranging, and a step of drying the bubbles of the mixture to form the structure composed of the formed product.

  In one embodiment, the step of arranging the mixture includes a step of preparing a solution mixed with the formed product, and a step of forming the mixture by forming the bubbles in the solution.

  In one embodiment, the step of disposing the mixture includes a step of preparing a solution, a step of forming the bubbles in the solution, a step of placing the bubbles of the solution on the surface of the base, and the base Forming the mixture by injecting the formation into the bubbles placed on the surface of a table.

  In one embodiment, the method further includes a step of forming a sandwiching body having the base, the mixture, and a cover that faces the base via the mixture.

  In a certain embodiment, the process of arrange | positioning the said mixture includes the process of mounting the said mixture on the said surface of the said base, before forming the said clamping body.

  In a certain embodiment, the process of forming the said clamping body includes the process of inject | pouring the said formation into the said bubble located between the said base and the said cover body.

  In one embodiment, after the step of drying, the method further includes a step of peeling off the base and the cover of the holding body and taking out the structure.

  In one embodiment, in the step of forming the holding body, at least one of the base and the cover has a release layer.

  In a certain embodiment, the process of forming the said clamping body includes the process of bonding the said base and the said cover body through a spacer.

  In one embodiment, the formation includes at least one of a metal, a metal salt, an oxide, a sulfide, a chloride, an organic fiber, a carbon nanotube, and a biomolecule.

  In one embodiment, the metal includes at least one of gold, silver, copper, nickel, platinum, aluminum, silicon, titanium, manganese, iron, cobalt, zinc, molybdenum, palladium, tantalum, and tin.

  In one embodiment, the metal salt is a silver salt ink or silver β-ketocarboxylate.

  In one embodiment, the formation has a particle or wire shape.

  According to the manufacturing method of the present invention, since a large-scale apparatus is not required and the process is simple, a mesh-shaped structure can be easily manufactured at low cost.

The structure manufactured by the structure manufacturing method of this invention is shown. It is a flowchart which shows the structure manufacturing method of this invention. It is a schematic diagram which shows the structure preparation method of this invention. It is a flowchart which shows the structure manufacturing method which concerns on Embodiment 1 of this invention. It is a schematic diagram which shows the solution used for the structure preparation method of this invention. 2 is a photograph showing a structure manufactured based on the method of Embodiment 1. FIG. It is a flowchart which shows the structure manufacturing method which concerns on Embodiment 2 of this invention. It is a schematic diagram which shows the process of producing the structure of Embodiment 2 of this invention. It is a flowchart which shows the structure manufacturing method which concerns on Embodiment 3 of this invention. It is a schematic diagram which shows the process of producing the structure of Embodiment 3 of this invention. It is a flowchart which shows the structure manufacturing method which concerns on Embodiment 4 of this invention. It is an expansion schematic diagram which shows 10A of structures.

  Hereinafter, the present invention will be described with reference to the drawings. Note that the present invention is not intended to be limited to the configurations described in the embodiments and drawings described below, and includes configurations equivalent to those configurations.

  FIG. 1 shows a structure 10 manufactured by the structure manufacturing method of the present invention. FIG. 1A is a schematic diagram of the structure 10, and FIG. 1B is an enlarged schematic diagram of a part (region A) of the structure 10. The structure 10 is formed on the surface 202 of the base 20 and includes a plurality of units 12 arranged in parallel. Each of the plurality of units 12 has a plurality of linear portions 122 to which adjacent end portions are connected, and a space 124 is surrounded by the plurality of linear portions 122. The line width of the plurality of linear portions 122 is 10 μm to 100 μm. Further, the diameter of the opening formed by the plurality of linear portions 122 is several hundred μm to several mm.

  Since the structure 10 includes a large number of linear portions 122, the specific surface area is large and lightweight. Furthermore, since light can be transmitted through the space 124 surrounded by the linear portion 122, the transparency is also excellent. Therefore, the structure 10 manufactured by the structure manufacturing method of the present invention has the characteristics of a mesh-shaped structure having high permeability, high specific surface area, and light weight, and various properties that require these properties. It can be suitably used in the field.

  FIG. 2 is a flowchart showing the structure manufacturing method of the present invention, and FIG. 3 is a schematic diagram showing the structure manufacturing method of the present invention. The structure manufacturing method of this invention is performed by process S1-S5.

  In step S1, a base 20 having a surface 202 is prepared. The base 20 is not particularly limited as long as it has a surface 202, and for example, a glass plate or a PET substrate can be used. In step S <b> 3, the mixture 300 including the formation 302 and the bubbles 304 is disposed on the surface 202 of the base 20. The formation 302 is contained in the bubble wall of the bubble 304. The main components of the bubbles 304 are water and a formed product, but a surfactant and a thickener may be added as necessary.

  In step S <b> 5, the bubbles 304 of the mixture 300 are dried to form the structure 10 composed of the formation 302. A triple point T called a plateau boundary exists between adjacent bubbles. After the bubble formation, the bubble film becomes thinner with the passage of time, and the liquid forming the bubble flows toward the triple point T. Accordingly, the formation 302 contained in the bubbles moves with the liquid flow and gathers at the triple point T in the course of drying the mixture 300. After the liquid is dried, the bubbles 304 disappear, but the formation 302 gathered at the triple point T is formed in the linear portion 122 of the unit 12, and the linear portion 122 formed from adjacent bubbles and the unit 12 are separated. Configure. For example, when metal nanowires having hardness and a high aspect ratio are used as the formation, the metal nanowires gathered at the triple point T are entangled to form the linear portion 122 having a certain strength. As a result, the structure 10 having a three-dimensional network structure is obtained. The drying method is, for example, air drying. However, it is not limited to air drying as long as the bubbles 304 can be eliminated by drying. It can be natural drying.

  The structure 10 of the present invention was produced by performing steps S1 to S5. The structure 10 has a mesh shape that takes the shape of a triple point T between bubbles. Characteristics of the structure 10 such as permeability, specific surface area, or weight depend on the diameter of the linear portion 122 of the unit 12 in the structural body 10 and the size of the space 124 surrounded by the linear portion 122. For example, if the unit 12 is large, the space 124 surrounded by the unit 12 is also widened, and more light can be transmitted, so that the transparency is improved. On the other hand, when the unit 12 is smaller, the number of the linear portions 122 included in the unit area increases, and the specific surface area increases.

  As described above, in the present invention, the unit 12 of the structure 10 is configured by the formation 302 included in the bubbles 304 gathering to form the linear portion 122, and thus the size of the bubbles 304 is adjusted. Thus, the size of the space 124 surrounded by the unit 12 can be controlled. Since the bubbles 304 can be formed from several hundred μm to several mm, according to the present invention, the structure 10 having an opening diameter of the space 124 of the unit 12 of several hundred μm to several mm can be produced. Moreover, since the bubble wall of the bubble 304 is very thin, the thin linear part 122 with a wire diameter of about 10 μm to 100 μm can be formed.

  In the present invention, the formation 302 can be dispersed or dissolved in a liquid that forms bubbles. For example, the formation 302 is a silver nanowire. When the formation 302 is formed from silver nanowires, the structure has conductivity and functions as a conductor. For example, it is suitably used for battery electrodes and current collectors. However, noble metals such as gold and platinum that have better corrosion resistance than silver, copper, nickel, aluminum, silicon, titanium, manganese, iron, cobalt, zinc, molybdenum, palladium, tantalum, depending on the purpose and environment of use. It is also possible to employ a metal such as tin, an alloy containing at least one of these noble metals and metals as a constituent element, as the material of the formation 302.

  The material of the formation 302 may be at least one of a metal salt, an oxide, a sulfide, a chloride, a carbon nanotube, an organic fiber, and a biomolecule. Examples of the metal salt include a silver salt in which conductive metallic silver is produced by heating and baking. For example, silver salt ink or silver β-ketocarboxylate. Among silver salts, silver β-ketocarboxylate is preferable because it can form metallic silver by low-temperature firing. Moreover, when the structure 10 is formed from the metal oxide containing copper and nickel, it can be used as a photocatalyst, for example. Furthermore, the structure 10 can be made into a conductor by further performing a reduction treatment.

  The formation 302 is not limited to metal nanowires, and metal nanoparticles can also be employed. Furthermore, it is also possible to employ a material in which the surface of particles of resin, carbon, ceramics, metal or the like is coated with metal by plating or the like. Furthermore, the formation 302 can be a mixture of different types of particles and nanowires.

[Embodiment 1]
FIG. 4 is a flowchart showing the structure manufacturing method according to Embodiment 1 of the present invention. FIG. 5 is a schematic view showing a solution used in the structure manufacturing method of the present invention. FIG. 5A shows the solution 30 containing the formed product 302, and FIG. 5B shows a state where bubbles 304 are formed in the solution 30.

  In Embodiment 1 of the present invention, the structure manufacturing method is performed by step S1, step S3a1, step S3a2, and step S5.

  In step S1, a base 20 having a surface 202 is prepared. The base 20 is not particularly limited as long as it has a surface 202, and for example, a glass plate or a PET substrate can be used. Moreover, although the surface 202 which the base 20 shown in FIG.1 and FIG.3 has was planar shape, this embodiment is not restricted to this. The surface 202 may be, for example, an arc surface, a corrugated surface, or another curved surface.

  In step S3a1, a solution 30 mixed with the formed product 302 is prepared. The solution 30 in which the formation 302 is mixed can be prepared, for example, by adding the formation 302 to the solution 30 and mixing them. The solution 30 can be selected according to the type of the formation 302. There is no particular limitation as long as the bubbles 304 can be formed. For example, an aqueous solution mixed with a surfactant can be used. As the surfactant, for example, sodium dodecyl sulfate or a commercially available detergent can be used. In order to improve the strength of the bubbles 304, it is preferable to add, for example, polyvinyl alcohol (PVA), lauryl dimethylamine oxide or the like as a thickener to the solution 30.

  In step S <b> 3 a 2, the mixture 300 is formed on the surface 202 of the base 20 by forming bubbles 304 in the solution 30. The mixture 300 can be formed by forming bubbles 304 in the solution 30 by means such as stirring or a foaming device. When the foaming device is used, more uniform bubbles 304 are obtained.

  In step S <b> 5, the bubbles 304 of the mixture 300 are dried to form the structure 10 composed of the formation 302. The bubbles 304 in the mixture 300 are dried by air drying.

  FIG. 6 is a photograph showing the structure 10 produced based on the method of Embodiment 1 described above. The structure 10 is a three-dimensional structure having a mesh shape, and has characteristics such as high permeability derived from the mesh shape, a high specific surface area, a high cavity ratio, and light weight. It is suitably used for current collectors of ion secondary batteries, capacitors, and fuel cells, photocatalysts, impregnated members, heat pipes, heat buffer materials, noise absorbing members, shock absorbers, lightweight frames, stretchable conductors, filters, and the like.

[Embodiment 2]
FIG. 7 is a flowchart showing a structure manufacturing method according to Embodiment 2 of the present invention. FIG. 8 is a schematic diagram showing a process of manufacturing the structure according to the second embodiment of the present invention. The manufacturing method of Embodiment 2 of the present invention is a method of manufacturing the structure 10 in the same manner as the method of Embodiment 1, and is the same as that of Embodiment 1 described above except that the step S3 of arranging the mixture 300 is different. Since the process is included, redundant description is omitted to avoid redundancy.

  The structure manufacturing method according to the second embodiment of the present invention is performed by step S1, step S3b1, step S3b2, step S3b3, step S3b4, and step S5.

  In step S1, a base 20 having a surface 202 is prepared. In step S3b1, a solution 30 is prepared. The solution 30 is the same as that in step S3a1 of the first embodiment described above, but the formed product 302 is not mixed in the solution 30. In step S3b2, bubbles 304 are formed in the solution 30. In step S3b2, bubbles 304 were formed in the solution 30 in the same manner as in step S3a2 of the first embodiment. In step S3b3, the bubbles 304 of the solution 30 are placed on the surface 202 of the base 20. In step S3b4, the mixture 300 is formed by injecting the formation 302 into the bubbles 304 placed on the surface 202 of the base 20.

  As shown in FIG. 8, the injection performed in step S <b> 3 b <b> 4 is performed, for example, by creating a dispersion 306 in which the formed product 302 is mixed with the solution, Is done by letting

  The mixture 300 was formed on the surface 202 of the base 20 by executing the steps S3b1 to S3b4. After that, when the mixture 300 is dried, as described with reference to FIGS. 2 and 3, the formation 302 is gathered at the triple point T to form the structure 10.

  In FIG. 1, FIG. 3 and FIG. 6, the structure 10 is composed of only one unit 12, but Embodiments 1 and 2 of the present invention are not limited to this. By adjusting the number of the bubbles 304 in the mixture 300, the structure 10 having one or more units 12 can be produced.

[Embodiment 3]
FIG. 9 is a flowchart showing a structure manufacturing method according to Embodiment 3 of the present invention. FIG. 10 is a schematic view showing a process for producing a structure according to Embodiment 3 of the present invention. Since the third embodiment of the present invention includes the same steps as those of the first embodiment described above except that the step S4 for forming the sandwiching body 50 and the step S7 for taking out the structure 10 are further included, redundancy is avoided. Therefore, the overlapping description is omitted.

  In Embodiment 3 of the present invention, the manufacturing method is performed by Step S1, Step S3a1, Step S3a2, Step S4, Step S5, and Step S7. In step S1, a base 20 having a surface 202 is prepared. In step S3a1, a solution 30 mixed with the formed product 302 is prepared. In step S <b> 3 a 2, the mixture 300 is formed on the surface 202 of the base 20 by forming bubbles 304 in the solution 30.

  In step S <b> 4, the sandwich body 50 having the base 20, the mixture 300, and the cover 40 is formed. The cover 40 is opposed to the base 20 through the mixture 300. The sandwiching body 50 is formed by placing the cover 40 on the surface 202 of the base 20 so as to sandwich the mixture 300 disposed on the surface 202 of the base 20 in the previous step. As the cover 40, for example, a glass plate is used in the same manner as the base 20, but there is no particular limitation as long as the mixture 300 can be sandwiched between the base 20 and the cover 40. By performing step S4, the bubbles 304 of the mixture 300 are sandwiched between the base 20 and the cover 40 and become thin and flat.

  In step S <b> 5, the bubbles 304 of the mixture 300 are dried to form the structure 10 composed of the formation 302. When step S5 is performed in a state where the bubbles 304 are sandwiched between the base 20 and the cover 40, a unit 12 having a very short linear portion 122 in the thickness direction is formed between the base 20 and the cover 40. .

  In step S7, the base 20 and the cover 40 of the holding body 50 are peeled off, and the structure 10 is taken out. If the base 20 and the cover 40 are peeled off and separated, the structure 10 is obtained.

  The structure 10 was produced by performing process S1, process S3a1, process S3a2, process S4, process S5, and process S7. Since it can be formed very thin, it can be suitably used when a thin structure is required. In the manufacturing method according to Embodiment 3, the thickness of the structure 10 can be controlled by adjusting the gap between the base 20 and the cover 40. Specifically, the method of adjusting the gap is performed, for example, by placing a spacer between the base 20 and the cover 40. By arranging the spacer, the size of the gap can be changed, and the structures 10 having various thicknesses can be formed.

[Embodiment 4]
FIG. 11 is a flowchart showing a structure manufacturing method according to Embodiment 4 of the present invention. The fourth embodiment of the present invention includes the same steps as those of the second embodiment described above except that the step S4 for forming the sandwiching body 50 and the step S7 for taking out the structure 10 are further included. Therefore, redundancy is avoided. Therefore, the overlapping description is omitted.

  In Embodiment 4 of the present invention, the manufacturing method is executed by Step S1, Step S3b1, Step S3b2, Step S3b3, Step S4, Step S3b4, and Step S5.

  In step S1, a base 20 having a surface 202 is prepared. In step S3b1, a solution 30 is prepared. In step S3b2, bubbles 304 are formed in the solution 30. In step S3b3, the bubbles 304 of the solution 30 are placed on the surface 202 of the base 20.

  In step S4, the sandwiching body 50 is formed. The sandwiching body 50 includes a base 20, a bubble 304, and a cover 40 that faces the base 20 via the bubble 304. The sandwiching body 50 is formed by placing the cover 40 on the surface 202 of the base 20 so as to sandwich the bubbles 304 arranged on the surface 202 of the base 20 in the same manner as in the third embodiment. By executing step S4, the bubbles 304 are sandwiched between the base 20 and the cover 40 and become thin and flat.

  In step S3b4, the mixture 300 is formed by injecting the formation 302 into the bubbles 304 sandwiched between the base 20 and the cover 40.

  In step S <b> 5, the bubbles 304 of the mixture 300 are dried to form the structure 10 composed of the formation 302. After the holding body 50 is dried, a unit 12 having a very short linear portion 122 in the thickness direction is formed between the base 20 and the cover 40.

  In step S7, the base 20 and the cover 40 of the holding body 50 are peeled off, and the structure 10 is taken out. If the base 20 and the cover 40 are peeled off and separated, the structure 10 is obtained.

  In Embodiment 3 and Embodiment 4 of the present invention, in order to facilitate removal of the structure 10 from the base 20 or the cover 40, the structure 10 is brought into contact with one or both of the base 20 and the cover 40. A release layer may be provided on the surface. The release layer can be made of, for example, polytetrafluoroethylene (PTFE).

  Moreover, when using the base 20 or the cover 40 which does not have a peeling layer, in process S7 which takes out the structure 10, when peeling and separating the base 20 and the cover 40, the thickness direction of the unit 12 is used. As shown in the enlarged schematic diagram shown in FIG. 12, the linear portion 122 is broken, and the structure 10 </ b> A including the linear portions 122 arranged in a single layer is formed on both the base 20 and the cover 40. .

  For example, when the structure 10A is formed as described above using silver nanowires as the formation 302, the structure 10A having a transmittance of about 76% and a sheet resistance of about 4.5Ω / □ is obtained. Such a structure 10A can be suitably used as a transparent conductive film because it is thin, has high transmittance, and has a sheet resistance that is approximately half that of a commonly used ITO film.

  In addition, the structure 10 obtained by the manufacturing method of the present invention can further increase its conductivity by further performing a heating step or a plating step. For example, if the structure 10 is heated at 200 ° C. for 20 minutes, the surfactant remaining in the structure 10 is removed, so that the conductivity is improved. When the plating step is performed, the linear portion 122 of the structure 10 becomes thicker and the area for conducting electricity increases, so that the conductivity is improved.

  The structure 10 obtained by the production method of the present invention includes, for example, an electrode of a solar cell, a Li-ion secondary battery, a current collector of a capacitor or a fuel cell, a photocatalyst, an impregnation member, a heat pipe, a heat buffer material, a sound deadening member, It is suitably used for shock absorbers, lightweight frames, stretchable conductors, filters, transparent conductive films and the like.

10, 10A Structure 12 Unit 122 Linear portion 124 Space 20 Base 202 Surface 30 Solution 302 Formation 304 Bubble 306 Dispersion

Claims (13)

A structure manufacturing method for manufacturing a mesh-shaped structure,
Preparing a base having a surface;
Disposing a mixture containing a formation and bubbles on the surface of the base;
And drying the bubbles of the mixture to form the structure composed of the formed product. Placing the mixture comprises:
Preparing a solution mixed with the formation,
Forming the mixture by forming the bubbles in the solution. Placing the mixture comprises:
Preparing a solution;
Forming the bubbles in the solution;
Placing the bubbles of the solution on the surface of the base;
The method for producing a structure according to claim 1, further comprising: forming the mixture by injecting the formation into the bubbles placed on the surface of the base.   The structure according to any one of claims 1 to 3, further comprising a step of forming a sandwiching body having the base, the mixture, and a cover that faces the base via the mixture. Body making method.   5. The structure manufacturing method according to claim 4, wherein the step of arranging the mixture includes a step of placing the mixture on the surface of the base before forming the sandwiched body.   The structure forming method according to claim 4, wherein the step of forming the sandwiching body includes a step of injecting the formed material into the bubbles positioned between the base and the cover.   The method for producing a structure according to any one of claims 4 to 6, further comprising a step of removing the base body and the cover body of the sandwiching body and taking out the structure body after the drying step. .   The structure manufacturing method according to claim 4, wherein in the step of forming the sandwiching body, at least one of the base and the cover has a release layer.   9. The structure manufacturing method according to claim 4, wherein the step of forming the sandwiching body includes a step of bonding the base and the cover through a spacer.   The structure according to claim 1, wherein the formation includes at least one of a metal, a metal salt, an oxide, a sulfide, a chloride, a carbon nanotube, an organic fiber, and a biomolecule. Body making method.   11. The metal according to claim 10, wherein the metal includes at least one of gold, silver, copper, nickel, platinum, aluminum, silicon, titanium, manganese, iron, cobalt, zinc, molybdenum, palladium, tantalum, and tin. Structure manufacturing method.   The method for producing a structure according to claim 10, wherein the metal salt is silver salt ink or silver β-ketocarboxylate.   The structure formation method according to any one of claims 1 to 12, wherein the formation has a particle or wire shape.