WO2018051522A1 - 立体構造体 - Google Patents
立体構造体 Download PDFInfo
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- WO2018051522A1 WO2018051522A1 PCT/JP2016/077596 JP2016077596W WO2018051522A1 WO 2018051522 A1 WO2018051522 A1 WO 2018051522A1 JP 2016077596 W JP2016077596 W JP 2016077596W WO 2018051522 A1 WO2018051522 A1 WO 2018051522A1
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- dimensional structure
- porous portion
- porous
- region
- etching
- Prior art date
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Images
Classifications
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
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- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- H—ELECTRICITY
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
Definitions
- the present invention relates to a three-dimensional structure, and particularly to a three-dimensional structure capable of supporting a functional material such as a solid electrolyte or a catalyst.
- the three-dimensional structure can be used for an anode body or a catalyst carrier of an electrolytic capacitor, but the use of the three-dimensional structure is not limited to the above and can be applied to various applications.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2008-177199
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-177200
- Patent Document 3 Japanese Patent Application Laid-Open No. 61-278124
- Patent Document 4 JP-A-2012-161718 is a prior document disclosing a catalyst carrier for supporting a catalyst.
- the catalyst carrier described in Patent Document 4 is made of an aluminum wire provided with a spongy structure layer by etching or the like.
- the three-dimensional structure includes many voids and has a high expansion ratio corresponding to the surface area of the three-dimensional structure.
- the surface expansion magnification of the three-dimensional structure is high.
- the present invention has been made in view of the above-described problems, and an object of the present invention is to provide a three-dimensional structure capable of obtaining a high surface expansion magnification while ensuring mechanical strength.
- the three-dimensional structure based on the present invention is a three-dimensional structure containing a conductive material.
- the three-dimensional structure includes a core part and a porous part located around the core part.
- the porosity per unit area of the porous portion located on the inner side by 3/20 of the diameter of the three-dimensional structure from the outer edge of the porous portion is 80% or less. .
- the region between the two is defined as a void forming region, in the above-mentioned arbitrary cross section, it is located on the inner side of the inner side by 1/20 of the diameter of the three-dimensional structure from the outer edge of the porous portion, and the void is formed.
- the porosity per unit area of the porous portion located in the region is 15% or more and 80% or less.
- the porosity per unit area of the porous portion located in the void forming region is 15% or more and 80% or less in the above arbitrary cross section.
- the porosity per unit area is at least a part of the outer region at a position that is 1/20 of the diameter of the three-dimensional structure from the outer edge of the porous portion.
- the porous part having a height of more than 80% is present.
- the second virtual shape that is in contact with the inner edge of the porous portion when the outer shape of the three-dimensional structure is reduced in a similar manner in the above arbitrary cross section, and the first virtual shape The interval between them is 10 ⁇ m or less.
- the three-dimensional structure according to one embodiment of the present invention is a three-dimensional structure containing a conductive material.
- the three-dimensional structure includes a core part and a porous part located around the core part.
- the porous portion may be provided by partially removing the base material by etching or the like, or may be provided by laminating a material on the base material by vapor deposition or sintering.
- the shape of the substrate may be a wire shape including a thread shape, a fiber shape and a round bar shape, or may be a block shape including a sphere shape, an ellipsoid shape, a pellet shape and a coin shape.
- the block shape does not include shapes having a thickness of 1 mm or less, such as a foil shape and a paper shape.
- FIG. 1 is a perspective view showing the shape of the base material of the first example.
- FIG. 2 is a perspective view showing the shape of the base material of the second example.
- FIG. 3 is a perspective view showing the shape of the base material of the third example.
- the shape of the base material 10a of the first example is such that the diameter of the cross section is r, the length is L, and r ⁇ L.
- the shape of the base material 10c of the third example is such that the diameter of the cross section is r, the length is L, and r> L.
- the size relationship between the diameter r and the length L of the cross section of the base material is not particularly limited, but when the length L of the base material and the length of the three-dimensional structure are the same, the base material is Since the process of cutting according to the length of the three-dimensional structure becomes unnecessary, the number of manufacturing processes of the three-dimensional structure can be reduced.
- the base material does not have a corner portion that is not rounded on the outer shape.
- the outer shape of the substrate has corners, when the voids are formed in order from the outer periphery to the center of the substrate by etching, the voids are combined with each other in the vicinity of the corners to form a large void. In this case, an increase in the surface area of the porous portion is suppressed, and it becomes difficult to obtain a high surface expansion magnification.
- the shape of the cross section of the substrate is preferably circular.
- the material constituting the base material is appropriately selected according to the use of the three-dimensional structure.
- a dielectric layer is formed on the surface of the porous portion.
- the dielectric layer is preferably composed of an oxide of a metal component constituting the porous portion. Therefore, when the porous portion is provided by removing a part of the base material by etching or the like, the base material is made of a valve metal such as aluminum, niobium or tantalum.
- the three-dimensional structure may be formed by partially removing the base material by etching or the like, or may be formed by laminating the material on the base material by vapor deposition or sintering. . Furthermore, the three-dimensional structure may be formed by cutting a base material provided with a porous portion.
- the external shape of the three-dimensional structure may be a wire shape or a block shape. The magnitude relationship between the diameter and length of the cross section of the three-dimensional structure is not particularly limited.
- FIG. 4 is a cross-sectional view showing a configuration of a three-dimensional structure according to an embodiment of the present invention.
- the three-dimensional structure 11 according to an embodiment of the present invention includes a core part 12 and a porous part 13 positioned around the core part 12.
- the state in which the inner edge 13 b of the porous portion 13 has minute radial irregularities over the entire circumference is exaggeratedly shown.
- the diameter of the cross section of the porous portion 13 is r.
- the three-dimensional structure 11 has a porous portion 13 located on the inner side of the inner position 11a by 3/20 of the diameter r of the three-dimensional structure 11 from the outer edge 13a of the porous portion 13 in an arbitrary cross section.
- the porosity per unit area is 80% or less.
- the porosity per unit area of the porous portion 13 located on the inner side of the position 11a is more preferably 75% or less.
- the porous portion 13 of the three-dimensional structure 11 does not have a portion where voids are excessively formed, the mechanical strength of the three-dimensional structure 11 can be ensured.
- the three-dimensional structure 11 may be formed by partially removing the base material by etching or the like, or may be formed by laminating materials on the base material by vapor deposition or sintering.
- a method for forming the three-dimensional structure 11 by partially removing the base material by etching or the like there are methods such as AC etching or chemical etching.
- the etchant for example, an aqueous solution containing hydrochloric acid can be used. From the viewpoint of uniformly forming voids in the porous portion 13, AC etching is preferable to chemical etching.
- the three-dimensional structure 11 when the voids are formed in order from the outer peripheral portion of the three-dimensional structure 11 toward the center, the three-dimensional structure 11 is formed from the outer edge 13a of the porous portion 13. From the point in time when the etching progresses inward from the position 11a on the inner side by 3/20 of the diameter r, the circulating amount of the etchant in the etching bath is increased as the etching progresses. Thereby, it is possible to forcibly circulate the etching solution that has entered the space located in the innermost part of the three-dimensional structure 11.
- the composition and temperature of the etching solution that has entered the innermost space in the three-dimensional structure 11 can be brought close to the composition and temperature of the etching solution in the etching bath outside the three-dimensional structure 11.
- the porosity per unit area of the porous portion 13 is from the outer edge 13a of the porous portion 13 to the porous portion 13 located on the inner side of the inner position 11a by 3/20 of the diameter r of the three-dimensional structure 11. It can be ensured that there are no more than 80% voids formed excessively.
- the particle size and density of particles to be deposited on the base material by vapor deposition or sintering are determined by changing the porous portion 13. It adjusts suitably with progress of lamination
- the heating temperature and the heating time are also adjusted as appropriate.
- FIG. 5 is a cross-sectional view showing a configuration of a three-dimensional structure according to a first modification of one embodiment of the present invention.
- the first virtual shape 13 c that first contacts the inner edge 13 b of the porous portion 13 when the outer shape of the three-dimensional structure 11 is reduced in a similar manner as indicated by an arrow S in an arbitrary cross section.
- a region between the outer edge 13a of the porous portion 13 and the void forming region 13t is a region between the outer edge 13a of the porous portion 13 and the void forming region 13t.
- the porosity per unit area of the porous portion 13 located in the void forming region 13t is 15% or more and 80% or less, and 20 % To 75% is more preferable.
- the porous portion 13 in the void forming region 13t When the porosity of the porous portion 13 in the void forming region 13t is 15% or more and 80% or less, the porous portion 13 in the void forming region 13t does not have a portion where voids are excessively formed.
- the porosity of the porous portion 13 in the region between the inner edge 13b and the first virtual shape 13c (hereinafter referred to as the deep layer region 13i) is 80% or less. Therefore, the mechanical strength of the three-dimensional structure 11 can be ensured.
- region 13t when a porosity is ensured 15% or more, a high surface expansion magnification can be obtained.
- FIG. 6 is a cross-sectional view illustrating a configuration of a three-dimensional structure according to a second modification of the embodiment of the present invention.
- the porosity per unit area of the porous portion 13 that is located inward of the inner position 11b by 20 and located in the void formation region 13t is 15% or more and 80% or less.
- a region located on the inner side of the inner position 11b by 1/20 of the diameter of the three-dimensional structure 11 from the outer edge 13a of the porous portion 13 and located in the void forming region 13t is defined as a main region 13s.
- the porosity per unit area of the porous portion 13 in the main region 13s is more preferably 20% or more and 75% or less.
- the porosity is 80% or less. Therefore, the mechanical strength of the three-dimensional structure 11 can be ensured. Moreover, in the porous portion 13 of the main region 13s, a high area expansion ratio can be obtained by ensuring a porosity of 15% or more.
- a region outside the position 11b that is 1/20 of the diameter of the three-dimensional structure 11 from the outer edge 13a of the porous portion 13 is defined as a surface layer region 13h.
- the porous portion 13 having a porosity per unit area higher than 80% exists in at least a part of the surface layer region 13h.
- the porosity per unit area of the porous portion 13 may be higher than 80%.
- the three-dimensional structure 11 can be configured so that the rigidity of the porous portion 13 in the surface layer region 13h is reduced and the surface layer region 13h is easily compressively deformed. Thereby, when a bending stress is applied to the three-dimensional structure 11, the bending stress is relaxed in the surface layer region 13h, so that the porous portion 13 in the main region 13s can be prevented from being cracked or cracked.
- the porosity is 80% or less in the porous portion 13 of the main region 13s and the deep layer region 13i, the mechanical strength of the three-dimensional structure 11 can be ensured.
- a high area expansion ratio can be obtained by ensuring a porosity of 15% or more.
- the alternating current etching is started. Reduce the AC frequency only in the initial stage. As a result, the voids can be formed excessively only in the porous portion 13 located in the surface layer region 13h.
- the porous portion 13 When the porous portion 13 is formed by laminating a material on the base material by vapor deposition or sintering, the porous portion having a porosity per unit area higher than 80% in at least a part of the surface layer region 13h.
- the particle size and density of the particles arranged in the surface layer region 13h are adjusted as appropriate so that 13 exists. For example, the particle diameter of the particles disposed in the surface layer region 13h is increased, and the density of the particles disposed in the surface layer region 13h is decreased.
- FIG. 7 is a cross-sectional view showing a configuration of a three-dimensional structure according to a third modification of one embodiment of the present invention.
- the outer shape of the three-dimensional structure 11 is reduced in a similar manner as indicated by an arrow S in an arbitrary cross section as shown in FIG.
- the distance m between the second virtual shape 13d that is in contact with the inner edge 13b of the porous portion 13 and the first virtual shape 13c at the time is made to be 10 ⁇ m or less.
- the interval m is 5 ⁇ m or less.
- the interval m is determined by the size of minute unevenness in the radial direction that appears over the entire circumference at the inner edge 13 b of the porous portion 13.
- the minute unevenness appears when the etching proceeds non-uniformly from the outer peripheral portion to the central portion of the three-dimensional structure 11.
- voids are concentrated and formed in a portion where etching has further progressed.
- the porosity varies depending on the location.
- the distance m is 10 ⁇ m or less, it is possible to suppress variation in the porosity of the porous portion 13 located in the vicinity of the inner edge 13b.
- the porous portion 13 of the main region 13s and the deep region 13i in addition to the porosity being 80% or less, excessive voids are formed in the porous portion 13 located in the vicinity of the inner edge 13b. In order to suppress this, the mechanical strength of the three-dimensional structure 11 can be ensured.
- the voids are combined to form a large void. Therefore, a high surface expansion magnification can be obtained.
- FIG. 8 is a cross-sectional view showing a configuration of a three-dimensional structure according to a fourth modification of the embodiment of the present invention.
- each of the outer edge 13 a and the inner edge 13 b of the porous portion 13 is circular in an arbitrary cross section.
- the inner edge 13b of the porous portion 13 has no minute unevenness in the radial direction.
- the outer edge 13a and the inner edge 13b of the porous part 13 are located concentrically. Therefore, the thickness of the porous portion 13 is constant.
- FIG. 9 is a cross-sectional view of a three-dimensional structure for explaining a method of measuring the porosity per unit area of the porous portion of the three-dimensional structure. .
- an image obtained by capturing the cross section of the three-dimensional structure 11 with a microscope is observed.
- the difference in the color tone of the image is not due to the difference in the composition of the observation target, but reflects the unevenness of the surface of the observation target.
- a place where the color tone is dark is a place where there are many voids.
- a straight line CP1 connecting an arbitrary point P1 on the outer edge 13a of the porous portion 13 and the center C of the three-dimensional structure 11 is drawn.
- an intersection P2 between the straight line CP1 rotated 45 degrees clockwise around the center C and the outer edge 13a of the porous portion 13 is obtained, and the straight line CP2 is drawn.
- intersections between the straight line rotated clockwise by 45 degrees and the outer edge 13a of the porous portion 13 are obtained, and eight straight lines CP1 to CP8 are drawn.
- each of the straight lines CP1 to CP8 is binarized using image analysis software.
- the porosity profile is measured in the range of 15 ⁇ m in width from each of the points P1 to P8 toward the center C around the straight lines CP1 to CP8.
- the eight measurement results on the straight lines CP1 to CP8 by calculating the arithmetic average of the porosity at the same distance from the outer edge 13a of the porous portion 13, the radial direction inside the porous portion 13 is obtained. Obtain the porosity distribution.
- an aqueous solution of ammonium adipate is used when the dielectric layer is thin, and an aqueous solution of ammonium borate is used when the dielectric layer is thick. Used as an aqueous solution for measuring the surface magnification. And the ratio of the electrostatic capacitance of the three-dimensional structure with respect to the electrostatic capacitance of a base material is calculated
- the size of the area expansion ratio depends on the capacitance of the electrolytic capacitor when the three-dimensional structure is used as the anode body of the electrolytic capacitor, and on the yield of the catalytic reaction when the three-dimensional structure is used as the catalyst carrier. affect.
- the width when the three-dimensional structure is bundled horizontally and the width of the vinyl chloride masking line tape to be used are approximately 2: 3. Adjust the number of three-dimensional structures and the width of the vinyl chloride masking line tape.
- the end of the FRP plate is fixed to the lower chuck of the tensile tester, and the gripping margin of the vinyl chloride masking line tape is fixed to the upper chuck of the tensile tester.
- the vinyl chloride masking line tape is peeled off from the three-dimensional structure at a peeling speed of 10 mm / sec.
- peel strength a value obtained by dividing the maximum load by the number of three-dimensional structures subjected to the test.
- the degree of adhesion of the porous portion peeled from the three-dimensional structure to the vinyl chloride masking line tape after being peeled off is visually observed to evaluate the mechanical strength of the three-dimensional structure.
- the three-dimensional structure according to Example 1 was manufactured using a columnar base material having a diameter of 0.2 mm.
- the component of the base material was aluminum having a purity of 99.99%.
- an etching solution is supplied to the base material in the axial direction of the base material so that the gap forming region has a thickness of about 55 ⁇ m while circulating the etching solution. AC etching was performed.
- the temperature of the etching solution was 35 ° C.
- the current density was 280 mA / cm 2
- the current waveform (half wave) was a triangular wave.
- the circulating amount of the etching solution in the etching bath was increased as the etching progressed. Specifically, the flow rate of supplying the etching solution was 40 cm / min at the start of etching, and thereafter the flow rate of the etching solution was gradually increased to 100 cm / min at the end of etching.
- the solid structure was subjected to acid treatment for the purpose of removing chlorine ions.
- Example 2 The three-dimensional structure according to Example 2 was subjected to acid treatment for the purpose of degreasing the surface of the base material and then subjected to AC etching under the same conditions as in Example 1 at a frequency of 0.5 Hz. Similar to Example 1, except that AC etching was performed and the circulation rate of the etching solution in the etching bath was maintained at the circulation rate before increasing the circulation rate in Example 1 during AC etching. A three-dimensional structure was produced.
- the three-dimensional structure according to the comparative example is the same as in Example 1 except that the circulating amount of the etching solution in the etching bath is maintained at the circulating amount before increasing the circulating amount in Example 1 during AC etching. A three-dimensional structure was produced.
- Table 1 is a table showing the distribution of the porosity of the porous portion and the measurement results of the interval m of the three-dimensional structures according to Example 1, Example 2, and Comparative Example.
- the surface layer region from the outer edge 13a to the position 11b of the porous portion 13, the first main region from the position 11b to the position 11a of the porous portion 13, and the porous portion 13 The range of the porosity in each of the second main region from the position 11a to the first virtual shape 13c and the deep layer region from the first virtual shape 13c to the inner edge 13b is shown.
- a region obtained by combining the first main region and the second main region is a main region.
- a region formed by combining the surface layer region and the main region is a void forming region.
- a region obtained by combining the void forming region and the deep layer region is the entire porous portion 13.
- Table 2 is a table showing the evaluation results of the expansion ratio, the mechanical strength of the three-dimensional structure, the peel strength, and the bending deformability of the three-dimensional structure of the three-dimensional structures according to Example 1, Example 2, and Comparative Example. is there.
- the value of the three-dimensional structure of the comparative example 1 is set to 100.
- the mechanical strength of the three-dimensional structure the amount of the porous portion adhering to the vinyl chloride masking line tape was visually confirmed, and the case where it was small was evaluated as “Good”, and the case where it was large was evaluated as “Insufficient”.
- FIG. 10 is a photograph of the cross section of the three-dimensional structure of Example 1 taken with a microscope.
- FIG. 11 is a photograph of a cross section of the three-dimensional structure of the comparative example taken with a microscope.
- 12 is a photograph showing a state in which the vinyl chloride masking line tape has been peeled off from the three-dimensional structure of Example 1.
- FIG. 13 is a photograph showing a state in which the vinyl chloride masking line tape is peeled off from the three-dimensional structure of the comparative example.
- the porosity of the entire porous portion was 80% or less, and the interval m was 3 ⁇ m.
- the porosity of the porous portion in the surface layer region was higher than 80%, and the interval m was 5 ⁇ m.
- the porosity of the porous portion in the surface layer region and the second main region was higher than 80%, and the interval m was 2 ⁇ m.
- the color tone in the porous portion 13 was substantially constant from the outer edge to the inner edge.
- excessive formation of voids in the vicinity of the inner edge of the porous portion 13 was not recognized.
- minute unevenness in the radial direction was observed over the entire circumference.
- the color tone in the porous portion 93 increases as it goes from the outer edge to the inner edge, and the color tone difference at the boundary between the core portion 92 and the porous portion 93 is It was big.
- the three-dimensional structure 91 of the comparative example it was confirmed that voids were excessively formed in the vicinity of the inner edge of the porous portion 93.
- the expansion ratio was 108, the mechanical strength of the three-dimensional structure was Good, the peel strength was 750, and the maximum radius of curvature of the three-dimensional structure was 200. .
- the surface expansion magnification was 102, the mechanical strength of the three-dimensional structure was Good, the peel strength was 730, and the maximum curvature radius was 75.
- the expansion ratio was 100, the mechanical strength of the three-dimensional structure was Insufficient, the peel strength was 100, and the maximum radius of curvature was 100.
- the porosity per unit area of the porous portion 13 located on the inner side from the inner position 11a by 3/20 of the diameter r of the three-dimensional structure 11 from the outer edge 13a of the porous portion 13 is 80% or less.
- Example 2 When comparing Example 1 and Example 2, Example 2 had a smaller maximum radius of curvature than Example 1. That is, in Example 2, the bending deformability of the three-dimensional structure was larger than that in Example 1. On the other hand, Example 1 and Example 2 were equivalent in the mechanical strength of the three-dimensional structure.
- the mechanical strength of the three-dimensional structure is maintained by making the porosity of the region outside the position 11b inside the outer edge 13a of the porous portion 13 by 1/20 of the diameter of the three-dimensional structure 11 higher than 80%.
- the bending deformability of the three-dimensional structure can be increased.
- FIG. 14 is a partial cross-sectional view illustrating a configuration of an electrolytic capacitor including a three-dimensional structure according to an embodiment of the present invention as an anode body.
- the separator is not shown.
- the electrolytic capacitor 6 includes an anode body 1, a dielectric body 2, an electrolyte 3, a dielectric body 4, and a cathode body 5.
- a method for forming the dielectric 2 on the surface of the three-dimensional structure to be the anode body 1 there is a method in which the three-dimensional structure is anodized in an aqueous solution such as ammonium borate, ammonium phosphate or ammonium adipate.
- Electrolyte 3 may be either an electrolytic solution or a solid electrolyte.
- an electrolytic solution using polyethylene glycol or ⁇ -butyrolactone as a solvent can be used.
- a solid electrolyte a solid electrolyte containing a conductive polymer such as polypyrrole, polythiophene, polyfuran, or polyaniline can be used.
- an aluminum foil can be used as the cathode body 5.
- the electrolyte 3 is a solid electrolyte, a laminate of a carbon layer and a silver paste layer can be used.
- the electrolytic capacitor further includes a separator sandwiched between the anode body and the cathode body, an anode terminal connected to the anode body, a cathode terminal connected to the cathode body, an aluminum case, and a sealing rubber.
- a separator sandwiched between the anode body and the cathode body, an anode terminal connected to the anode body, a cathode terminal connected to the cathode body, an aluminum case, and a sealing rubber.
- the dielectric 2 is formed on the surface of the anode body 1 by anodic oxidation, and then the anode terminal is connected to the anode body 1 by laser welding or the like.
- the cathode body 5 to which the cathode terminal is connected is wound on the outer side to form a multi-roll body.
- the multi-roll body is impregnated with the electrolytic solution.
- the multiple roll body impregnated with the electrolytic solution is accommodated in an aluminum case, and the opening of the aluminum case is sealed with a sealing rubber.
- the dielectric 2 is formed on the surface of the anode body 1 by anodic oxidation, and then the anode terminal is connected to the anode body 1 by laser welding or the like.
- the cathode body 5 to which the cathode terminal is connected is wound on the outer side to form a multi-roll body.
- a solid electrolyte layer is formed on the multi-roll body by chemical oxidative polymerization, electrolytic polymerization, or application of a dispersion solution.
- the multiple roll body on which the solid electrolyte layer is formed is accommodated in an aluminum case, and the opening of the aluminum case is sealed with a sealing rubber.
- the capacitance of the electrolytic capacitor 6 is a combined capacitance in which a capacitor composed of the anode body 1, the dielectric body 2 and the electrolyte 3 and a capacitor composed of the electrolyte body 3, the dielectric body 4 and the cathode body 5 are connected in series. It becomes.
- the capacitance of the electrolytic capacitor 6 is equal to the capacitance of the capacitor composed of the anode body 1, the dielectric 2 and the electrolyte 3. It is greatly influenced by the value.
- an electrolytic capacitor having a high capacitance can be manufactured by using the three-dimensional structure according to the present embodiment having a high surface expansion magnification while ensuring mechanical strength.
- the characteristics required for the electrolytic capacitor 6 are not only the capacitance but also a low leakage current. Since the dielectric 2 has defects and is not a complete insulator, when a DC voltage is applied to the electrolytic capacitor 6, a slight leakage current is generated, which adversely affects the circuit to which the electrolytic capacitor 6 is connected. Sometimes. In particular, when the area occupied by the cut surface of the three-dimensional structure is large in the surface area of the three-dimensional structure, the influence of leakage current becomes large.
- the electrolytic capacitor 6 when used as a noise filter such as a low-pass filter, the electrolytic capacitor 6 is disposed in parallel with the signal line, and the electrolytic capacitor 6 is connected to the ground. As a result, a signal having a high frequency that causes noise can be removed from the signal line.
- Formula 1 is a formula which shows the relationship of an impedance, a frequency, and an electrostatic capacitance at the time of using an electrolytic capacitor as a noise filter.
- the inductor is not considered.
- the impedance of the electrolytic capacitor 6 decreases as the frequency increases, a signal having a high frequency is easily separated from the signal line and flows into the electrolytic capacitor 6.
- leakage current flows from the electrolytic capacitor 6.
- the dielectric formed on the surface of the anode body breaks down due to the leakage current, the effect as a noise filter such as a low-pass filter is reduced. Therefore, it is necessary to reduce the leakage current.
- the leakage current of the electrolytic capacitor 6 can be kept low, and the performance of the electrolytic capacitor 6 as a noise filter is improved. Can do.
- the catalyst body can be used in a precise chemical reaction system such as a microreactor.
- the three-dimensional structure is anodized in an acidic electrolyte.
- the hydration treatment is performed after the anodization, and the firing treatment is further performed at a temperature of 300 ° C. or higher and 550 ° C. or lower.
- the metal having catalytic activity to be supported on the three-dimensional structure is not particularly limited, and a metal, alloy, or metal oxide having catalytic activity such as platinum-based metal can be used.
- an impregnation method in which the three-dimensional structure is immersed in an aqueous solution containing metal ions having catalytic activity can be used.
- one key is how many metals having catalytic activity can be supported on the catalyst carrier. That is, a high yield can be obtained in the catalytic reaction by using the three-dimensional structure according to the present embodiment having a high surface expansion ratio while ensuring mechanical strength.
- the three-dimensional structure according to the present embodiment can be used for applications that require high surface expansion magnification while ensuring mechanical strength.
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Abstract
Description
以下、比較例および実施例に係る立体構造体の特性について検証した実験例について説明する。まず、立体構造体の各特性の評価方法について説明する。
図9は、立体構造体の多孔質部の単位面積当たりの空隙率を測定する方法を説明するための、立体構造体の横断面図である。
図5に示すように、立体構造体11の横断面をマイクロスコープにて撮像する。第1仮想形状13cと、立体構造体11の外形との間の間隔を、空隙形成領域の厚さとする。
測定周波数120HzのLCRメーターにて、立体構造体および基材の各々の静電容量を、アジピン酸アンモニウム水溶液中またはホウ酸アンモニウム水溶液中にて測定する。なお、拡面倍率の測定に用いる水溶液は、下記のように使い分けてもよい。立体構造体に誘電体層を陽極酸化によって形成する場合は、陽極酸化の際に用いる水溶液を拡面倍率の測定用の水溶液として用いる。誘電体層を陽極酸化以外の方法によって形成する場合に、誘電体層の形成厚さが薄いときはアジピン酸アンモニウム水溶液を、誘電体層の形成厚さが厚いときはホウ酸アンモニウム水溶液を、拡面倍率の測定用の水溶液として用いる。そして、基材の静電容量に対する立体構造体の静電容量の比率を求め、これを拡面倍率とする。
複数の立体構造体を横一列に約2mmの幅になるように並べて束ね、その長さ方向の両端を、厚さが1mmであるFRP(Fiber Reinforced Plastics)製の板にセロファンテープで貼って固定する。複数の立体構造体に、幅が3mm、厚さが0.12mm、ステンレス板に対する引き剥がし粘着力が450gf/15mmである塩化ビニルマスキングラインテープを貼り付ける。塩化ビニルマスキングラインテープを複数の立体構造体に貼り付ける際には、2kgfのローラが立体構造体の全長を2往復するように押し付ける。
立体構造体を20Vの印加電圧で陽極酸化した後、曲率半径の異なる丸棒に立体構造体を沿わせ、立体構造体が破断した時の丸棒の最大曲率半径を求める。この最大曲率半径が小さいほど、立体構造体の曲げ変形能が大きい。
(Z:インピーダンス、f:周波数、C:静電容量)
式1は、電解コンデンサをノイズフィルタとして用いた場合の、インピーダンス、周波数および静電容量の関係を示す式である。なお、式1においては、インダクタは考慮していない。式1から分かるように、電解コンデンサ6のインピーダンスは周波数が高いほど低くなるため、周波数が高い信号は信号ラインから離脱して、電解コンデンサ6に流れやすくなる。
Claims (5)
- 導電性材料を含有する立体構造体であって、
芯部と、
前記芯部の周囲に位置する多孔質部とを備え、
前記立体構造体の任意の横断面において、前記多孔質部の外縁から前記立体構造体の径の3/20だけ内側の位置より内側に位置する前記多孔質部の単位面積当たりの空隙率が80%以下である、立体構造体。 - 前記任意の横断面において、前記立体構造体の外形を相似状に縮小させた際に前記多孔質部の内縁と最初に接する第1仮想形状と、前記多孔質部の外縁との間の領域を、空隙形成領域と規定した場合、
前記任意の横断面において、前記多孔質部の外縁から前記立体構造体の径の1/20だけ内側の位置より内側に位置し、かつ、前記空隙形成領域に位置する、前記多孔質部の単位面積当たりの空隙率が15%以上80%以下である、請求項1に記載の立体構造体。 - 前記任意の横断面において、前記空隙形成領域に位置する前記多孔質部の単位面積当たりの空隙率が15%以上80%以下である、請求項2に記載の立体構造体。
- 前記任意の横断面において、前記多孔質部の外縁から前記立体構造体の径の1/20だけ内側の位置の外側の領域の少なくとも一部に、単位面積当たりの空隙率が80%より高い前記多孔質部が存在している、請求項2に記載の立体構造体。
- 前記任意の横断面において、前記立体構造体の外形を相似状に縮小させた際に前記多孔質部の内縁と最後に接する第2仮想形状と、前記第1仮想形状との間の間隔が、10μm以下である、請求項2から請求項4のいずれか1項に記載の立体構造体。
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EP16916302.9A EP3489976B1 (en) | 2016-09-16 | 2016-09-16 | Three-dimensional structure |
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KR1020197010166A KR102218601B1 (ko) | 2016-09-16 | 2016-09-16 | 입체 구조체 |
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EP3489976B1 (en) | 2023-04-12 |
JPWO2018051522A1 (ja) | 2019-07-18 |
KR20190049823A (ko) | 2019-05-09 |
KR102218601B1 (ko) | 2021-02-22 |
EP3489976A1 (en) | 2019-05-29 |
US10529497B2 (en) | 2020-01-07 |
CN109716467B (zh) | 2020-10-30 |
CN109716467A (zh) | 2019-05-03 |
TWI704589B (zh) | 2020-09-11 |
TW201814747A (zh) | 2018-04-16 |
JP6750179B2 (ja) | 2020-09-02 |
EP3489976A4 (en) | 2019-09-25 |
US20180277308A1 (en) | 2018-09-27 |
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