JP6059089B2 - Carbon nanofiber aggregate manufacturing method and manufacturing apparatus, and conductive wire manufacturing method and manufacturing apparatus - Google Patents

Description

  The present invention relates to a carbon nanofiber aggregate manufacturing method and manufacturing apparatus, and a conductive wire manufacturing method and manufacturing apparatus.

  Carbon as a material for transparent electrodes, semiconductor thin films, electrode materials for lithium ion batteries, electrode materials for fuel cells, electrode materials for electric double layer capacitors, electrode materials for metal-air batteries, filler materials for composite materials, lightweight conductive wires, etc. Nanotubes are drawing attention.

  For the production of carbon nanotubes, a CVD (Chemical Vapor Deposition) method using a gas as a raw material is usually used. In the CVD method, carbon nanotubes grow from a catalyst supported on a substrate in an atmosphere of high-temperature source gas or hydrogen gas. At this time, a carbon nanofiber aggregate formed by assembling oriented carbon nanofibers is manufactured on the substrate. This carbon nanofiber assembly can be used as it is for transparent electrodes, semiconductor thin films, electrode materials for lithium ion batteries, electrode materials for fuel cells, and electrode materials for electric double layer capacitors, producing lightweight conductive wires, etc. It can also be used to For this reason, it is desired to mass-produce carbon nanofiber assemblies.

  As a method for mass-producing carbon nanofiber aggregates, conventionally, a method in which a large number of flat substrates are placed on a belt-like driving body and continuously put into a furnace for growing carbon nanotubes by a CVD method. Is known (Patent Documents 1 and 2 below).

JP 2001-234341 A Japanese Patent No. 4621896

  However, the manufacturing methods described in Patent Documents 1 and 2 have the following problems.

  That is, in the above manufacturing method, since a large number of plate-like substrates are used, carbon nanofiber aggregates are produced in large quantities, but the obtained carbon nanofiber aggregates are not integrated. There was a limit to the length of the conductive wire obtained from the assembly. On the other hand, it is conceivable to increase the area of the substrate, but in this case, it is necessary to increase the size of the furnace accordingly, and the entire manufacturing equipment including the furnace is increased in size.

  The present invention has been made in view of the above circumstances, and manufacture of a carbon nanofiber assembly capable of manufacturing a carbon nanofiber assembly capable of forming a sufficiently long conductive wire without increasing the size of the manufacturing apparatus. It is an object of the present invention to provide a method and a manufacturing apparatus, and a conductive wire manufacturing method and a manufacturing apparatus.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following invention.

That is, the present invention provides a catalyst layer forming step of continuously forming at least one catalyst layer on the surface of a rotating cylindrical substrate, and a raw material gas is supplied to the at least one catalyst layer from the outside of the cylindrical substrate. Supplying and forming a carbon nanofiber aggregate formed by assembling carbon nanofibers on the at least one catalyst layer, and collecting the carbon nanofiber aggregate from the substrate And a cleaning step of cleaning the surface of the substrate, and in the carbon nanofiber assembly forming step, the carbon nanofiber among the cylindrical substrates is heated by a heating device provided inside the cylindrical substrate. This is a method for producing a carbon nanofiber aggregate in which a portion where the fiber aggregate is formed is heated .

According to this method for producing a carbon nanofiber aggregate, at least one catalyst layer is continuously formed on the surface of a rotating cylindrical substrate, and the carbon nanofiber aggregate is formed on the catalyst layer. The carbon nanofiber aggregate is recovered from the substrate, and the surface of the substrate is cleaned. For this reason, a carbon nanofiber aggregate can be manufactured continuously. Therefore, it is possible to manufacture a carbon nanofiber assembly capable of manufacturing a sufficiently long conductive wire. Moreover, it is not necessary to increase the size of the carbon nanofiber assembly manufacturing apparatus. Therefore, according to the method for producing a carbon nanofiber aggregate of the present invention, a carbon nanofiber aggregate capable of forming a sufficiently long conductive wire can be produced without increasing the size of the production apparatus.

The present invention also provides a cylindrical base that is rotatably supported, a catalyst layer forming portion that forms at least one catalyst layer on the surface of the base, and an outer side of the cylindrical base. A raw material gas supply unit for supplying a raw material gas to the at least one catalyst layer from the outside of the cylindrical substrate, and an inner side of the cylindrical substrate, and the carbon nanofiber aggregate is formed in the cylindrical substrate. A heating device for heating a portion to be formed, a carbon nanofiber assembly forming part for forming a carbon nanofiber assembly formed by collecting carbon nanofibers on the at least one catalyst layer, and the carbon nanofiber from the substrate. An apparatus for producing a carbon nanofiber aggregate, comprising: a collection unit that collects a fiber assembly; and a cleaning unit that cleans the surface of the substrate.

  According to this carbon nanofiber assembly manufacturing apparatus, the substrate is rotated, and at least one catalyst layer is formed on the surface of the substrate by the catalyst layer forming unit. And a carbon nanofiber aggregate is formed on a catalyst layer by a carbon nanofiber aggregate formation part. The carbon nanofiber aggregate is recovered from the substrate by the recovery unit, and the surface of the substrate is cleaned by the cleaning unit. For this reason, it becomes possible to form a catalyst layer continuously on a base | substrate by a catalyst formation part. Therefore, according to the carbon nanofiber aggregate manufacturing apparatus of the present invention, the carbon nanofiber aggregate can be continuously manufactured. Therefore, it is possible to manufacture a carbon nanofiber assembly capable of manufacturing a sufficiently long conductive wire. Moreover, it is not necessary to increase the size of the carbon nanofiber assembly manufacturing apparatus. Therefore, according to the carbon nanofiber aggregate manufacturing apparatus of the present invention, a carbon nanofiber aggregate capable of forming a sufficiently long conductive wire can be manufactured without increasing the size of the manufacturing apparatus.

The present invention also provides a catalyst layer forming step of continuously forming at least one catalyst layer on the surface of a rotating cylindrical substrate, and a raw material gas is applied to the at least one catalyst layer from the outside of the cylindrical substrate. Supplying and forming a carbon nanofiber aggregate formed by assembling carbon nanofibers on the at least one catalyst layer, and drawing out the carbon nanofibers from the carbon nanofiber aggregate A collecting step for collecting the carbon nanofiber aggregate as a conductive wire and a cleaning step for cleaning the surface of the base body , wherein the carbon nanofiber aggregate forming step is provided inside the cylindrical base body. The carbon nanofiber aggregate out of the cylindrical substrate by a heating device A moiety formed is a manufacturing method of the conductive wire to heat.

According to this method for producing a conductive wire, at least one catalyst layer is continuously formed on the surface of a rotating cylindrical substrate, and a carbon nanofiber aggregate is formed on the catalyst layer. Carbon nanofibers are drawn out from the nanofiber aggregate, and the carbon nanofiber aggregate is recovered as a conductive wire. Then, the surface of the substrate is cleaned. For this reason, a carbon nanofiber aggregate can be manufactured continuously. Therefore, it is possible to manufacture a carbon nanofiber assembly capable of manufacturing a sufficiently long conductive wire. Further, since the carbon nanofiber aggregate can be continuously manufactured, it is not necessary to increase the size of the conductive wire manufacturing apparatus. Therefore, according to the method for manufacturing a conductive wire of the present invention, a sufficiently long conductive wire can be formed without increasing the size of the manufacturing apparatus.

  Further, the recovery step includes a peeling step of peeling the carbon nanofiber aggregate from the base, and a movement of the tip of the carbon nanofiber aggregate peeled from the base while regulating the movement of the carbon nanofiber aggregate. It is preferable to include a drawing step of drawing out the carbon nanofiber from the tip portion.

  In this case, when pulling out the carbon nanofiber from the tip of the carbon nanofiber assembly, excessive tension is applied to the tip of the carbon nanofiber assembly, and even if the entire carbon nanofiber assembly is about to be in tension, The movement of the tip of the carbon nanofiber aggregate is regulated. For this reason, it is suppressed enough that the whole carbon nanofiber aggregate will be in a tension state. As a result, separation between the carbon nanofiber aggregate being formed and the catalyst layer in the carbon nanofiber aggregate formation process is sufficiently suppressed. Therefore, in the carbon nanofiber aggregate formation step, the carbon nanofiber aggregate can be recovered after the carbon nanofibers are sufficiently grown on the catalyst layer.

  In the conductive wire manufacturing method, in the collecting step, it is preferable that the carbon nanofibers are drawn from the carbon nanofiber aggregate while rotating around the drawing direction.

  When pulling out carbon nanofibers, usually a plurality of carbon nanofibers are pulled out from the carbon nanofiber. Therefore, if the carbon nanofibers are pulled out while rotating around the pulling direction, the carbon nanofibers are sufficiently adhered to each other. Will fit. For this reason, the electroconductivity of the obtained conductive wire can be improved more.

The present invention also provides a cylindrical base that is rotatably supported, a catalyst layer forming portion that forms at least one catalyst layer on the surface of the base, and an outer side of the cylindrical base. A raw material gas supply unit for supplying a raw material gas to the at least one catalyst layer from the outside of the cylindrical substrate, and an inner side of the cylindrical substrate, and the carbon nanofiber aggregate is formed in the cylindrical substrate. A heating device that heats a portion to be formed, a carbon nanofiber assembly forming section that forms a carbon nanofiber assembly by assembling carbon nanofibers on the at least one catalyst layer, and the carbon nanofiber assembly The carbon nanofibers are pulled out from the collection unit for collecting the carbon nanofiber aggregates as conductive wires, and the surface of the substrate is cleaned. And a cleaning unit for packaging, said recovery unit is a production apparatus of the conductive wire having a pull-out device to draw the carbon nanofibers from the tip of the carbon nano fiber aggregate.

  According to this conductive wire manufacturing apparatus, the substrate is rotated, and at least one catalyst layer is formed on the substrate by the catalyst layer forming unit. And a carbon nanofiber aggregate is formed on a catalyst layer by a carbon nanofiber aggregate formation part. Then, the carbon nanofibers are pulled out from the carbon nanofiber aggregate by the pulling device of the collecting unit, collected as a conductive wire, and the surface of the substrate is cleaned by the cleaning unit. For this reason, it becomes possible to form a catalyst layer continuously on a base | substrate by a catalyst formation part, and a carbon nanofiber aggregate | assembly can be manufactured continuously. Therefore, a sufficiently long conductive wire can be manufactured. Further, since the carbon nanofiber aggregate can be continuously manufactured, it is not necessary to increase the size of the conductive wire manufacturing apparatus. Therefore, according to the conductive wire manufacturing apparatus of the present invention, a sufficiently long conductive line can be formed without increasing the size of the manufacturing apparatus.

  In the conductive wire manufacturing apparatus, the recovery unit separates and guides the carbon nanofiber aggregate from the base, and a tip of the carbon nanofiber aggregate separated from the base by the guide section. It is preferable to further include a restricting part that restricts the movement of the part.

  In this case, the carbon nanofibers are pulled out from the front end portion of the carbon nanofiber aggregate by the collection device of the collection unit. At this time, even if excessive tension is applied to the tip of the carbon nanofiber assembly and the entire carbon nanofiber assembly is about to be in tension, the movement of the tip of the carbon nanofiber assembly is restricted by the restricting portion. The For this reason, it is suppressed enough that the whole carbon nanofiber aggregate will be in a tension state. As a result, the occurrence of separation between the carbon nanofiber aggregate being formed and the catalyst layer is sufficiently suppressed by the carbon nanofiber aggregate formation portion. Therefore, the carbon nanofiber aggregate can be recovered after the carbon nanofibers are sufficiently grown on the catalyst layer.

  In the conductive wire manufacturing apparatus, it is preferable that the collection unit can rotate the carbon nanofibers drawn from the carbon nanofiber aggregate around the drawing direction.

  When pulling out carbon nanofibers, usually a plurality of carbon nanofibers are pulled out from the carbon nanofiber. Therefore, if the carbon nanofibers are pulled out while rotating around the pulling direction, the carbon nanofibers are sufficiently adhered to each other. Will fit. For this reason, the electroconductivity of the conductive wire obtained can be improved.

  In the present invention, “carbon nanofiber” refers to a hollow or solid fibrous body made of carbon and having a thickness of 50 nm or less.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the carbon nanofiber aggregate which can manufacture the carbon nanofiber aggregate which can form a sufficiently long conductive wire, without enlarging the manufacturing apparatus of a carbon nanofiber aggregate, and A manufacturing apparatus, a manufacturing method of a conductive wire, and a manufacturing apparatus are provided.

It is a fragmentary sectional view which shows the carbon nanofiber structure used in order to manufacture an electroconductive wire. 1 is a partial cross-sectional view schematically showing a first embodiment of a conductive wire manufacturing apparatus according to the present invention. It is a fragmentary sectional view which shows schematically 2nd Embodiment of the manufacturing apparatus of the electrically conductive wire which concerns on this invention. It is a top view which shows schematically 3rd Embodiment of the manufacturing apparatus of the electrically conductive wire which concerns on this invention. It is a top view which shows roughly 4th Embodiment of the manufacturing apparatus of the electrically conductive wire which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In all the drawings, the same or equivalent components are denoted by the same reference numerals, and redundant description is omitted.

<First Embodiment>
First, a first embodiment of the method for manufacturing a conductive wire of the present invention will be described.

  First, prior to the description of the first embodiment of the method for manufacturing a conductive wire, the first embodiment of the conductive wire manufacturing apparatus for performing this manufacturing method will be described.

  First, a carbon nanofiber assembly used for manufacturing a conductive wire will be described with reference to FIG. FIG. 1 is a partial cross-sectional view showing a carbon nanofiber assembly for manufacturing a conductive wire to be manufactured.

  As shown in FIG. 1, the carbon nanofiber aggregate B is composed of an aggregate of carbon nanofibers F oriented in a certain direction, and is formed on the catalyst layer A provided on the surface 10a of the substrate 10. Is.

  Next, a first embodiment of the conductive wire manufacturing apparatus will be described with reference to FIG. FIG. 2 is a partial cross-sectional view showing a first embodiment of the conductive wire manufacturing apparatus of the present invention.

  As shown in FIG. 2, the conductive wire manufacturing apparatus 100 includes a cylindrical substrate 10 that is rotatably supported, and a coating liquid that includes a catalyst material for forming the catalyst layer A on the outer peripheral surface 10 a of the substrate 10. 20, a temperature control device 71 for controlling the temperature of the substrate 10 in the vicinity of the catalyst coating device 30 to a temperature at which the coating solution 20 can be coated, a drying device 40 for drying the coating solution 20, and a catalyst material A reductive gas supply device 50 for forming a catalyst layer A activated by supplying a reductive gas, and a carbon nanofiber aggregate formed by assembling carbon nanofibers F oriented in a certain direction on the catalyst layer A The carbon nanofiber aggregate forming portion 60 that forms B and the exposed catalyst material after drying are heated and fired, and the portion of the substrate 10 where the carbon nanofiber aggregate B is formed is also included. A heating device 70 that heats, a recovery unit 80 that recovers the carbon nanofiber assembly B as the conductive wire 62 by pulling out the carbon nanofiber F from the carbon nanofiber assembly B, and the carbon nanofiber assembly B is recovered. An oxidizing gas supply unit 90 is provided as a cleaning unit that supplies an oxidizing gas to the exposed outer peripheral surface 10a of the substrate 10 to clean the outer peripheral surface 10a. In the present embodiment, the catalyst coating device 30, the temperature control device 71, the drying device 40, and the reducing gas supply device 50 constitute a catalyst layer forming unit.

  Examples of the material constituting the substrate 10 include metals such as stainless steel, titanium, copper, and aluminum, semiconductors such as silicon, and inorganic materials such as quartz and ceramics. The structure of the substrate 10 may be made of a single material or a plurality of materials. Examples of ceramics include those made of silica, alumina, zirconia, titania, and the like. The ceramic structure may be a sintered body or a crystalline body. Among these, alumina is preferable because the carbon nanofiber F can be effectively grown.

  A rotation shaft (not shown) along the extending direction may be passed through the inside of the base body 10 and both ends thereof may be held by bearing portions (not shown), or the outer peripheral portions at both ends of the base body 10 may be extended. And you may hold | maintain with a some rotary body (not shown) as a bearing part (not shown). In this way, the base 10 is rotatably supported. In addition, it is preferable that the manufacturing apparatus 100 has a rotating device (not shown) that rotates the rotating shaft or the rotating body to rotate the base 10. In addition, as a material which comprises a rotating shaft or the extended bearing part, what is necessary is just a material which has the heat resistance which can withstand the temperature which forms the carbon nanofiber aggregate B, and the mechanical strength which can hold | maintain the shape of the base | substrate 10. 10 may be the same as or different from the material constituting 10.

  The thickness of the substrate 10 is usually 200 to 20000 μm, but preferably 500 to 10,000 μm. In this case, as compared with the case where the thickness of the base body 10 is out of the above range, the structural breakdown of the base body 10 due to distortion caused by the thermal history during manufacture is prevented, and the minimum structure for maintaining the structure of the base body 10 is maintained. There is an advantage that it can have a limited strength and it is easy to obtain in-plane thermal uniformity of the substrate 10.

  The carbon nanofiber assembly forming unit 60 has a chamber 61. A gas supply port 61a is formed in the chamber 61, and a source gas supply unit (not shown) for supplying source gas and a carrier gas supply unit (not shown) for supplying carrier gas are connected to the gas supply port 61a. ing. The chamber 61 is also formed with an exhaust port 61b.

  The heating device 70 is composed of, for example, a near infrared heater or an infrared heater. The heating device 70 is preferably provided inside the base body 10. In this case, it is sufficiently suppressed that the heating device 70 unnecessarily decomposes the raw material gas by direct heating to generate soot, and as a result, the growth of the carbon nanofiber aggregate B on the catalyst layer A is prevented. Is sufficiently suppressed.

  The temperature control device 71 is constituted by, for example, a water-cooled copper block or a blower. The installation position of the temperature control device 71 may be either inside or outside the substrate 10. Here, at least a part of the temperature control device 71 is opposed to an intermediate portion between the first portion of the substrate 10 that faces the oxidizing gas supply unit 90 and the second portion that faces the catalyst coating device 30. It is preferable. In this case, when the coating liquid 20 is applied to the second part, the second part can be set to a temperature suitable for application of the coating liquid 20. For example, as shown in FIG. 2, the temperature control device 71 is installed such that a part thereof faces the intermediate portion and the remaining portion faces the second portion. However, the entire temperature control device 71 is located in the intermediate portion. You may install so that it may oppose.

  The collection unit 80 includes a drawing device 81 that collects the carbon nanofiber aggregate B as the conductive wire 62. The drawing device 81 is constituted by a winding bobbin, for example. Here, the drawing device 81 can rotate the conductive wire 62 around its drawing direction.

  Next, a method for manufacturing the conductive wire 62 using the conductive wire manufacturing apparatus 100 described above will be described.

  First, the cylindrical substrate 10 is rotated. The peripheral speed of the substrate 10 may be set to 1 to 100 cm / min, for example. At this time, in FIG. 1, a partition wall indicated by a two-dot chain line extending radially with respect to the outer peripheral surface 10 a of the base 10 is formed. The partition wall can be formed by spraying an inert gas such as argon toward the outer peripheral surface 10 a of the substrate 10. The reason why the partition walls are formed in this way is to enable the atmosphere between adjacent spaces to be set independently through the partition walls.

  Next, the temperature control device 71 controls the temperature of the outer peripheral surface 10a of the substrate 10 approaching the catalyst coating device 30 to a temperature at which the coating solution 20 can be applied uniformly. In this case, the temperature of the outer peripheral surface 10a of the substrate 10 in the vicinity of the catalyst coating device 30 is overheated, and when the coating liquid 20 comes into contact with the outer peripheral surface 10a, boiling and scattering are sufficiently suppressed. The liquid 20 can be uniformly formed on the substrate 10. Here, specifically, this temperature is preferably a temperature from room temperature to the boiling point of the coating liquid 20 or less.

  Next, the coating liquid 20 containing the catalyst material for forming one catalyst layer A is continuously applied to the outer peripheral surface 10 a of the base 10 by the catalyst coating device 30.

  As the catalyst material, a known metal catalyst used for growing the carbon nanofiber F can be used. Examples of such metal catalysts include V, Mo, Fe, Co, Ni, Pd, Pt, Rh, Ru, W, Al, Au, and Ti. These can be used alone or in combination of two or more. Among these, V, Mo, Fe, Co, Ni, Pd, Pt, Rh, Ru, and W are preferable because the carbon nanofiber F can be grown more effectively.

  Next, the coating liquid 20 is dried by the drying device 40.

  Next, the coating liquid 20 is heated and baked by the heating device 70. Thus, a fired body is obtained.

  Next, the reducing gas is supplied to the fired body by the reducing gas supply device 50 to form the activated catalyst layer A (catalyst layer forming step). The catalyst layer A is composed of a granular catalyst.

  As the reducing gas, for example, hydrogen gas or an inert gas (argon gas or nitrogen gas) having an extremely low oxygen partial pressure can be used. For example, oxygen gas or water vapor can be used as the oxidizing gas.

  The average particle diameter of the granular catalyst constituting the catalyst layer A is usually 1 to 50 nm, but preferably 2 to 25 nm. In this case, the carbon nanofibers F can be grown more effectively than when the average particle diameter of the granular catalyst is outside the range of 2 to 25 nm.

  Next, the carbon nanofiber aggregate B is formed on the catalyst layer A by the carbon nanofiber aggregate formation unit 60 (carbon nanofiber aggregate formation step). At this time, the heating device 70 also heats the portion of the substrate 10 where the carbon nanofiber aggregate B is formed.

  In the present embodiment, the source gas is supplied from the source gas supply unit into the chamber 61 through the gas supply port 61a, and the carrier gas is supplied from the carrier gas supply unit into the chamber 61 through the gas supply port 61a. Then, the exhaust gas is discharged out of the chamber 61 through the exhaust port 61b. Then, the carbon nanofiber aggregate B is formed on the catalyst layer A by the CVD method. In FIG. 1, only the carbon nanofiber aggregate B is shown on the base 10, and the catalyst layer A between the carbon nanofiber aggregate B and the base 10 is omitted.

  Next, the carbon nanofiber assembly B is recovered as the conductive wire 62 by pulling out the carbon nanofiber F from the carbon nanofiber assembly B by the drawing device 81 of the recovery unit 80 (recovery step). In the present embodiment, the carbon nanofiber aggregate B is not peeled off from the base 10 and the carbon nanofiber aggregate B is in close contact with the base 10, and the carbon nanofiber F is applied from the tip of the carbon nanofiber aggregate B. Pull out.

  Thereafter, the outer peripheral surface 10a of the substrate 10 is cleaned (cleaning step). In the present embodiment, the outer peripheral surface 10 a of the base 10 is cleaned using the oxidizing gas supply device 90. Specifically, an oxidizing gas is supplied to the outer peripheral surface 10a of the substrate 10 where the carbon nanofiber aggregate B is recovered and exposed. Thereby, the carbon remaining on the substrate 10 is oxidized and removed from the substrate 10 as carbon dioxide. In this way, the outer peripheral surface 10a of the base 10 is cleaned.

  Similarly, the catalyst layer A is formed on the outer peripheral surface 10a of the substrate 10 as described above, the carbon nanofiber aggregate B is formed and recovered, and the outer peripheral surface 10a of the substrate 10 is cleaned. .

  In this way, the carbon nanofiber aggregate B can be continuously manufactured. Therefore, a sufficiently long conductive wire 62 can be manufactured. Moreover, according to the said manufacturing method, since the carbon nanofiber aggregate B can be manufactured continuously, it is not necessary to enlarge the manufacturing apparatus 100 of a conductive wire. Therefore, according to the manufacturing method of the conductive wire, the sufficiently long conductive wire 62 can be formed without increasing the size of the manufacturing apparatus 100.

  For this reason, the obtained conductive wire 62 is used for a wire harness for automobiles and the like, and is useful as a conductive wire that requires weight reduction and strength.

  Moreover, in the said manufacturing method of a conductive wire, it is preferable to rotate the conductive wire 62 to the surroundings of the drawing | extracting direction with the drawing-out apparatus 81. FIG.

  When the carbon nanofiber F is pulled out, a plurality of carbon nanofibers are usually pulled out from the carbon nanofiber F. Therefore, when the carbon nanofiber F is pulled out while rotating around the pulling direction, the carbon nanofibers F are brought together. It will be in close contact with each other. For this reason, the electroconductivity of the obtained conductive wire 62 can be improved more.

Second Embodiment
Next, 2nd Embodiment of the manufacturing method of the electrically conductive wire which concerns on this invention is described using FIG.

  FIG. 3 is a view showing a manufacturing apparatus for carrying out a second embodiment of the method for manufacturing a conductive wire according to the present invention. As shown in FIG. 3, the manufacturing apparatus 200 includes a guide part 202 that peels and guides the carbon nanofiber aggregate B from the base body 10, and a tip of the carbon nanofiber aggregate B peeled from the base body 10 by the guide part 202. It differs from the manufacturing apparatus 100 of 1st Embodiment by the point which further has the control part 203 which controls the motion of a part.

  According to the manufacturing apparatus 200, the carbon nanofibers F are drawn from the tip of the carbon nanofiber aggregate B by the drawing device 81. At this time, even if excessive tension is applied to the tip of the carbon nanofiber assembly B and the entire carbon nanofiber assembly B is about to be in a tension state, the movement of the tip of the carbon nanofiber assembly B is restricted. 203. For this reason, the entire carbon nanofiber assembly B is sufficiently suppressed from being in a tension state. As a result, the occurrence of separation between the carbon nanofiber assembly B being formed and the catalyst layer A by the carbon nanofiber assembly forming unit 60 is sufficiently suppressed. Therefore, the carbon nanofiber aggregate B can be recovered after the carbon nanofibers F are sufficiently grown on the catalyst layer A.

  The present invention is not limited to the first and second embodiments. For example, in the second embodiment, only one catalyst layer A is formed on the outer peripheral surface 10a of the substrate 10 and the carbon nanofiber aggregate B is formed thereon, but the outer surface 10a of the substrate 10 is formed. A plurality of catalyst layers A may be formed along the extending direction of the substrate 10 (direction parallel to the rotation axis), and the carbon nanofiber aggregate B may be formed on each catalyst layer A (see FIG. 4). . In this case, as shown in FIG. 4, the carbon nanofibers 204 are pulled out from each carbon nanofiber aggregate B, and the twisted carbon nanofibers 206 are further twisted through the rollers 205 to be wound around the rollers 207 as the conductive wires 62. It is possible to take. In this case, there is an advantage that the conductive wire 62 having a larger diameter and higher strength can be obtained. The twisted carbon nanofibers 206 may be recovered as they are without being twisted as they are.

  In the second embodiment, the carbon nanofibers F are drawn out from one carbon nanofiber assembly B guided by the guide portion 202. As shown in FIG. The tip part may be divided into a plurality of parts by the slitter 301, and the carbon nanofibers 204 may be pulled out from each divided part. In this case, it is possible to pull out the carbon nanofibers 204 from each divided portion, twist the carbon nanofibers 206 twisted together via the roller 205, and wind them around the rollers 207 as the conductive wires 62. In this case, there is an advantage that the conductive wire 62 having a larger diameter and higher strength can be obtained. The twisted carbon nanofibers 206 may be recovered as they are without being twisted as they are.

  Furthermore, in the said 1st Embodiment, although the coating liquid 20 containing the catalyst material for forming the catalyst layer A on the outer peripheral surface 10a of the base | substrate 10 is apply | coated by the catalyst application apparatus 30, sputtering apparatus (not shown). ), A catalyst material layer made of a catalyst material may be formed. In this case, the drying device 40 is unnecessary.

  In the first and second embodiments, the coating liquid 20 containing the catalyst material is directly applied onto the outer peripheral surface 10a of the base 10 by the catalyst coating device 30. A catalyst support layer made of a physical layer may be formed, and the coating solution 20 may be applied on the catalyst support layer. When a sputtering apparatus is used instead of the catalyst coating apparatus 30, a catalyst support layer made of a metal oxide layer is formed on the outer peripheral surface 10a of the substrate 10, and a catalyst material layer is formed on the catalyst support layer. May be.

  Further, in the first and second embodiments, the oxidizing gas supply device 90 is used as the cleaning unit, but a reverse sputtering device may be used. The reverse sputtering apparatus includes a first electrode provided inside the cylindrical substrate 10 and a second electrode provided outside the substrate 10. A voltage is applied between the first electrode and the second electrode, and the conductive material remaining on the outer peripheral surface 10a of the base 10 is adhered to the second electrode, whereby the outer peripheral surface 10a of the base 10 is cleaned. .

  Moreover, in the said embodiment, although the catalyst layer formation part has the temperature control apparatus 71, the temperature control apparatus 71 is not necessarily required and can be abbreviate | omitted.

  In the first and second embodiments, the cylindrical base 10 is used, but the base 10 may be columnar.

  Furthermore, in the said 1st Embodiment and 2nd Embodiment, although the carbon nanofiber aggregate B is collect | recovered as the electrically conductive wire 62, the carbon nanofiber aggregate B may be collect | recovered as it is as the carbon nanofiber aggregate B. . In this case, the conductive wire manufacturing apparatuses 100 and 200 become the carbon nanofiber aggregate manufacturing apparatus as they are. The carbon nanofiber aggregate B recovered in this manner can be used to form an electrode by pressure-bonding it to a conductive substrate for an electrode using a conductive adhesive film or the like. The carbon nanofiber electrode thus obtained can be used as an electrode for a dye-sensitized solar cell, a lithium ion secondary battery, a lithium ion capacitor, an electric double layer capacitor, a fuel cell, a metal-air battery, a transparent electrode for a touch panel, etc. It is.

DESCRIPTION OF SYMBOLS 10 ... Base | substrate 10a ... Surface A ... Catalyst layer B ... Carbon nanofiber aggregate F ... Carbon nanofiber 20 ... Catalyst coating apparatus (catalyst layer formation part)
40 ... Drying device (catalyst layer forming part)
50. Reducing gas supply device (catalyst layer forming section)
DESCRIPTION OF SYMBOLS 60 ... Carbon nanofiber assembly formation part 62 ... Conductive wire 70 ... Heating device 71 ... Temperature control device 80 ... Collection | recovery part 81 ... Drawer 90 ... Oxidizing gas supply apparatus (cleaning part)
DESCRIPTION OF SYMBOLS 100,200 ... Manufacturing apparatus of conductive wire 202 ... Guide part 203 ... Control part

Claims (8)

A catalyst layer forming step of continuously forming at least one catalyst layer on the surface of a rotating cylindrical substrate;
A carbon nanofiber assembly that forms a carbon nanofiber aggregate by supplying a raw material gas to the at least one catalyst layer from the outside of the cylindrical substrate, and collecting the carbon nanofibers on the at least one catalyst layer Body formation process,
A recovery step of recovering the carbon nanofiber aggregate from the substrate;
A cleaning step of cleaning the surface of the substrate;
Including
In the carbon nanofiber assembly forming step, a carbon nanofiber assembly that heats a portion of the cylindrical substrate where the carbon nanofiber assembly is formed by a heating device provided inside the cylindrical substrate. Manufacturing method. A cylindrical base that is rotatably supported;
A catalyst layer forming part for forming at least one catalyst layer on the surface of the substrate;
A raw material gas supply unit that is provided outside the cylindrical substrate and supplies a raw material gas to the at least one catalyst layer from the outside of the cylindrical substrate;
A heating device that is provided inside the cylindrical substrate and that heats a portion of the cylindrical substrate where the carbon nanofiber aggregate is formed;
A carbon nanofiber aggregate forming part for forming a carbon nanofiber aggregate formed by assembling carbon nanofibers on the at least one catalyst layer;
A collection unit for collecting the carbon nanofiber aggregate from the substrate;
A cleaning unit for cleaning the surface of the substrate;
An apparatus for producing a carbon nanofiber assembly comprising: A catalyst layer forming step of continuously forming at least one catalyst layer on the surface of a rotating cylindrical substrate;
A carbon nanofiber assembly that forms a carbon nanofiber aggregate by supplying a raw material gas to the at least one catalyst layer from the outside of the cylindrical substrate, and collecting the carbon nanofibers on the at least one catalyst layer Body formation process,
A recovery step of recovering the carbon nanofiber aggregate as a conductive wire by pulling out the carbon nanofiber from the carbon nanofiber aggregate;
A cleaning step of cleaning the surface of the substrate;
Including
In the carbon nanofiber assembly forming step, a conductive wire manufacturing method for heating a portion of the cylindrical substrate where the carbon nanofiber assembly is formed by a heating device provided inside the cylindrical substrate. . The recovery step comprises
A peeling step of peeling the carbon nanofiber aggregate from the substrate;
And a drawing step of pulling out the carbon nanofibers from the tip part of the carbon nanofiber aggregate while restricting the movement of the tip part of the carbon nanofiber aggregate peeled from the substrate. Wire manufacturing method.   5. The method for producing a conductive wire according to claim 3, wherein, in the collecting step, the carbon nanofibers are pulled out from the carbon nanofiber aggregate while rotating around the drawing direction. A cylindrical base that is rotatably supported;
A catalyst layer forming part for forming at least one catalyst layer on the surface of the substrate;
A raw material gas supply unit that is provided outside the cylindrical substrate and supplies a raw material gas to the at least one catalyst layer from the outside of the cylindrical substrate;
A heating device that is provided inside the cylindrical substrate and that heats a portion of the cylindrical substrate where the carbon nanofiber aggregate is formed;
A carbon nanofiber aggregate forming part for forming a carbon nanofiber aggregate formed by assembling carbon nanofibers on the at least one catalyst layer;
A recovery unit for recovering the carbon nanofiber aggregate as a conductive wire by pulling out the carbon nanofiber from the carbon nanofiber aggregate;
A cleaning unit for cleaning the surface of the substrate,
The conductive wire manufacturing apparatus, wherein the recovery unit includes a drawing device that pulls out the carbon nanofibers from a tip of the carbon nanofiber aggregate. The collection unit is
A guide portion for peeling and guiding the carbon nanofiber aggregate from the substrate;
The conductive wire manufacturing apparatus according to claim 6, further comprising: a restricting portion that restricts movement of a tip portion of the carbon nanofiber aggregate separated from the base body by the guide portion. The conductive wire manufacturing apparatus according to claim 6 or 7, wherein the collection unit is capable of rotating the carbon nanofibers drawn from the carbon nanofiber aggregate around the drawing direction.

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