WO2015053411A1 - Matériau composite métallique et son procédé de production - Google Patents

Matériau composite métallique et son procédé de production Download PDF

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WO2015053411A1
WO2015053411A1 PCT/JP2014/077478 JP2014077478W WO2015053411A1 WO 2015053411 A1 WO2015053411 A1 WO 2015053411A1 JP 2014077478 W JP2014077478 W JP 2014077478W WO 2015053411 A1 WO2015053411 A1 WO 2015053411A1
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composite material
carbon
plating solution
swcnt
metal composite
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PCT/JP2014/077478
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English (en)
Japanese (ja)
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新井　進
貢 上島
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日本ゼオン株式会社
国立大学法人信州大学
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Priority to JP2015541664A priority Critical patent/JP6483616B2/ja
Publication of WO2015053411A1 publication Critical patent/WO2015053411A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires

Definitions

  • the present invention relates to a metal composite material in which a metal that can be plated and a carbon nanostructure are combined.
  • the present invention also relates to a method for producing the above-described metal composite material.
  • Metals particularly copper, are widely used as conductive materials such as wiring materials and electric wires because of their high conductivity and excellent rollability.
  • carbon fiber is excellent in conductivity, thermal conductivity, sliding characteristics, mechanical characteristics, etc., so application to a wide range of applications is being studied.
  • thermal conductivity the thermal conductivity
  • composites with metals such as copper the development of composites with metals such as copper is also underway.
  • Patent Document 1 fine carbon fibers are mixed in a plating solution, and a plating film is formed by the plating solution. Techniques for compounding have been proposed.
  • Patent Document 1 it is necessary to mix a large amount of fine carbon fibers when compositing a metal and fine carbon fibers, but as a result, it is difficult to disperse the fine carbon fibers. In some cases, excellent conductivity and thermal conductivity could not be obtained.
  • the present invention advantageously solves the above-mentioned problems, and advantageously reduces the amount of carbon nanostructures such as fine carbon fibers and reduces the properties of the matrix metal without degrading the properties of the matrix metal. It aims at providing the metal composite material which improves property. Moreover, an object of this invention is to provide the manufacturing method of the metal composite material excellent in said electroconductivity and heat conductivity.
  • the inventors have intensively studied to develop a metal composite material excellent in conductivity and thermal conductivity.
  • the inventors investigated the cause of failure to obtain the desired conductivity and thermal conductivity in the technique of the above-mentioned Patent Document 1.
  • the following knowledge was obtained.
  • the fine carbon fiber described in Patent Document 1 cannot be said to have a sufficient specific surface area, and a sufficient amount of metal particles may not be deposited on the surface of the carbon nanostructure.
  • the inventors have conducted further detailed studies on the dispersion state and the composite state when various carbon nanostructures are used in order to solve the above-described problems caused by the properties of the carbon nanostructures.
  • Utilizing single-walled carbon nanotubes as carbon nanostructures is extremely effective in solving the above-mentioned problems, and as a result, excellent conductivity and thermal conductivity are obtained in composite materials of metal and carbon nanostructures.
  • the knowledge that it was obtained was obtained.
  • the present invention has been completed based on the above findings and further studies.
  • the gist configuration of the present invention is as follows. 1. A metal composite material in which a metal that can be plated and a carbon nanostructure are composited, wherein the carbon nanostructure includes single-walled carbon nanotubes.
  • the carbon nanostructure coarse dispersion plating solution in which the carbon nanostructure including single-walled carbon nanotubes is added to the plating solution together with the dispersing agent is subjected to a dispersion treatment in which a cavitation effect or a crushing effect is obtained.
  • a metal composite material having both excellent electrical conductivity and thermal conductivity can be obtained by utilizing single-walled carbon nanotubes as carbon nanostructures.
  • the metal composite material of the present invention is a composite of a metal that can be plated and a carbon nanostructure.
  • the metal that can be plated include nickel, tin, platinum, chromium, zinc, and composite metals thereof, including copper, and copper having excellent conductivity and thermal conductivity is used. It is preferable.
  • the “carbon nanostructure” is a general term for nano-sized substances composed of carbon atoms, and specifically includes single- or multi-walled carbon nanotubes, coil-like structures, and the like. Examples thereof include carbon nanocoils, carbon nanotwists in which carbon nanotubes are twisted, carbon nanotubes with beads in which beads are formed on carbon nanotubes, carbon nanobrushes having a large number of carbon nanotubes, and spherical shell-like fullerenes. These carbon nanostructures can be manufactured by, for example, a catalytic chemical vapor deposition method using a raw material gas disclosed in International Publication No. 2005/118473.
  • SWCNT single-walled carbon nanotube
  • SWCNT has a small diameter and a large specific surface area compared to other carbon nanostructures such as multi-walled carbon nanotubes, so that it can be composited with a metal in a small amount and is advantageous in terms of homogeneous composite. Therefore, by including single-walled carbon nanotubes as the carbon nanostructure, the electrical conductivity and thermal conductivity of the metal composite material can be improved.
  • the proportion of SWCNT in the carbon nanostructure is preferably 1% by mass or more from the viewpoint of the performance of the obtained metal composite material. More preferably, it is 10 mass% or more.
  • the total amount of carbon nanostructures may be SWCNT (100% by mass).
  • the ratio of the carbon nanostructure in the metal composite material of the present invention is preferably in the range of 1 to 60% by mass. This is because if it is less than 1% by mass, the desired property improving effect cannot be obtained, and if it exceeds 60% by mass, mechanical properties such as bending properties of the metal composite material deteriorate. More preferably, it is in the range of 5 to 50% by mass.
  • the specific surface area of SWCNT is preferably 600 m 2 / g or more in an unopened state. This is because the conductivity and thermal conductivity of the metal composite material can be improved satisfactorily. From the viewpoint of satisfactorily expressing the characteristics of the metal composite material, it is more preferable to set the range of 800 to 1,200 m 2 / g in an unopened state. Further, if the specific surface area of SWCNT is within the above range, the dispersibility of SWCNT at the time of dispersion treatment that can obtain the crushing effect described later can be improved, and damage to SWCNT can be sufficiently prevented.
  • the specific surface area in this invention means the BET specific surface area by BET method.
  • SWCNT preferably has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. Note that there is no RBM in the Raman spectrum of multi-walled carbon nanotubes of three or more layers.
  • RBM Radial Breathing Mode
  • SWCNT preferably has a G-band peak intensity ratio (G / D ratio) of 1 to 20 in the Raman spectrum. If the G / D ratio is 1 or more and 20 or less, even if the amount of SWCNT is small, the conductivity and thermal conductivity of the metal composite material can be sufficiently improved.
  • G / D ratio G-band peak intensity ratio
  • SWCNTs preferably have an average diameter (Av) and a diameter distribution (3 ⁇ ) satisfying 0.60> 3 ⁇ / Av> 0.20.
  • the average diameter (Av) and the diameter distribution (3 ⁇ ) are obtained by multiplying the average value and the standard deviation ( ⁇ ) by 3 when the diameter of 100 carbon nanotubes is randomly measured with a transmission electron microscope, respectively. Is.
  • the standard deviation in this specification is a sample standard deviation.
  • SWCNT preferably has a ratio of diameter distribution (3 ⁇ ) to average diameter (Av) (3 ⁇ / Av) of more than 0.25 and less than 0.60, more than 0.50 and less than 0.60. Is more preferable. This is because the use of SWCNTs with 3 ⁇ / Av satisfying the above range can sufficiently improve the conductivity and thermal conductivity of the metal composite material even if the amount of SWCNT is small. .
  • the average diameter (Av) of SWCNT is preferably 0.5 nm or more and 15 nm or less, and more preferably 1 nm or more and 10 nm or less, from the viewpoint of obtaining high conductivity and thermal conductivity. If the average diameter (Av) of SWCNT is 0.5 nm or more, aggregation of SWCNT is suppressed and the dispersibility in the plating solution can be further enhanced. On the other hand, if the average diameter (Av) of SWCNT is 15 nm or less, the electrical conductivity and thermal conductivity of the metal composite material can be improved.
  • the average diameter (Av) and diameter distribution (3 ⁇ ) of the SWCNTs described above may be adjusted by changing the SWCNT manufacturing method and manufacturing conditions, or a plurality of SWCNTs obtained by different manufacturing methods may be combined. You may adjust by.
  • SWCNT measures the diameter of 100 carbon nanotubes randomly using a transmission electron microscope, plots the diameter on the horizontal axis and the frequency on the vertical axis, and takes a normal distribution when approximated by Gaussian. Things are usually used.
  • the SWCNT preferably has a plurality of micropores.
  • SWCNTs preferably have micropores having a pore size smaller than 2 nm, and the micropore volume is a micropore volume determined by the following method, preferably 0.40 mL / g or more, more preferably It is 0.43 mL / g or more, more preferably 0.45 mL / g or more, and the upper limit is usually about 0.65 mL / g. It is preferable that SWCNT have the above micropores from the viewpoint of improving dispersibility.
  • the micropore volume can be adjusted, for example, by appropriately changing the SWCNT preparation method and preparation conditions.
  • P is a measurement pressure at the time of adsorption equilibrium
  • P0 is a saturated vapor pressure of liquid nitrogen at the time of measurement
  • M is an adsorbate (nitrogen) molecular weight of 28.010
  • ⁇ is an adsorbate (nitrogen).
  • the micropore volume can be determined using, for example, “BELSORP (registered trademark) -mini” (manufactured by Nippon Bell Co., Ltd.).
  • SWCNTs can be obtained as an aggregate (CNT aligned aggregate) oriented in a substantially vertical direction on a substrate having a catalyst layer for carbon nanotube growth on the surface according to the super growth method described later.
  • the height (length) of the aggregate at that time is preferably 100 ⁇ m or more and 5,000 ⁇ m or less. This is because the conductivity and thermal conductivity are improved by setting the height of the aggregate during synthesis to 100 ⁇ m or more.
  • the thickness is 5,000 ⁇ m or less, it is possible to sufficiently suppress the occurrence of SWCNT damage during the plating solution dispersion treatment. More preferably, it is 300 ⁇ m or more and 2,000 ⁇ m or less.
  • the mass density of SWCNTs as the aggregate is preferably 0.002 g / cm 3 or more and 0.2 g / cm 3 or less. If the mass density is 0.2 g / cm 3 or less, the connection between SWCNTs becomes weak, so that SWCNTs can be dispersed more uniformly. On the other hand, if the mass density is 0.002 g / cm 3 or more, the integrity of SWCNTs can be improved and the scattering of SWCNTs can be suppressed, so that handling becomes easy.
  • the SWCNT having the above-described properties can be obtained by, for example, supplying a raw material compound and a carrier gas onto a substrate having a catalyst layer for growing carbon nanotubes on the surface, and performing chemical vapor deposition (CVD) on carbon.
  • CVD chemical vapor deposition
  • the catalyst layer can be formed on the surface of the material by a wet process, and can be efficiently produced by using a raw material gas containing acetylene as a main component (for example, a gas containing 50% by volume or more of acetylene).
  • SWCNTs are usually separated from the aggregate by, for example, a physical, chemical, or mechanical peeling method, specifically, an electric field, a magnetic field, a centrifugal force, or a surface tension. It is peeled from the substrate by a method of mechanically peeling directly using tweezers or a cutter blade, or a method of peeling with pressure or heat such as suction by a vacuum pump, and used in a bulk state or a powder state.
  • a physical, chemical, or mechanical peeling method specifically, an electric field, a magnetic field, a centrifugal force, or a surface tension. It is peeled from the substrate by a method of mechanically peeling directly using tweezers or a cutter blade, or a method of peeling with pressure or heat such as suction by a vacuum pump, and used in a bulk state or a powder state.
  • the fine carbon fiber referred to in the present invention refers to a nano-sized carbon fiber, and multi-walled carbon nanotubes, carbon fibers and the like are particularly suitable.
  • the average diameter of the fine carbon fibers may be larger than the average diameter of SWCNT, but specifically, it is in the range of 10 to 200 nm.
  • a multi-wall carbon nanotube as a fine carbon fiber, it is suitable to make it the same as that of SWCNT mentioned above about the physical property.
  • the fine carbon fiber used for this invention can be manufactured by the method as described in the said international publication 2005/118473, for example.
  • the proportion of fine carbon fibers in the carbon nanostructure is preferably in the range of 1 to 60% by mass. This is because if the proportion of fine carbon fibers is less than 1% by mass, a desired property improving effect cannot be obtained, whereas if it exceeds 60% by mass, mechanical properties such as bending properties of the metal composite material deteriorate. . More preferably, it is in the range of 5 to 50% by mass.
  • the carbon nanostructure used in the present invention contains SWCNT as an essential component, and preferably further contains fine carbon fibers.
  • the remainder other than SWCNT or other than SWCNT and fine carbon fibers is composed of other carbon nanostructures other than those described above.
  • SWCNT 1 to 50% by mass, fine carbon fiber 0 to 60% by mass, and other carbon nanostructures The body is preferably 0 to 99% by mass.
  • the method for producing a metal composite material according to the present invention is a dispersion treatment in which a carbon nanostructure coarsely dispersed plating solution obtained by adding a carbon nanostructure containing SWCNT together with a dispersant to a plating solution can obtain a cavitation effect or a crushing effect.
  • a plating solution of a metal that can be plated as described above may be prepared.
  • a plating solution prepared from copper sulfate pentahydrate, glyoxylic acid, disodium ethylenediaminetetraacetic acid or the like is preferable to use.
  • the dispersant is not particularly limited, and a known dispersant capable of assisting the dispersion of the carbon nanostructure can be used.
  • Specific examples include surfactants and polysaccharides. Of these, surfactants are preferable, and in particular, when electroplating is performed, it is preferable to use a cationic or nonionic surfactant.
  • SDS sodium dodecyl sulfate
  • hydroxypropyl cellulose and the like.
  • the carbon nanostructure and the dispersing agent are added to the plating solution described above and stirred to obtain a carbon nanostructure coarse dispersion plating solution.
  • the amount of the carbon nanostructure added to the coarsely dispersed plating solution is preferably in the range of 0.01 to 10 g / L. More preferably, it is in the range of 0.1 to 2 g / L.
  • concentration of the dispersing agent in carbon nanostructure rough dispersion plating liquid should just be more than a critical micelle density
  • the carbon nanostructure coarse dispersion plating solution obtained as described above is subjected to a dispersion treatment for obtaining a cavitation effect or a crushing effect, whereby the carbon nanostructure is obtained. It is important to obtain a body dispersion plating solution.
  • a dispersion treatment for obtaining a cavitation effect or a crushing effect, whereby the carbon nanostructure is obtained.
  • the dispersion process that provides the cavitation effect and the dispersion process that provides the crushing effect are classified according to whether cavitation occurs or does not occur.
  • the case where cavitation is not generated includes the case where cavitation is not substantially generated.
  • cavitation refers to a phenomenon in which bubbles are generated due to local low pressure in the liquid due to the movement of the liquid.
  • Dispersion treatment that provides a cavitation effect is a dispersion method that uses shock waves generated by the bursting of vacuum bubbles generated in water when high energy is applied to the liquid.
  • the nanostructure can be uniformly dispersed in the plating solution, and as a result, the conductivity and thermal conductivity of the metal composite material formed as a plating film can be improved.
  • dispersion treatment examples include dispersion treatment using ultrasonic waves, dispersion treatment using a jet mill, and dispersion treatment using high shear stirring. These distributed processes may be performed only one, or may be performed in combination. More specifically, for example, an ultrasonic homogenizer, a jet mill, and a high shear stirrer are preferably used. These devices may be conventionally known devices.
  • the carbon nanostructure When an ultrasonic homogenizer is used for dispersion of the carbon nanostructure, the carbon nanostructure may be added to the plating solution and the plating solution may be irradiated with ultrasonic waves by the ultrasonic homogenizer.
  • the irradiation time may be appropriately set depending on the amount of the carbon nanostructure and the type of the dispersant, for example, preferably 3 minutes or more, more preferably 30 minutes or more, and preferably 5 hours or less, preferably 2 hours or less. More preferred.
  • the output is preferably 100 W to 500 W and the temperature is preferably 15 ° C. or more and 50 ° C. or less.
  • the number of treatments may be appropriately set depending on the amount of the carbon nanostructure and the type of the dispersant, for example, preferably 2 times or more, more preferably 5 times or more, and preferably 100 times or less. 50 times or less is more preferable.
  • the pressure is preferably 20 MPa to 250 MPa
  • the temperature is preferably 15 ° C. to 50 ° C.
  • surfactant it is preferable to use surfactant as a dispersing agent. This is because the viscosity is lower than that of the polysaccharide dispersant and the load on the apparatus can be reduced, so that the jet mill apparatus can be stably operated.
  • a carbon nanostructure may be added to the plating solution and the plating solution may be treated with a high shear stirring device.
  • the operation time (the time during which the machine is rotating) is preferably 3 minutes to 4 hours
  • the peripheral speed is 5 m / s to 50 m / s
  • the temperature is preferably 15 ° C. to 50 ° C.
  • the dispersion treatment for obtaining the above-described cavitation effect it is more preferable to perform the dispersion treatment for obtaining the above-described cavitation effect at a temperature of 50 ° C. or lower. This is because a change in concentration due to volatilization of the plating solution is suppressed.
  • a nonionic surfactant when used as a dispersant, the function of the dispersant is better when the dispersion treatment is performed at a low temperature such that the dispersant does not freeze or falls below the cloud point of the nonionic surfactant. And preferred.
  • the dispersion treatment that can produce a crushing effect can also be applied.
  • the dispersion treatment that provides this crushing effect is not only capable of uniformly dispersing the carbon nanostructures in the plating solution, but, as compared with the dispersion treatment that provides the above-described cavitation effect, such as SWCNT caused by shock waves when the bubbles disappear. Since damage to the carbon nanostructure can be suppressed, it is further advantageous in this respect.
  • the above-mentioned coarse dispersion plating solution is subjected to a shearing force to crush and disperse the aggregates of carbon nanostructures in the coarse dispersion plating solution, and further, back pressure is applied to the dispersion plating solution.
  • the carbon nanostructure can be uniformly dispersed in the plating solution while suppressing the occurrence of cavitation.
  • the back pressure applied to the dispersion plating solution may be reduced to atmospheric pressure all at once, but it is preferable to reduce the back pressure in multiple stages.
  • a dispersion system having a disperser having the following structure may be used. That is, the disperser has a disperser orifice having an inner diameter d1, a dispersion space having an inner diameter d2, and a terminal portion having an inner diameter d3 from the inflow side to the outflow side of the coarse dispersion plating solution (where d2> d3 > D1).
  • the flowing high-pressure (usually 10 to 400 MPa, preferably 50 to 250 MPa) coarse dispersion plating solution passes through the disperser orifice so that the pressure decreases and the flow rate of the fluid is high. And flows into the dispersion space. Thereafter, the coarse dispersion plating solution having a high flow rate flowing into the dispersion space flows at high speed in the dispersion space, and receives a shearing force at that time. As a result, the flow rate of the coarsely dispersed plating solution decreases and the carbon nanostructures in the coarsely dispersed plating solution are well dispersed. Then, a fluid having a pressure (back pressure) lower than the pressure of the inflowing coarse dispersion plating solution flows out from the terminal portion as the dispersion plating solution.
  • back pressure back pressure
  • the back pressure of the dispersion plating solution can be applied by applying a load to the flow of the dispersion plating solution.
  • a load for example, by disposing a multistage step-down device described later on the downstream side of the dispersion device, the dispersion plating solution A desired back pressure can be applied to the.
  • this multistage pressure reducer By reducing the back pressure of the dispersion plating solution in multiple stages by this multistage pressure reducer, it is possible to suppress the generation of bubbles in the dispersion plating solution when the dispersion plating solution is finally released to atmospheric pressure.
  • this disperser may be provided with a heat exchanger or a cooling liquid supply mechanism for cooling the dispersal plating solution.
  • a heat exchanger or a cooling liquid supply mechanism for cooling the dispersal plating solution.
  • the metal composite material of the present invention can be obtained as a plating film by plating the substrate surface using the carbon nanostructure-dispersed plating solution obtained by performing the dispersion treatment as described above.
  • the plating method is not limited to electroplating, and electroless plating can also be applied.
  • electroplating it is not limited to direct current plating, A current reversal plating method and a pulse plating method can also be employ
  • the plating treatment conditions are not particularly limited, and may be according to a conventional method.
  • substrate material The board
  • the manufacturing method of the present invention performs plating by dispersing carbon nanostructures in a plating solution.
  • SWCNTs are then formed on a substrate, and thereafter Complicated in the SWCNT lodging / compression process, which is indispensable for the method in which SWCNTs oriented vertically to the substrate are horizontally flattened by compressing and compressing, and then the SWCNTs are immersed in a plating solution such as copper and electroplated. Since the pretreatment process can be eliminated and the cost is excellent, it is extremely advantageous in terms of mass productivity.
  • SWCNT-1 Synthesis of carbon nanotubes
  • SWCNT-1 was obtained by the super-growth method according to the description of WO 2006/011655.
  • the obtained SWCNT-1 has a BET specific surface area of 1,050 m 2 / g and a spectrum of a radial breathing mode (RBM) in a low wavenumber region of 100 to 300 cm ⁇ 1 characteristic of SWCNT in measurement with a Raman spectrophotometer. was observed.
  • RBM radial breathing mode
  • SWCNT-2 was obtained by the same method except that the thickness of the iron thin film layer of the metal catalyst of Synthesis Example 1 was changed.
  • the obtained SWCNT-2 has a BET specific surface area of 820 m 2 / g, and a spectrum of radial breathing mode (RBM) is observed in a low frequency region of 100 to 300 cm ⁇ 1 characteristic of SWCNT in measurement with a Raman spectrophotometer. It was done.
  • average diameter (Av) was 5.9 nm
  • diameter distribution (3 ⁇ ) was 3.2 nm
  • (3 ⁇ / Av) Was 0.54.
  • the micropore volume was 0.41 mL / g.
  • Example 1 A plating solution comprising copper sulfate pentahydrate 0.06 mol / L, glyoxylic acid 0.03 mol / L, ethylenediaminetetraacetic acid disodium salt 0.1 mol / L was prepared, and synthesis example 1 as a carbon nanostructure These were added to the plating solution so that the concentration of SWCNT-1 prepared in Step 2 was 0.2 g / L, and the concentration of sodium dodecyl sulfate (SDS) and hydroxypropyl cellulose as a dispersant was 1 g / L, respectively. Stir with a stirrer for minutes.
  • SDS sodium dodecyl sulfate
  • the carbon nanostructure coarsely dispersed plating solution thus obtained was treated 20 times under the condition of 50 MPa using a jet mill (product name “JN-20”, manufactured by Joko Co., Ltd.), which is a dispersion device utilizing the cavitation effect. Thereafter, the pH of the solution was adjusted to about 12 using an aqueous potassium hydroxide solution to obtain a carbon nanostructure-dispersed plating solution containing SWCNT-1. Next, the surface of the 30 mm size copper substrate was sensitized and activated, and immersed in a carbon nanostructure dispersion plating solution stirred at a stirring speed of 1050 rpm using a stirrer while being maintained at 60 ° C.
  • a metal composite material 1 made of SWCNT-1 / copper was obtained.
  • the surface of the obtained metal composite material 1 was observed with a scanning electron microscope at a magnification of 100,000, it was observed that SWCNT-1 was combined with matrix copper at the nano level (FIG. 1). .
  • Such a metal composite material 1 exhibits desired conductivity and thermal conductivity.
  • Example 2 The SWCNT-1 used in Example 1 was changed to the SWCNT-2 produced in Synthesis Example 2, and the dispersion treatment of the solution containing SWCNT-2 was changed to a high-pressure homogenizer [product name “BERYU SYSTEM].
  • a metal composite material 2 made of SWCNT-2 / copper is obtained in the same manner as in Example 1 except that the dispersion treatment using the “PRO” (manufactured by Mieken Co., Ltd.) is changed to a dispersion treatment. It was. However, the dispersion treatment was performed four times under the condition of pressure: 100 MPa. When the surface of the obtained metal composite material 2 was observed with a scanning electron microscope, it was observed that SWCNT-2 was complexed with matrix copper at the nano level as in Example 1. Such a metal composite material 2 exhibits desired conductivity and thermal conductivity.
  • Example 3 In addition to SWCNT-1, VGCF-H (manufactured by Showa Denko, average diameter 150 nm) was used as fine carbon fiber, and the respective compounding amounts were 0.5 g / L and 0.5 g / L. 1 to obtain a metal composite material 3 made of SWCNT-1 / VGCF-H / copper.
  • a metal composite material 3 made of SWCNT-1 / VGCF-H / copper.
  • SWCNT-1 and VGCF-H formed an advanced network at the nano level as in Example 1, and the matrix A state of being compounded with copper was observed (FIG. 2).
  • Such a metal composite material 3 exhibits desired conductivity and thermal conductivity.
  • Example 4 In addition to SWCNT-1, VGCF-H (manufactured by Showa Denko, average diameter 150 nm) and Baytube (manufactured by Bayer MaterialScience, average diameter 13 nm) are used as fine carbon fibers, and the respective compounding amounts are 0.4 g / L, A metal composite material 4 made of SWCNT-1 / VGCF-H / Baytube / copper was obtained in the same manner as in Example 1 except that the amounts were 0.3 g / L and 0.3 g / L.

Abstract

La présente invention concerne un matériau composite métallique qui est obtenu par formation d'un complexe d'une nanostructure de carbone et d'un métal qui peut être plaqué. La nanostructure de carbone est configurée pour contenir des nanotubes de carbone à paroi unique.
PCT/JP2014/077478 2013-10-08 2014-10-08 Matériau composite métallique et son procédé de production WO2015053411A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019194662A1 (fr) 2018-04-06 2019-10-10 주식회사 엘지화학 Électrode, batterie secondaire la comprenant et son procédé de fabrication
JP2021517352A (ja) * 2018-04-06 2021-07-15 エルジー・ケム・リミテッド 電極、該電極を含む二次電池、および該電極の製造方法

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