CN110915008A - Carbon nanotube composite and method for producing same - Google Patents
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- CN110915008A CN110915008A CN201880047426.9A CN201880047426A CN110915008A CN 110915008 A CN110915008 A CN 110915008A CN 201880047426 A CN201880047426 A CN 201880047426A CN 110915008 A CN110915008 A CN 110915008A
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The present invention provides a carbon nanotube composite having excellent thermoelectric conversion characteristics. A carbon nanotube composite according to an embodiment of the present invention includes carbon nanotubes and a conductive polymer having a specific structure, and 90% by mass or more of the carbon nanotubes are semiconducting carbon nanotubes.
Description
Technical Field
The present invention relates to a carbon nanotube composite and a method for manufacturing the same.
Background
In recent years, carbon nanotubes have attracted attention as a material that can be used in the fields of thermoelectric conversion elements, field effect transistors, sensors, integrated circuits, rectifier elements, solar cells, catalysts, electroluminescence, and the like. Carbon-based thermoelectric conversion materials represented by carbon nanotubes are considered to be portable and flexible materials for thermoelectric conversion devices because of their light weight and structural flexibility derived from carbon-carbon bonds.
For example, a composite of carbon nanotubes and a conductive polymer has been proposed as a thermoelectric conversion material. Patent document 1 discloses a thermoelectric conversion material containing a conductive polymer and a thermal excitation assistant. Further, patent document 2 discloses a thermoelectric conversion material containing carbon nanotubes and a conjugated polymer. Non-patent document 1 describes a composite material using a complex of PEDOT (poly (3, 4-ethylenedioxythiophene)) and poly (styrenesulfonic acid) (PEDOT: PSS), meso-tetrakis (4-carboxyphenyl) porphine (TCPP), and carbon nanotubes. Non-patent document 2 describes that p-type and n-type carbon nanotube composites are obtained by using a conjugated multivalent electrolyte. In addition, non-patent document 3 reports thermoelectric conversion characteristics of a semiconducting carbon nanotube film obtained using a polyfluorene derivative.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2013/047730 (published 4 months and 4 days in 2013);
patent document 2: international publication No. 2013/065631 (published 5/10 in 2013).
Non-patent document
Non-patent document 1: moriarty, G.P.et., EnergyTechnol.1,265-272,2013
Non-patent document 2: mai, c. -k.et.al., Energy environ.sci.8,2341-2346,2015
Non-patent document 3: avery, a.d.et.al., Nature energy1,16033,2016
Disclosure of Invention
Problems to be solved by the invention
However, in the above-described conventional techniques, thermoelectric conversion characteristics such as seebeck coefficient, electric conductivity, and output factor are insufficient, and there is still room for improvement.
An object of one embodiment of the present invention is to provide a carbon nanotube composite having excellent thermoelectric conversion characteristics.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have found that a carbon nanotube composite containing semiconducting carbon nanotubes at high purity can be realized by using a conductive polymer having a specific structure, and have completed the present invention. The present invention includes the following aspects.
<1> a carbon nanotube composite, comprising: a carbon nanotube and a conductive polymer represented by the following formula (1) or the following formula (2),
[ chemical formula 1]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
[ chemical formula 2]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, X is a 2-valent aromatic group, and n is an integer of 3 or more)
90% by mass or more of the carbon nanotubes are semiconducting carbon nanotubes.
<2> the carbon nanotube composite according to <1>, wherein the conductive polymer is represented by the following formula (3).
[ chemical formula 3]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
<3> the carbon nanotube composite according to <1> or <2>, wherein 95% or more by mass of the carbon nanotubes are semiconducting carbon nanotubes.
<4> the carbon nanotube composite according to any one of <1> to <3>, further comprising a p-type dopant or an n-type dopant.
<5> an ink comprising the carbon nanotube composite according to any one of <1> to <4> and a solvent.
<6> A method for producing a carbon nanotube composite, which comprises
A dispersion step of dispersing carbon nanotubes in a solvent containing a conductive polymer represented by the following formula (1) or formula (2); and
a separation step of separating a carbon nanotube composite in which carbon nanotubes include at least 90 mass% of semiconducting carbon nanotubes from the carbon nanotube dispersion liquid obtained in the dispersion step,
[ chemical formula 4]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
[ chemical formula 5]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, X is a 2-valent aromatic group, and n is an integer of 3 or more)
<7> the method for producing a carbon nanotube composite according to <6>, wherein the conductive polymer is represented by the following formula (3).
[ chemical formula 6]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
<8> the method for producing a carbon nanotube composite according to <6> or <7>, wherein the carbon nanotube composite in which the carbon nanotubes include 95 mass% or more of semiconducting carbon nanotubes is separated in the separation step.
<9> the method for producing a carbon nanotube composite according to any one of <6> to <8>, which comprises a doping step of bringing a p-type dopant or an n-type dopant into contact with the carbon nanotube composite.
Effects of the invention
According to one embodiment of the present invention, the following effects can be obtained: it is possible to provide a carbon nanotube composite having excellent thermoelectric conversion characteristics.
Drawings
Fig. 1 is a graph showing an infrared spectrum of the carbon nanotube film of example 1.
Fig. 2 is a graph showing an infrared spectrum of the carbon nanotube film of comparative example 1.
Fig. 3 is a graph showing thermoelectric conversion characteristics of the carbon nanotube films of examples 1 to 4 and the carbon nanotube films of comparative examples 2 and 3.
Fig. 4 is a graph showing thermoelectric conversion characteristics of the p-type carbon nanotube film of example 5, the n-type carbon nanotube film of example 6, and the p-type carbon nanotube film of comparative example 4.
Fig. 5 is a view showing a scanning electron microscope image of the carbon nanotube film of example 1.
Detailed Description
Hereinafter, an example of the embodiment of the present invention will be described in detail, but the present invention is not limited to this. In the present specification, "a to B" indicating a numerical range means "a or more and B or less" unless otherwise specified.
[1. index relating to thermoelectric conversion characteristics ]
First, an index relating to thermoelectric conversion characteristics will be described.
<1-1. output factor >
The output factor (power factor) can be obtained by the following equation (i).
PF＝α2σ (i)
In the formula (i), PF represents an output factor, α represents a seebeck coefficient, and σ represents conductivity.
In the carbon nanotube composite according to one embodiment of the present invention, for example, the output factor is preferably 100 μ at 310KW/mK2Above, more preferably 200. mu.W/mK2Above, particularly preferably 400. mu.W/mK2The above. If the output factor of the carbon nanotube composite is 100 muW/mK at 310K2The above value is preferably the same as or more than that of the conventional carbon nanotube composite. In order to obtain such a high-output carbon nanotube composite, it is conceivable to increase either or both of the seebeck coefficient and the electrical conductivity.
<1-2. Seebeck coefficient >
The seebeck coefficient refers to the ratio of the open circuit voltage with respect to the temperature difference between the high temperature junction and the low temperature junction of the circuit representing the seebeck effect (from the third edition of the mcgrao-hill science and terminology dictionary). The seebeck coefficient can be measured using, for example, a seebeck measuring device (manufactured by MMR Technologies) or a thermoelectric conversion characteristic evaluating device (manufactured by ADVANCE RIKO, inc., ZEM-3) used in examples described later. The larger the absolute value of the seebeck coefficient is, the larger the thermoelectromotive force is.
In addition, the seebeck coefficient can be used as an index for judging the polarity of an electronic material such as a carbon nanotube. Specifically, for example, an electronic material in which the seebeck coefficient appears to be a positive value can be said to have p-type conductivity. In contrast, an electronic material in which the seebeck coefficient exhibits a negative value can be said to have n-type conductivity.
In the carbon nanotube composite, the absolute value of the seebeck coefficient is preferably 20 μ V/K or more, more preferably 30 μ V/K or more, and still more preferably 40 μ V/K or more.
<1-3. conductivity >
The conductivity can be measured by, for example, a 4-probe method using a resistivity meter (Mitsubishi Chemical analytical tech co., ltd., Loresta GP) or a thermoelectric conversion characteristic evaluation device (advanced RIKO, inc., ZEM-3) used in examples described later.
In the carbon nanotube composite, the electrical conductivity is preferably 10S/cm or more, more preferably 100S/cm or more. The conductivity is preferably 1500S/cm or less, more preferably 1000S/cm or less. If the electrical conductivity is within the above range, a high-output carbon nanotube composite having a balance between the seebeck coefficient and the electrical conductivity is obtained, which is preferable.
<1-4.ZT>
Another index relating to thermoelectric conversion characteristics includes a dimensionless performance index ZT. ZT is determined by the following formula (ii).
ZT＝PF·T/κ (ii)
In the formula (ii), PF represents an output factor (═ α)2σ), T represents temperature, and κ represents thermal conductivity. The larger ZT indicates more excellent thermoelectric conversion material. As can be seen from the equation (ii), in order to increase ZT, it is preferable to increase the output factor, that is, the absolute value of the seebeck coefficient and the conductivity.
Further, as is clear from the formula (ii), in order to increase ZT, it is preferable that the thermal conductivity be small. This corresponds to the thermoelectric conversion material utilizing the temperature difference. When the thermal conductivity of the thermoelectric conversion material is large, the temperature in the substance becomes uniform, and a temperature difference is less likely to occur. Therefore, the thermoelectric conversion material having a high thermal conductivity tends to be difficult to efficiently generate electricity.
[2. carbon nanotube composite ]
A carbon nanotube composite according to one embodiment of the present invention comprises a carbon nanotube and a conductive polymer represented by the following formula (1) or the following formula (2),
[ chemical formula 7]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
[ chemical formula 8]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, X is a 2-valent aromatic group, and n is an integer of 3 or more)
90% by mass or more of the carbon nanotubes are semiconducting carbon nanotubes.
Metallic carbon nanotubes and semiconducting carbon nanotubes are present in the carbon nanotubes. The conductive polymer selectively wraps the semiconducting carbon nanotube due to its structure and electronic properties. Therefore, the semiconducting carbon nanotubes are dispersed in the solvent with good selectivity. As a result, a carbon nanotube composite containing semiconducting carbon nanotubes with high purity can be obtained by using the above conductive polymer. That is, in the carbon nanotube composite, the conductive polymer is in a state of being wound around the carbon nanotube.
The carbon nanotube composite can be considered for various applications and uses such as a thermoelectric conversion device. The thermoelectric conversion device composed of the carbon nanotube composite has flexibility. Therefore, the thermoelectric conversion device can be brought into close contact with a complicated three-dimensional surface such as a human body and piping, and body temperature, waste heat, and the like can be effectively utilized.
The carbon nanotube composite may be molded into a desired shape. For example, the carbon nanotube composite may be aggregated to form a film. The film may have a thickness of, for example, 0.1 to 1000. mu.m. The density of the film is not particularly limited, and may be 0.05 to 1.0g/cm3Or may be 0.1 to 0.5g/cm3. The film may be formed in a non-woven fabric-like structure in such a manner that the carbon nanotube composites are entangled with each other. Therefore, the film is lightweight and flexible. Such a film can be preferably used as a thermoelectric conversion device.
<2-1. carbon nanotubes >
The carbon nanotube composite includes carbon nanotubes. In addition, more than 90% by mass of the carbon nanotubes are semiconducting carbon nanotubes. In other words, when the carbon nanotube composite contains 100% by mass of carbon nanotubes, 90% by mass or more of the carbon nanotubes are semiconducting carbon nanotubes.
Carbon nanotubes synthesized by known synthesis methods, or commercially available carbon nanotubes, generally contain metallic carbon nanotubes and semiconducting carbon nanotubes in a mass ratio of about 1: 2 (see cambres, s.et., ACS Nano, vol.4, No.11,6717-6724, 2010). When a thermoelectric conversion material is produced using such carbon nanotubes, the thermal conductivity is high due to the metallic carbon nanotubes, and the seebeck coefficient is low. Therefore, when the content ratio of the metallic carbon nanotube is large, the ZT becomes small, and therefore sufficient thermoelectric conversion characteristics cannot be obtained. Therefore, the carbon nanotube composite preferably contains semiconducting carbon nanotubes with high purity.
In the above-mentioned patent documents 1 and 2 and non-patent documents 1 and 2, nothing is mentioned about improving the content ratio of the semiconductive carbon nanotubes. Therefore, it is considered that the conventional techniques described in these documents do not exhibit sufficient thermoelectric conversion characteristics.
The mass ratio of the metallic carbon nanotubes to the semiconducting carbon nanotubes can be determined by, for example, infrared spectrophotometry. First, an infrared spectrum is obtained in a sample that does not contain a substance that can affect the mass ratio of metallic carbon nanotubes to semiconducting carbon nanotubes (e.g., a conductive polymer used in one embodiment of the present invention). The infrared spectrum of this sample was used as a control. It is considered that the sample contains metallic carbon nanotubes and semiconducting carbon nanotubes in the above-described mass ratio of 1: 2. Then, the infrared spectrum of the sample for which the mass ratio of the metallic carbon nanotube to the semiconducting carbon nanotube is to be determined is compared with the infrared spectrum of the control, and the change in the band size of the absorbance from the plasmon resonance of the metallic carbon nanotube is evaluated. From the degree of change in the size of the band, the amount of change in the content ratio of the metallic carbon nanotube as compared with the control sample can be calculated. Thus, the mass ratio of the metallic carbon nanotubes to the semiconducting carbon nanotubes in a desired sample can be determined.
The carbon nanotubes preferably contain 95 mass% or more, more preferably 99 mass% or more, and still more preferably 99.9 mass% or more of the semiconducting carbon nanotubes in 100 mass%. The higher the content ratio of the semiconductive carbon nanotube is, the higher the output factor and ZT can be.
The diameter of the carbon nanotube may be appropriately determined in consideration of the structure of the conductive polymer. In addition, the diameter of the carbon nanotube means the diameter of a cross section perpendicular to the longitudinal direction. For example, the diameter of the carbon nanotube is preferably 1 to 5nm, more preferably 1 to 2nm, further preferably 1 to 1.7nm, and particularly preferably 1 to 1.4 nm. If the diameter of the carbon nanotube is in the above range, the conductive polymer described later is easily adsorbed. The diameter of the carbon nanotube can be measured by observation with an electron microscope, spectroscopic method, or the like.
Carbon nanotubes can be formed into bundles (small bundles). The diameter of the beam is preferably 5nm or less, more preferably 3nm or less. If the diameter of the bundle is 5nm or less, it is considered that the carbon nanotubes are well dispersed and can be uniformly doped.
The carbon nanotube may have a single-layer structure or a multi-layer structure (two, three, four or more layers). That is, the carbon nanotube may be a single-wall carbon nanotube (SWNT) or a multi-wall carbon nanotube (MWNT). However, the multilayered carbon nanotube may have both a semiconductive layer and a metallic layer. Therefore, from the viewpoint of improving the purity of the semiconducting carbon nanotubes, single-walled carbon nanotubes are preferably used.
The content of the carbon nanotubes in the carbon nanotube composite of 100 mass% is preferably 50 to 90 mass%, more preferably 65 to 85 mass%. If the content of the carbon nanotubes is within the above range, the properties derived from the carbon nanotubes in the carbon nanotube composite can be sufficiently exhibited.
<2-2. conductive Polymer >
The carbon nanotube composite contains a conductive polymer represented by the following formula (1) or the following formula (2).
[ chemical formula 9]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
[ chemical formula 10]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, X is a 2-valent aromatic group, and n is an integer of 3 or more)
The alkyl group is considered to be easily entangled with the carbon nanotube. In addition to such a structure, the conductive polymer is considered to be easily adsorbed to the semiconductive carbon nanotube due to the electronic properties of the aromatic group. Therefore, the conductive polymer can selectively and well adsorb the semiconductive carbon nanotubes. As the conductive polymer, can be mixed with 2 or more.
The polyfluorene derivative described in non-patent document 3 is insulating. Therefore, in non-patent document 3, when a polyfluorene derivative is used as a dispersant, the polyfluorene derivative must be removed in order to improve conductivity. On the other hand, if the conductive polymer is used, it is not necessary to remove it.
The number of carbon atoms of the alkyl group is preferably 7 to 20, and more preferably 10 to 14. If the number of carbon atoms is in the above range, the carbon nanotube can be more easily entangled by the alkyl group.
From the viewpoint of good separation efficiency of the semiconducting carbon nanotubes, n is preferably an integer of 5 or more. The upper limit of n is not particularly limited, but n is preferably an integer of 10 or less, more preferably an integer of 9 or less, from the viewpoint of high solubility of the conductive polymer.
The conductive polymer may have any structure other than the repeating unit represented by the formula (1) or the formula (2), but preferably includes the repeating unit represented by the formula (1) or the formula (2).
Examples of the X (aromatic group having a valence of 2) include: 2,1, 3-benzothiadiazole skeleton (benzothiadiazole skeleton), 5-fluoro-2, 1, 3-benzothiadiazole skeleton, 5, 6-difluoro-2, 1, 3-benzothiadiazole skeleton, thieno [3,4-c ] pyrrole-4, 6-dione skeleton (thienopyrrolodione skeleton), 1,4,5, 8-naphthalenediimide skeleton, 2, 5-dihydropyrrolo [3,4-c ] pyrrole-1, 4-dione skeleton (diketopyrrolopyrrole skeleton), and naphtho [1, 2-c: 5,6-c' ] bis [1,2,5] thiadiazole skeleton (naphthothiadiazole skeleton), and the like. In addition, in the present specification, a 2-valent aromatic group means a structure having at least 1 aromatic ring and 2 bonding sites. That is, the aromatic group having a valence of 2 can be said to have a structure derived from an aromatic compound having a functionality of 2. When the conductive polymer has X, more preferable electronic properties are exhibited. More preferably, X is a benzothiadiazole backbone. That is, the conductive polymer is more preferably represented by the following formula (3).
[ chemical formula 11]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
In view of the above, the conductive polymer is further preferably represented by the following formula (4) or the following formula (5).
[ chemical formula 12]
(wherein n is an integer of 3 or more)
[ chemical formula 13]
(wherein n is an integer of 3 or more)
The mass ratio of the carbon nanotubes to the conductive polymer in the carbon nanotube composite can be adjusted according to the application, and can be 1: 99-99: 1. In the case of using as a thermoelectric conversion material, the conductive polymer is preferably 1 to 40 parts by mass, more preferably 10 to 35 parts by mass, per 100 parts by mass of the carbon nanotube. When the content ratio of the conductive polymer is in the above range, the conductive polymer can be adsorbed to the carbon nanotube to be thin.
<2-3. p-type dopant and n-type dopant >
The carbon nanotube composite may further include a p-type dopant or an n-type dopant. Thus, the carbon nanotube composite can be used as a p-type thermoelectric conversion material or an n-type thermoelectric conversion material.
In the present specification, the p-type dopant means a dopant whose seebeck coefficient of a doped object is a positive value. Examples of the p-type dopant include: thiocyanate ion (SCN)-) Perchlorate ion (ClO)4 -) Permanganate ion (MnO)4 -) Tetrafluoroborate ion (BF)4 -) Iodate Ion (IO)3 -) Hexafluorophosphate ion (PF)6-) Triflate anion (TfO)-) Bis (trifluoromethanesulfonyl) amine anion (TFSI)-) Iodide ion (I)-) Bromide ion (Br)-) Chloride ion (Cl)-) Nitrate ion (NO)3 -) Or tosylate ion (Tos)-) Hydrogen acid and metal salts. Examples of the metal salt include a silver salt and a copper salt.
In the present specification, the n-type dopant means a dopant whose seebeck coefficient of a doped object is a negative value. Examples of the n-type dopant include: hydroxyl ion (OH)-) Alkoxy ion (CH)3O-，CH3CH2O-，i-PrO-And t-BuO-Etc.), mercapto ions (SH)-And alkylmercapto ion (CH)3S-And C2H5S-Etc.)), cyanuric acid ion (CN)-) Or a carboxyl ion (CH)3COO-Etc.) with cyclic ethylene oxide. Examples of the alkali metal contained in the alkali metal salt include: lithium ions, sodium ions and potassium ions. The cyclic oxirane may be a crown ether.
It is presumed that the anions contained in these p-type dopants or n-type dopants interact with the nanomaterial to be doped or cause a chemical reaction based on their unshared electron pairs.
[3. ink ]
An ink of an embodiment of the present invention contains a carbon nanotube composite of an embodiment of the present invention and a dispersion medium. In this case, the ink is preferably prepared by dispersing the carbon nanotube composite (unshaped carbon nanotube composite) in a dispersion medium. For example, a thermoelectric conversion function can be imparted to a desired member by applying the ink to the member and then removing the dispersion medium.
<3-1. Dispersion Medium >
The dispersion medium is not particularly limited as long as it is a dispersion medium in which the carbon nanotube composite can be dispersed. Examples of the dispersion medium include water and an organic solvent. Examples of the organic solvent include: toluene, o-dichlorobenzene, o-xylene, m-xylene, p-xylene, tetrahydrofuran, chloroform and the like.
[4. method for producing carbon nanotube composite ]
A method for producing a carbon nanotube composite according to an embodiment of the present invention includes:
a dispersion step of dispersing carbon nanotubes in a solvent containing a conductive polymer represented by the following formula (1) or formula (2), and
and a separation step of separating a carbon nanotube composite in which the carbon nanotubes include at least 90 mass% of semiconducting carbon nanotubes from the carbon nanotube dispersion liquid obtained in the dispersion step. Note that the matters already described in [ 1] to [ 3] ink, which are indexes relating to thermoelectric conversion characteristics, are not described below, and the above description is appropriately referred to.
[ chemical formula 14]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more)
[ chemical formula 15]
(in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, X is a 2-valent aromatic group, and n is an integer of 3 or more)
The conductive polymer selectively wraps the semiconducting carbon nanotube due to its structure and electronic properties. Therefore, in the dispersing step, the semiconducting carbon nanotubes can be selectively and well dispersed in the solvent. On the other hand, metallic carbon nanotubes are less dispersible than semiconducting carbon nanotubes wrapped in a conductive polymer. Therefore, since the metallic carbon nanotubes are easily removed in the separation step, the carbon nanotube composite containing the semiconducting carbon nanotubes with high purity can be separated.
<4-1. Dispersion step >
The dispersion step is a step of dispersing the carbon nanotubes in a solvent containing the conductive polymer represented by the formula (1) or the formula (2). Thus, the conductive polymer is adsorbed to the semiconducting carbon nanotubes, and the semiconducting carbon nanotubes are selectively and well dispersed.
The solvent is not particularly limited as long as it dissolves the conductive polymer, and examples thereof include: toluene, o-xylene, m-xylene, p-xylene, o-dichlorobenzene, tetrahydrofuran, chloroform and the like. Among them, the solvent is preferably toluene, o-xylene, m-xylene, or p-xylene from the viewpoint of the polarity of the solvent.
Examples of a method of dispersing the carbon nanotubes in the solvent include a method using a homogenizer. Examples of the homogenizing device include a stirring homogenizer and an ultrasonic homogenizer. From the viewpoint of more uniform dispersion, it is preferable to disperse the carbon nanotubes in the solvent using an ultrasonic homogenizer.
The temperature in the dispersing step is preferably 0 to 10 ℃ from the viewpoint of suppressing the introduction of defects.
<4-2. isolation Process >
The separation step is a step of separating a carbon nanotube composite in which the carbon nanotubes include at least 90 mass% of semiconducting carbon nanotubes from the carbon nanotube dispersion liquid obtained in the dispersion step. In other words, when the carbon nanotubes contained in the separated carbon nanotube composite are 100 mass%, 90 mass% or more thereof are semiconducting carbon nanotubes. That is, the separation step is a step of removing most of the metallic carbon nanotubes that are not adsorbed to the conductive polymer.
In the separation step, the carbon nanotube composite in which the carbon nanotubes include 95 mass% or more of semiconducting carbon nanotubes is preferably separated. By increasing the purity of the semiconducting carbon nanotubes, a carbon nanotube composite having more excellent thermoelectric conversion characteristics can be obtained.
The method for performing the separation step is not particularly limited as long as it is a method capable of separating the semiconducting carbon nanotubes with high purity. Examples of such a method include a method using a centrifuge. By centrifuging the carbon nanotube dispersion liquid using a centrifuge, most of the metallic carbon nanotubes can be precipitated, and a supernatant liquid containing the semiconducting carbon nanotubes with high purity can be separated. By recovering the supernatant, a carbon nanotube composite can be separated, wherein the carbon nanotubes contain 90 mass% or more of semiconducting carbon nanotubes.
The solvent may be further removed from the recovered supernatant. Further, by replacing the solvent with the dispersion medium, the ink according to an embodiment of the present invention can be obtained.
<4-3. Molding Process >
The above-described manufacturing method may include a molding step of molding the carbon nanotube composite obtained by the separation step into a desired shape (for example, a film). As a method of forming the carbon nanotube composite into a desired shape, for example, a method of forming the carbon nanotube composite into a desired shape by aggregating the carbon nanotube composite is exemplified.
As such a method, there is a method of molding a membrane by filtering a dispersion liquid containing a carbon nanotube composite on a membrane filter. Specifically, the dispersion containing the carbon nanotube composite is filtered using a membrane filter having 0.1 to 2 μm pores, and the carbon nanotube composite collected on the membrane filter is dried and molded into a membrane. The dispersion may be the supernatant liquid or the ink according to an embodiment of the present invention.
<4-4. doping Process >
The manufacturing method may include a step of bringing a p-type dopant or an n-type dopant into contact with the carbon nanotube composite. Thus, the carbon nanotube composite can be used as a p-type thermoelectric conversion material or an n-type thermoelectric conversion material.
Examples of the method of performing the doping step after the forming step include a method of immersing the carbon nanotube composite formed into a desired shape in a solution containing a p-type dopant or an n-type dopant, and a method of applying a solution containing a p-type dopant or an n-type dopant to the carbon nanotube composite formed into a desired shape.
The solvent of the solution containing the p-type dopant or the n-type dopant may be water or an organic solvent. The solvent is preferably an organic solvent, and more preferably methanol, ethanol, propanol, butanol, acetonitrile, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, or the like. These solvents can be removed by drying the carbon nanotube composite impregnated or coated as described above.
The concentration of the p-type dopant or the n-type dopant in the solution can be adjusted according to the desired thermoelectric characteristics. The concentration may be, for example, 0.001 to 1mol/L or 0.01 to 0.1 mol/L.
The doping step may be performed before or after the dispersing step or the separating step. In this case, a method of adding a p-type dopant or an n-type dopant to a solvent containing the conductive polymer, a carbon nanotube dispersion, or a supernatant recovered in the separation step can be employed.
The present invention is not limited to the above embodiments, and various modifications can be made within the scope shown in the protection scope, and embodiments obtained by appropriately combining technical means disclosed in the respective different embodiments are also included in the technical scope of the present invention.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. Hereinafter, the compound of formula (4) having a poly (cyclopentadithiophene) skeleton may be referred to as PCPDT, and the compound of formula (5) having a poly (cyclopentadithiophene) skeleton and a benzothiadiazole skeleton may be referred to as PCPDTBT. In addition, carbon nanotubes are sometimes referred to as CNTs.
[ evaluation of physical Properties ]
< Infrared Spectroscopy >
The absorbance was measured by fourier transform infrared spectroscopy on the films obtained in example 1 and comparative example 1 described later using an infrared microscope (manufactured by Bruker Corporation, hyperon 2000). In addition, instead of the PCPDTBT of example 1 and comparative example 1, an aqueous solution containing 1 mass% of Pluronic (registered trademark) F127 (manufactured by BASF corporation) was used, and the absorbance was measured for a sample in which carbon nanotubes were dispersed in the same manner. This sample was used as an untreated sample (control sample). That is, the sample contained metallic CNTs and semiconducting CNTs at a mass ratio of about 1: 2. The obtained infrared spectra were compared, and the degree of separation of semiconducting CNTs was evaluated from the decrease in band from plasmon resonance of metallic CNTs.
< thermoelectric conversion characteristics >
(a) Electrical conductivity of
The electric conductivity of the films obtained in the examples and comparative examples described later was measured by a 4-probe method using a thermoelectric conversion characteristic evaluation apparatus (manufactured by ADVANCE RIKO, inc., ZEM-3). The measurement temperature was 310K (37 ℃).
(b) Seebeck coefficient
The seebeck coefficient of the film obtained in the example and the comparative example described later was measured using a thermoelectric conversion characteristic evaluation apparatus (manufactured by ADVANCE RIKO, inc., ZEM-3). The measurement temperature was 310K (37 ℃).
(c) Output factor
The output factor PF of the films obtained in examples and comparative examples described later was calculated from the above formula (i) using the conductivity σ and the seebeck coefficient α obtained by the above methods.
[ thermoelectric conversion characteristics (I) of undoped CNT composite ]
< example 1>
PCPDTBT is synthesized by reference to the prior art (Kettle, J.et.al., Solar Energy Materials and Solar Cells, Volume95, Issue8, Pages2186-2193,2011). The PCPDTBT thus obtained is represented by the formula (5) wherein n is about 5 to 10. 8mg of single-walled carbon nanotubes (RN-020, manufactured by Raymor, having a diameter of about 1.1 to 1.7nm) were put in 20mL of toluene in which 2.5mg of PCPDTBT was dissolved. The single-walled carbon nanotubes were dispersed in toluene at about 4 ℃ for 60 minutes using an ultrasonic homogenizer (Q125, manufactured by Qsonica).
The thus obtained dispersion was centrifuged at 10000rpm for 60 minutes by a centrifuge (KUBOTA Corporation co., ltd., Tabletop cooled centrifuge 5500). From the centrifuged dispersion, 70 vol% of the supernatant was recovered.
The recovered supernatant was filtered by suction filtration through a 0.2 μm pore membrane filter (manufactured by Merck millipore, Omnipore membrane filter JGWP02500) to deposit a CNT film. The obtained CNT film was placed on a PET film, and in this state, the infrared spectrum and the thermoelectric conversion characteristics were measured.
Fig. 1 is a graph showing an infrared spectrum of the CNT film of example 1. The vertical axis represents normalized absorbance, and the horizontal axis represents photon energy. In addition, 5,6, 7, 8, and 9 of 0.1eV or less on the horizontal axis represent 0.05, 0.06, 0.07, 0.08, and 0.09, respectively. In addition, 2, 3,4, 5,6, 7, 8, 9 between 0.1eV and 1eV of the horizontal axis represent 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively. The black line (F127 dispersion) shows data obtained from the dispersion using Pluronic F127, and the gray line (PCPDTBT dispersion) shows data obtained from the dispersion using PCPDTBT. In fig. 1, it is understood that in the F127 dispersion, although there are bands derived from plasmon resonance of the metallic CNTs in the region smaller than 0.09eV, these bands almost disappear in the PCPDTBT dispersion. Therefore, it is considered that the semiconducting CNTs are contained in an amount of 99 mass% or more based on 100 mass% of the CNTs contained in the CNT film of example 1.
In addition, the interband transition S from semiconducting CNTs11The peak of (2) shows that the center of the diameter distribution of the CNT is 1.0 to 1.2 nm.
In addition, in the commercially available semiconducting CNTs, a plasma resonance band is seen even with high purity due to doping during the preparation process (see Morimoto, t., ethylene. acsnano, vol.8, No.10, 9897-. The semiconducting CNTs obtained in example 1 were subjected to the same plasma resonance, and as a result, were not more than the observation limit, and it was found that the semiconducting CNTs had not been significantly doped, nor had their semiconductor purity been extremely high. That is, it can be said that example 1 is a method for producing a semiconducting CNT having a quality much higher than that of the conventional one.
Fig. 5 is a view showing a scanning electron microscope image of the carbon nanotube film of example 1. The CNTs observed in fig. 5 all had diameters of 5nm (resolution) or less. The typical CNT band is 20 to 30nm, and it is found that the CNT is well dispersed in consideration of this point. That is, it is considered that the semiconducting CNTs are well dispersed by the conductive polymer being selectively and well entangled to the semiconducting CNTs.
< comparative example 1>
A CNT film was obtained in the same manner as in example 1 except that a single-walled carbon nanotube (registered trademark) of Tuball (diameter about 1.75 to 1.85nm), manufactured by OCSiAl corporation was used, and the infrared spectrum and the thermoelectric conversion property thereof were measured.
Fig. 2 is a graph showing an infrared spectrum of the CNT film of comparative example 1. The vertical and horizontal axes are the same as in fig. 1. The black line (F127 dispersion) represents data obtained from the dispersion using pluronic F127, and the gray line (PCPDTBT dispersion) represents data obtained from the dispersion using PCPDTBT. As can be seen from fig. 2, in the F127 dispersion, the band derived from the plasmon resonance of the metallic CNT existing in the region lower than 0.09eV was slightly reduced (about 15%) in the PCPDTBT dispersion. The mass ratio of the metallic CNT to the semiconducting CNT in the commercially available CNT is generally 1: 2, and in consideration of this, it is considered that the semiconducting CNT is contained in about 80 mass% with respect to 100 mass% of the CNT contained in the CNT film of comparative example 1.
< comparison of thermoelectric conversion characteristics >
The measurement results of the thermoelectric conversion characteristics of example 1 and comparative example 1 are shown in table 1.
[ Table 1]
As is apparent from table 1, in example 1 in which the semiconducting CNTs were contained at high purity, the seebeck coefficient was dramatically improved, and the CNT film was expressed as a semiconductor.
[ thermoelectric conversion characteristics (II) of undoped CNT composite ]
< example 2>
A CNT film was obtained in the same manner as in example 1, except that PCPDT was used instead of PCPDTBT. The PCPDT used is such that n in the formula (4) is about 25 to 35.
< example 3>
A CNT film was obtained in the same manner as in example 1 except that HP, manufactured by KH Chemicals, was used as CNT instead of RN-020, manufactured by Raymor.
< example 4>
A CNT film was obtained in the same manner as in example 2 except that HP, manufactured by KH Chemicals, was used as CNT instead of RN-020, manufactured by Raymor.
< comparative example 2>
A CNT film was obtained in the same manner as in example 1, except that a compound represented by the following formula (6) (hereinafter, also referred to as PFD) having a polyfluorene skeleton was used instead of PCPDTBT. The PFD used is such that n is about 300 to 740 in the above formula (6).
[ chemical formula 16]
< comparative example 3>
A CNT film was obtained in the same manner as in comparative example 2 except that HP, manufactured by KH Chemicals, was used as CNT instead of RN-020, manufactured by Raymor.
< comparison of thermoelectric conversion characteristics >
The CNT films obtained in examples 2 to 4 and comparative example 2 were placed on a PET film, and the thermoelectric conversion characteristics were measured. Although not shown, it was confirmed by the same method as in example 1 that the semiconducting CNTs were 90 mass% or more with respect to 100 mass% of the CNTs included in the CNT film in examples 2 to 4 and comparative examples 2 and 3.
Fig. 3 is a graph showing thermoelectric conversion characteristics of the CNT films of examples 1 to 4 and comparative examples 2 and 3, fig. 3 shows a relationship between the electric conductivity σ and the seebeck coefficient α, fig. 3 shows that 6 and 8 below 100 respectively represent 60 and 80, 2, 4,6 and 8 between 100 and 1000 respectively represent 200, 400, 600 and 800, and 2 above 1000 represents 2000 in the vertical axis of fig. 3, and in addition, 6 below 0.1 represents 0.06, 2, 4 and 6 between 0.1 and 1 respectively represent 0.2, 0.4, 0.6, and 2 above 10 represents 20 in the horizontal axis of fig. 3.
As can be seen from fig. 3, examples 1 and 2 have higher seebeck coefficients than comparative example 2. The purity of the semiconducting CNTs was example 1> example 2> comparative example 2. Similarly, as can be seen from fig. 3, examples 3 and 4 have higher seebeck coefficients than comparative example 3. The purity of the semiconducting CNTs was example 3> example 4> comparative example 3.
[ thermoelectric conversion characteristics of the doped CNT composite completed ]
< example 5>
The obtained CNT film was immersed in a butanol solution of AgTFSI of 0.01 to 4mg/mL for 5 minutes in the same manner as in example 1. Thereafter, the CNT film was dried at room temperature under reduced pressure for 60 minutes to obtain a p-type CNT film. The obtained p-type CNT film was placed on a PET film, and in this state, the thermoelectric conversion characteristics were measured.
< example 6>
An n-type CNT film was obtained in the same manner as in example 2, except that a KOH/benzene-18-crown-6-ether butanol solution of 0.005 to 0.075mol/mL was used instead of the AgTFSI butanol solution. The obtained n-type CNT film was placed on a PET film, and in this state, the thermoelectric conversion characteristics were measured.
< comparative example 4>
5mg of single-walled carbon nanotubes (RN-020, manufactured by Raymor, having a diameter of about 1.1 to 1.7nm) were put into an aqueous solution containing 1 mass% of Pluronic (registered trademark) F127 (manufactured by BASF). The single-walled carbon nanotubes were dispersed in the aqueous solution at about 4 ℃ for 60 minutes using an ultrasonic homogenizer (Q125, manufactured by Qsonica).
The thus obtained dispersion was centrifuged at 10000rpm for 60 minutes by a centrifuge (KUBOTA Corporation co., ltd., Tabletop cooled centrifuge 5500). From the centrifuged dispersion, 70 vol% of the supernatant was recovered.
The recovered supernatant was filtered by suction filtration through a 0.2 μm pore membrane filter (manufactured by Merck millipore, Omnipore membrane filter JGWP02500) to deposit a CNT film.
The CNT film obtained is immersed in an AgTFSI butanol solution of 0.01 to 4mg/mL for 5 minutes. Then, the CNT film was dried at room temperature under reduced pressure for 60 minutes to obtain a p-type CNT film. The obtained p-type CNT film was placed on a PET film, and in this state, the thermoelectric conversion characteristics were measured. The p-type CNT film comprises metallic CNTs and semiconducting CNTs in a mass ratio of about 1: 2.
< comparison of thermoelectric conversion characteristics >
Fig. 4 is a graph showing thermoelectric conversion characteristics of the p-type CNT film of example 5, the n-type CNT film of example 6, and the p-type CNT film of comparative example 4, fig. 4 (a) is a graph showing a relationship between conductivity σ and absolute value | α | of seebeck coefficient in the p-type CNT film of example 5, the n-type CNT film of example 6, and the p-type CNT film of comparative example 4, and fig. 4 (a) is the same as fig. 3 in the vertical axis reading method, and it is clear from fig. 4 (a) that the absolute value of seebeck coefficient changes with a change in conductivity in both p-type doping and n-type doping when the purity of semiconducting CNTs is improved using PCPDTBT.
Fig. 4 (b) is a graph showing the relationship between the conductivity σ and the output factor PF in the p-type CNT film of example 5, the n-type CNT film of example 6, and the p-type CNT film of comparative example 4. As shown in fig. 4 (b), when the purity of the semiconducting CNTs is improved by using PCPDTBT, a high output factor is obtained in both p-type doping and n-type doping when the conductivity is 100S/cm or more. Particularly, in the case where the conductivity of the p-type CNT film of example 5 is about 100S/cm, it is possible to obtain more than 400. mu.W/mK2Among them, there are also output factors which appear to exceed 500. mu.W/mK2The output factor of (1).
Industrial applicability
The present invention can be used for, for example, a thermoelectric conversion material.
Claims (9)
1. A carbon nanotube composite comprising a carbon nanotube and a conductive polymer represented by the following formula (1) or the following formula (2),
in the formula, R1And R2Each independently an alkyl group having 4 to 24 carbon atoms, n is an integer of 3 or more,
in the formula, R1And R2Independently of each other, is an alkyl group having 4 to 24 carbon atoms, X is a 2-valent aromatic group, n is an integer of 3 or more,
at least 90% by mass of the carbon nanotubes are semiconducting carbon nanotubes.
2. The carbon nanotube composite according to claim 1, wherein the conductive polymer is represented by the following formula (3),
in the formula, R1And R2Each independently represents an alkyl group having 4 to 24 carbon atoms, and n is an integer of 3 or more.
3. The carbon nanotube composite according to claim 1 or 2, wherein 95% by mass or more of the carbon nanotubes are semiconducting carbon nanotubes.
4. The carbon nanotube composite according to any one of claims 1 to 3, further comprising a p-type dopant or an n-type dopant.
5. An ink comprising the carbon nanotube composite according to any one of claims 1 to 4 and a solvent.
6. A method for producing a carbon nanotube composite, comprising:
a dispersion step of dispersing carbon nanotubes in a solvent containing a conductive polymer represented by the following formula (1) or formula (2); and
a separation step of separating a carbon nanotube composite in which carbon nanotubes include at least 90 mass% of semiconducting carbon nanotubes from the carbon nanotube dispersion liquid obtained in the dispersion step,
in the formula, R1And R2Each independently an alkyl group having 4 to 24 carbon atoms, n is an integer of 3 or more,
in the formula, R1And R2Each independently is an alkyl group having 4 to 24 carbon atoms, X is a 2-valent aromatic group, and n is an integer of 3 or more.
7. The method for producing a carbon nanotube composite according to claim 6,
the conductive polymer is represented by the following formula (3),
in the formula, R1And R2Each independently of the other, is the number of carbon atomsIs an alkyl group of 4 to 24, and n is an integer of 3 or more.
8. The method for producing a carbon nanotube composite according to claim 6 or 7, wherein in the separation step, the carbon nanotube composite is separated, and wherein the carbon nanotubes in the carbon nanotube composite contain 95 mass% or more of semiconducting carbon nanotubes.
9. The method for producing a carbon nanotube composite according to claim 1, comprising a doping step of bringing a p-type dopant or an n-type dopant into contact with the carbon nanotube composite.
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| CN102268165A (en) * | 2011-07-04 | 2011-12-07 | 海南大学 | Preparation method of carbon nano tube/polymer conductive composite material |
| CN103030130A (en) * | 2012-12-14 | 2013-04-10 | 同济大学 | Method for self-assembling carbon nano tubes in water by regulating temperature to guide polymer to modify carbon nano tubes |
| JP2013098299A (en) * | 2011-10-31 | 2013-05-20 | Fujifilm Corp | Thermoelectric conversion material and thermoelectric conversion element |
| JP2014033170A (en) * | 2011-10-31 | 2014-02-20 | Fujifilm Corp | Thermoelectric conversion material and thermoelectric element |
| JP2014239092A (en) * | 2013-06-06 | 2014-12-18 | 公立大学法人首都大学東京 | Thermoelectric conversion material and thermoelectric conversion element |
| JP2015035599A (en) * | 2013-07-08 | 2015-02-19 | 富士フイルム株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and thermoelectricity-generating article and sensor-use power source using the same |
| CN105585728A (en) * | 2015-11-26 | 2016-05-18 | 中国科学院金属研究所 | Method for coating polymeric microsphere with carbon nano tube |
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| CN102268165A (en) * | 2011-07-04 | 2011-12-07 | 海南大学 | Preparation method of carbon nano tube/polymer conductive composite material |
| JP2013098299A (en) * | 2011-10-31 | 2013-05-20 | Fujifilm Corp | Thermoelectric conversion material and thermoelectric conversion element |
| JP2014033170A (en) * | 2011-10-31 | 2014-02-20 | Fujifilm Corp | Thermoelectric conversion material and thermoelectric element |
| CN103030130A (en) * | 2012-12-14 | 2013-04-10 | 同济大学 | Method for self-assembling carbon nano tubes in water by regulating temperature to guide polymer to modify carbon nano tubes |
| JP2014239092A (en) * | 2013-06-06 | 2014-12-18 | 公立大学法人首都大学東京 | Thermoelectric conversion material and thermoelectric conversion element |
| JP2015035599A (en) * | 2013-07-08 | 2015-02-19 | 富士フイルム株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and thermoelectricity-generating article and sensor-use power source using the same |
| CN105585728A (en) * | 2015-11-26 | 2016-05-18 | 中国科学院金属研究所 | Method for coating polymeric microsphere with carbon nano tube |
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