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WO2014178284A1 - Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article pour la génération de puissance thermoélectrique, et alimentation électrique pour capteurs - Google Patents

Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article pour la génération de puissance thermoélectrique, et alimentation électrique pour capteurs Download PDF

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WO2014178284A1
WO2014178284A1 PCT/JP2014/060844 JP2014060844W WO2014178284A1 WO 2014178284 A1 WO2014178284 A1 WO 2014178284A1 JP 2014060844 W JP2014060844 W JP 2014060844W WO 2014178284 A1 WO2014178284 A1 WO 2014178284A1
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thermoelectric conversion
group
general formula
conversion element
integer
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Japanese (ja)
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亮 浜崎
西尾　亮
丸山　陽一
野村　公篤
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Fujifilm Corp
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Definitions

  • the present invention relates to a thermoelectric conversion material, a thermoelectric conversion element, an article for thermoelectric power generation using these, and a power source for sensors.
  • thermoelectric conversion materials that can mutually convert heat energy and electrical energy are used in thermoelectric conversion elements such as thermoelectric power generation elements and Peltier elements.
  • thermoelectric power generation using thermoelectric conversion materials and thermoelectric conversion elements can directly convert thermal energy into electric power, does not require moving parts, and is used for wristwatches that operate at body temperature, power supplies for remote areas, power supplies for space, etc. ing.
  • thermoelectric conversion performance is a dimensionless figure of merit ZT (hereinafter, simply referred to as a figure of merit ZT).
  • This figure of merit ZT is represented by the following formula (A).
  • thermoelectromotive force hereinafter sometimes referred to as thermoelectromotive force
  • conductivity ⁇ per absolute temperature 1K Reduction of thermal conductivity ⁇ is important.
  • thermoelectric conversion materials are required to have good thermoelectric conversion performance, and inorganic materials are mainly put into practical use at present.
  • the inorganic material has a complicated processing process for the thermoelectric conversion element, is expensive, and may contain harmful substances.
  • organic thermoelectric conversion elements can be manufactured at a relatively low cost and can be easily processed such as film formation, research has been actively conducted in recent years. Has been reported.
  • an organic material having a high Seebeck coefficient and electrical conductivity and low thermal conductivity is required.
  • a thermoelectric conversion material made of a conductive polymer has been proposed (see Patent Document 1).
  • thermoelectric conversion layer As a conductive organic material, a nanoconductive material (a nanometer-sized conductive material) such as a carbon nanotube is known.
  • nano-conductive materials tend to aggregate due to intermolecular forces and have very poor dispersibility. Therefore, when a thermoelectric conversion layer is formed using a thermoelectric conversion material containing a nano-conductive material, adhesion with a base material or an electrode is deteriorated, resulting in a decrease in thermoelectric conversion performance.
  • the present invention has a good dispersibility of the nano-conductive material, a thermoelectric conversion material having a high thermoelectromotive force, and uses this for the thermoelectric conversion layer, and is excellent in adhesion between the thermoelectric conversion layer and the electrode and thermoelectric conversion performance. It is an object of the present invention to provide a thermoelectric conversion element, a thermoelectric power generation article using the thermoelectric conversion element, and a sensor power source.
  • the present inventors have studied an organic material that can enhance the dispersibility of the nanoconductive material by coexisting with the nanoconductive material in the thermoelectric conversion layer of the thermoelectric conversion element. As a result, it was found that by using an ionic compound having a specific structure together with the nanoconductive material, the dispersibility of the nanoconductive material is improved and a thermoelectric conversion material having a high thermoelectromotive force can be obtained. .
  • the thermoelectric conversion element using the material for the thermoelectric conversion layer is excellent in adhesion between the thermoelectric conversion layer and the electrode and exhibits high thermoelectric conversion performance.
  • the present invention has been completed based on these findings.
  • thermoelectric conversion element having a first electrode, a thermoelectric conversion layer, and a second electrode on a base material, wherein the thermoelectric conversion layer includes a nano-conductive material and the following general formulas (1a) to (3b):
  • the thermoelectric conversion element containing the at least 1 sort (s) of compound selected from the compound represented by this.
  • X ⁇ represents a counter anion.
  • R 11 to R 13 each independently represents an alkyl group or a heteroaryl group.
  • R 12 and R 13 may combine with each other to form a ring.
  • n represents an integer of 2 or 3.
  • X p- represents a p-valent counter anion, and p represents an integer of 1 to 3.
  • k represents an integer of 1 to 3.
  • L represents an n-valent linking group or a single bond.
  • R ⁇ 12 > and R ⁇ 13 > are synonymous with General formula (1a).
  • the plurality of R 12 and R 13 may be the same or different.
  • X ⁇ represents a counter anion.
  • R 21 to R 24 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Any two groups selected from R 21 to R 24 may be bonded to each other to form a ring.
  • n represents an integer of 2 or 3.
  • X p- represents a p-valent counter anion, and p represents an integer of 1 to 3.
  • k represents an integer of 1 to 3.
  • n kp.
  • L represents an n-valent linking group or a single bond.
  • R 22 to R 24 have the same meaning as in general formula (2a). The plurality of R 22 to R 24 may be the same or different.
  • X ⁇ represents a counter anion.
  • A represents a nitrogen-containing heterocyclic group.
  • R 31 and R 32 each independently represents an alkyl group, an aryl group, or a heteroaryl group. R 31 may combine with A to form a ring.
  • m represents 0 or 1
  • m is 0 when A is a nitrogen-containing aromatic heterocyclic group
  • m is 1 when A is a nitrogen-containing aliphatic heterocyclic group.
  • n represents an integer of 2 or 3.
  • X p- represents a p-valent counter anion, and p represents an integer of 1 to 3.
  • k represents an integer of 1 to 3.
  • n kp.
  • L represents an n-valent linking group or a single bond.
  • A, R 32 and m have the same meanings as in the general formula (3a).
  • a plurality of A and R 32 may be the same or different.
  • thermoelectric conversion element according to ⁇ 1> wherein in the general formulas (1a) and (1b), R 11 to R 13 are alkyl groups.
  • X ⁇ or X p ⁇ is a conjugate base of a strong acid.
  • thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 5>, wherein the compounds represented by the general formulas (1a) to (3b) have a melting point of 100 ° C. or lower.
  • the content ratio of the nanoconductive material and the compounds represented by the general formulas (1a) to (3b) in the thermoelectric conversion layer is 1: 9 to 9: 1 on a mass basis, ⁇ 1> to ⁇ 1
  • ⁇ 8> The thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 7>, wherein the nano conductive material is a carbon nanotube.
  • thermoelectric conversion according to any one of ⁇ 1> to ⁇ 8>, wherein the first electrode and the second electrode are each independently formed of aluminum, gold, silver, or copper. element.
  • thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 9>, wherein the thermoelectric conversion layer contains a conjugated polymer.
  • thermoelectric conversion layer contains a conjugated polymer.
  • thermoelectric conversion material for forming a thermoelectric conversion layer of a thermoelectric conversion element comprising a nano-conductive material and at least one compound selected from compounds of the following general formulas (1a) to (3b).
  • thermoelectric conversion material according to ⁇ 13> which contains an organic solvent.
  • thermoelectric conversion material according to ⁇ 14> wherein the nanoconductive material is dispersed in an organic solvent.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the xxx group when the xxx group is referred to as a substituent, the xxx group may have an arbitrary substituent.
  • the repeating structure represented by each formula includes different repeating structures as long as they are within the range represented by the formula, even if they are not exactly the same repeating structure.
  • the repeating structure represented by each formula may be only a repeating structure having a methyl group, and has another alkyl group such as an ethyl group in addition to the repeating structure having a methyl group. It may contain a repeating structure.
  • thermoelectric conversion material of the present invention has good dispersibility of the nano-conductive material and has a high thermoelectromotive force.
  • the heat conversion element of the present invention using the material for the thermoelectric conversion layer is excellent in adhesion between the thermoelectric conversion layer and the electrode, and exhibits high thermoelectric conversion performance.
  • thermoelectric power-generating article and sensor power source of the present invention using the thermoelectric conversion element exhibit excellent thermoelectric conversion performance.
  • thermoelectric conversion element of this invention It is a figure which shows typically the cross section of an example of the thermoelectric conversion element of this invention.
  • the arrows in FIG. 1 indicate the direction of the temperature difference applied when the element is used.
  • FIG. 2 shows typically the cross section of another example of the thermoelectric conversion element of this invention.
  • thermoelectric conversion element of the present invention has a first electrode, a thermoelectric conversion layer, and a second electrode on a base material.
  • the thermoelectric conversion layer is formed on the substrate by the thermoelectric conversion material of the present invention containing a nano conductive material and at least one compound selected from the compounds represented by the following general formulas (1a) to (3b). Molded.
  • thermoelectric conversion performance of the thermoelectric conversion element of the present invention can be expressed by a figure of merit ZT represented by the following formula (A).
  • Figure of merit ZT S 2 ⁇ ⁇ ⁇ T / ⁇ (A)
  • thermoelectric conversion element is used for a wristwatch, a power source for remote areas, a power source for space, and the like, it is also required that the initial thermoelectric conversion performance can be maintained over a long period of time.
  • thermoelectric conversion element functions to transmit the temperature difference in the thickness direction or the surface direction in a state where the temperature difference is generated in the thickness direction or the surface direction of the thermoelectric conversion layer. Therefore, it is necessary to form the thermoelectric conversion layer by forming it into a shape having a thickness of 2 mm. For this reason, when the thermoelectric conversion layer is formed by coating, the thermoelectric conversion material is required to have good coatability and film formability.
  • the thermoelectric conversion material of the present invention has good dispersibility of the nano-conductive material, excellent coating properties and film formability, and is suitable for molding and processing into a thermoelectric conversion layer.
  • thermoelectric conversion material of the present invention and then the thermoelectric conversion element of the present invention will be described.
  • thermoelectric conversion material of the present invention is a thermoelectric conversion composition for forming a thermoelectric conversion layer of a thermoelectric conversion element, and is selected from nano-conductive materials and compounds represented by the following general formulas (1a) to (3b) Containing at least one compound.
  • thermoelectric conversion material of the present invention first, each component used for the thermoelectric conversion material of the present invention will be described.
  • the nano conductive material used in the present invention may be any material having conductivity at least on one side and having a nanometer size, and a carbon material having conductivity of a nanometer size (hereinafter referred to as nano carbon material).
  • a metal material having a nanometer size hereinafter sometimes referred to as a nano metal material.
  • the nanoconductive materials used in the present invention are carbon nanotubes, carbon nanofibers, fullerenes, graphite, graphene and carbon nanoparticle nanocarbon materials, and metal nanowires, which will be described later, respectively. Carbon nanotubes are particularly preferable from the viewpoint of improving conductivity and improving dispersibility in a solvent.
  • the content of the nano conductive material in the thermoelectric conversion material is preferably 10 to 90% by mass in the total solid content of the thermoelectric conversion material, that is, in the thermoelectric conversion layer in terms of thermoelectric conversion performance, and preferably 15 to 85%. More preferably, it is 20% by weight, and particularly preferably 20-80% by weight.
  • a nano electroconductivity material may be used individually by 1 type, and may use 2 or more types together. When two or more types are used together as the nano-conductive material, at least one type of nano-carbon material and nano metal material may be used in combination, or two types of nano-carbon material or nano metal material may be used in combination. .
  • Nano-carbon material is a carbon material having a nanometer size and conductivity.
  • a carbon-carbon bond composed of sp 2 hybrid orbitals of carbon atoms. Is a nanometer-sized conductive material formed by chemically bonding carbon atoms together.
  • fullerenes including metal-encapsulated fullerenes and onion-like fullerenes
  • carbon nanotubes including peapods
  • carbon nanohorns with one side closed, carbon nanofibers, carbon nanowalls
  • carbon Examples thereof include nanofilaments, carbon nanocoils, vapor grown carbon (VGCF), graphite, graphene, carbon nanoparticles, and cup-shaped nanocarbon materials having holes in the heads of carbon nanotubes.
  • various carbon blacks having a graphite-type crystal structure and exhibiting conductivity can be used as the nanocarbon material, such as ketjen black and acetylene black. Specifically, the trade name “Vulcan” And carbon black.
  • nanocarbon materials can be manufactured by a conventional manufacturing method. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, gas phase flow method, carbon monoxide is reacted with iron catalyst at high temperature and high pressure in the gas phase. Examples include HiPco method and oil furnace method for growth.
  • the nanocarbon material produced in this way can be used as it is, or a material purified by washing, centrifugation, filtration, oxidation, chromatography, or the like can be used.
  • the nanocarbon material should be pulverized using a ball-type kneading device such as a ball mill, vibration mill, sand mill, roll mill, etc., or cut short by chemical or physical treatment, etc., as necessary. You can also.
  • a ball-type kneading device such as a ball mill, vibration mill, sand mill, roll mill, etc., or cut short by chemical or physical treatment, etc., as necessary. You can also.
  • the size of the nano conductive material used in the present invention is not particularly limited as long as it is a nanometer size.
  • the nano-conductive material is a carbon nanotube, carbon nanohorn, carbon nanofiber, carbon nanofilament, carbon nanocoil, vapor grown carbon (VGCF), cup-shaped nanocarbon material, etc.
  • the average length is not particularly limited, but is preferably 0.01 to 1000 ⁇ m and more preferably 0.1 to 100 ⁇ m from the viewpoints of manufacturability, film formability, conductivity, and the like.
  • the diameter is not particularly limited, but is preferably 0.4 to 100 nm, more preferably 50 nm or less, and still more preferably 15 nm or less from the viewpoint of durability, transparency, film formability, conductivity, and the like. .
  • carbon nanotubes are preferable, and carbon nanotubes are particularly preferable.
  • CNT is a single-layer CNT in which one carbon film (graphene sheet) is wound in a cylindrical shape, a two-layer CNT in which two graphene sheets are wound in a concentric shape, and a plurality of graphene sheets in a concentric shape
  • multi-walled CNTs wound around In the present invention, single-walled CNTs, double-walled CNTs, and multilayered CNTs may be used alone, or two or more kinds may be used in combination.
  • the symmetry of the helical structure based on the hexagonal orientation of graphene on the graphene sheet is called axial chiral
  • the two-dimensional lattice vector from the reference point of a 6-membered ring on graphene is a chiral vector. That's it.
  • the (n, m) obtained by indexing this chiral vector is called a chiral index, and is divided into metallicity and semiconductivity by this chiral index.
  • a material having nm that is a multiple of 3 indicates metallic properties
  • a material that is not a multiple of 3 indicates semiconductor properties.
  • the single-walled CNT used in the present invention may be semiconducting or metallic, and both may be used in combination.
  • a metal or the like may be included in the CNT, and a substance in which a molecule such as fullerene is included (in particular, a substance in which fullerene is included is referred to as a peapod) may be used.
  • CNT can be produced by an arc discharge method, a chemical vapor deposition method (hereinafter referred to as a CVD method), a laser ablation method, or the like.
  • the CNT used in the present invention may be obtained by any method, but is preferably obtained by an arc discharge method and a CVD method.
  • fullerenes, graphite, and amorphous carbon may be produced as by-products at the same time. You may refine
  • the method for purifying CNTs is not particularly limited. In addition to the above-described purification methods, acid treatment with nitric acid, sulfuric acid or the like and ultrasonic treatment are effective for removing impurities. In addition, it is more preferable to perform separation and removal using a filter from the viewpoint of improving purity.
  • CNT After purification, the obtained CNT can be used as it is. Moreover, since CNT is generally produced in a string shape, it may be cut into a desired length depending on the application. CNTs can be cut into short fibers by acid treatment with nitric acid, sulfuric acid or the like, ultrasonic treatment, freeze pulverization method or the like. In addition, it is also preferable to perform separation using a filter from the viewpoint of improving purity. In the present invention, not only cut CNTs but also CNTs produced in the form of short fibers in advance can be used in the same manner.
  • Such short fibrous CNTs are formed by, for example, forming a catalytic metal such as iron or cobalt on a substrate, and thermally decomposing a carbon compound at 700 to 900 ° C. on the surface by CVD to cause vapor growth of the CNTs.
  • a shape oriented in the direction perpendicular to the substrate surface is obtained.
  • the short fiber CNTs thus produced can be taken out by a method such as peeling off from the substrate.
  • the short fibrous CNTs can be obtained by supporting a catalytic metal on a porous support such as porous silicon or an anodic oxide film of alumina and growing the CNTs on the surface by the CVD method.
  • short fiber CNTs oriented on the SiC single crystal surface can be obtained by an epitaxial growth method.
  • Nano metal materials are nanometer-sized fibrous or particulate metal materials, specifically, fibrous metal materials (also called metal fibers), particulate metal materials (metal nanoparticles). Also). The metal nanowire described later is preferable as the nanometal material.
  • the metal fiber preferably has a solid structure or a hollow structure.
  • a metal fiber having a solid structure with an average minor axis length of 1 to 1,000 nm and an average major axis length of 1 to 100 ⁇ m is called a metal nanowire, and an average minor axis length of 1 to 1,000 nm.
  • a metal fiber having an average major axis length of 0.1 to 1,000 ⁇ m and having a hollow structure is called a metal nanotube.
  • the metal fiber material may be any metal having conductivity, and can be appropriately selected according to the purpose.
  • the long period table International Pure and Applied Chemistry Union (IUPAC), 1991 revision
  • At least one metal selected from the group consisting of 4 periods, 5th period, and 6th period is preferable, at least one metal selected from Group 2 to Group 14 is more preferable, and Group 2, Group 8 is more preferable. More preferably, at least one metal selected from Group 9, Group 10, Group 11, Group 12, Group 12, Group 13, and Group 14.
  • metals examples include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, Lead or an alloy thereof can be used.
  • silver and an alloy with silver are preferable in terms of excellent conductivity.
  • the metal used in the alloy with silver include platinum, osmium, palladium, and iridium.
  • a metal may be used individually by 1 type and may use 2 or more types together.
  • the shape of the metal nanowire is not particularly limited as long as the metal nanowire is formed in the above-described metal in a hollow structure, and can be appropriately selected according to the purpose.
  • it can take any shape such as a columnar shape, a rectangular parallelepiped shape, a columnar shape with a polygonal cross section, and the corners of the cylindrical shape and the polygonal shape of the cross section are rounded in that the transparency of the thermoelectric conversion layer is increased.
  • a cross-sectional shape is preferred.
  • the cross-sectional shape of the metal nanowire can be examined by observing with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average minor axis length of metal nanowires (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 50 nm or less, more preferably 1 to 50 nm from the same viewpoint as the above-described nanoconductive material. Preferably, 10 to 40 nm is more preferable, and 15 to 35 nm is particularly preferable.
  • the average short axis length can be calculated as the average value of the short axis lengths of 300 metal nanowires using, for example, a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.). In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the longest axis.
  • the average major axis length (sometimes referred to as the average length) of the metal nanowire is preferably 1 ⁇ m or more, more preferably 1 to 40 ⁇ m, still more preferably 3 to 35 ⁇ m, and particularly preferably 5 to 30 ⁇ m.
  • the average major axis length can be calculated as an average value of the major axis lengths of 300 metal nanowires using, for example, a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX).
  • TEM transmission electron microscope
  • the long axis length is a value calculated from the radius and the curvature in consideration of a circle having the arc.
  • the metal nanowire may be manufactured by any manufacturing method, but the metal ions are reduced while heating in a solvent in which a halogen compound and a dispersion additive are dissolved, as described in JP 2012-230881 A. It is preferable to manufacture by a manufacturing method. Details of halogen compounds, dispersion additives and solvents, heating conditions, and the like are described in Japanese Patent Application Laid-Open No. 2012-230881. In addition to this production method, for example, JP 2009-215594 A, JP 2009-242880 A, JP 2009-299162 A, JP 2010-84173 A, and JP 2010-86714 A. A metal nanowire can also be manufactured by the manufacturing method described in each of the above.
  • the shape of the metal nanotube is not particularly limited as long as it is formed of the above-described metal in a hollow structure, and may be a single layer or a multilayer.
  • the metal nanotubes are preferably single-walled because they are excellent in electrical conductivity and thermal conductivity.
  • the thickness of the metal nanotube (difference between the outer diameter and the inner diameter) is preferably 3 to 80 nm and more preferably 3 to 30 nm from the viewpoints of durability, transparency, film formability, conductivity, and the like.
  • the average long axis length of the metal nanotubes is preferably 1 to 40 ⁇ m, more preferably 3 to 35 ⁇ m, and even more preferably 5 to 30 ⁇ m, from the same viewpoint as the above-described nanoconductive material.
  • the average minor axis length of the metal nanotube is preferably the same as the average minor axis length of the metal nanowire.
  • the metal nanotube may be manufactured by any manufacturing method, for example, by the manufacturing method described in US Patent Application Publication No. 2005/0056118.
  • the metal nanoparticles may be particulate or powdery metal fine particles formed of the above-mentioned metal, and the surface of the metal fine particles or metal fine particles may be coated with a protective agent, and further the surface coated. May be dispersed in a dispersion medium.
  • Preferred examples of the metal used for the metal nanoparticles include silver, copper, gold, palladium, nickel, rhodium and the like. Also, an alloy composed of at least two of these, an alloy of at least one of these and iron, and the like can be used.
  • Examples of the two alloys include platinum-gold alloy, platinum-palladium alloy, gold-silver alloy, silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium-palladium alloy, silver-rhodium alloy, Examples thereof include copper-palladium alloy and nickel-palladium alloy.
  • Examples of alloys with iron include iron-platinum alloys, iron-platinum-copper alloys, iron-platinum-tin alloys, iron-platinum-bismuth alloys, and iron-platinum-lead alloys. These metals or alloys can be used alone or in combination of two or more.
  • the average particle diameter (dynamic light scattering method) of the metal nanoparticles is preferably 1 to 150 nm from the viewpoint of excellent conductivity.
  • a protective agent described in JP2012-2222055 is preferably exemplified, and a protective agent having a linear or branched alkyl chain having 10 to 20 carbon atoms, particularly a fatty acid.
  • aliphatic amines, aliphatic thiols or aliphatic alcohols are more preferable.
  • the carbon number is 10 to 20
  • the storage stability of the metal nanoparticles is high and the conductivity is excellent.
  • the fatty acids, aliphatic amines, aliphatic thiols and aliphatic alcohols are preferably those described in JP-A-2012-2222055.
  • the metal nanoparticles may be produced by any production method, for example, gas deposition method, sputtering method, metal vapor synthesis method, colloid method, alkoxide method, coprecipitation method, uniform precipitation method, thermal decomposition. Method, chemical reduction method, amine reduction method and solvent evaporation method.
  • gas deposition method for example, gas deposition method, sputtering method, metal vapor synthesis method, colloid method, alkoxide method, coprecipitation method, uniform precipitation method, thermal decomposition.
  • Method chemical reduction method, amine reduction method and solvent evaporation method.
  • a known reducing agent or the like can be appropriately used in addition to selecting and using the above-mentioned protective agent as necessary.
  • thermoelectric conversion material of the present invention contains at least one compound selected from the compounds represented by the following general formulas (1a) to (3b) in addition to the above-described nanoconductive material.
  • the content ratio between the nano-conductive material and the compounds represented by the general formulas (1a) to (3b) in the thermoelectric conversion material is preferably 1: 9 to 9: 1 on a mass basis. More preferably, it is ⁇ 8: 2. By setting the content ratio of both in the above range, the coating property and film forming property of the material are improved.
  • the mechanism for improving the adhesion with the electrode and the thermoelectric conversion performance is not clear, but the following mechanism is used. It is presumed that the dispersibility of the nanoconductive material in the thermoelectric conversion layer is improved. If the dispersibility of the nano-conductive material is poor, when a thermoelectric conversion material is applied and formed on the electrode, film thickness unevenness or partial aggregation is likely to occur, and it is difficult to form a uniform film. As a result, the adhesion between the film and the electrode decreases.
  • the concentration of the nano-conductive material increases as the dispersion medium in the material decreases, and re-aggregation occurs using the nano-conductive material that is not sufficiently dispersed as the core. it is conceivable that.
  • the dispersibility of the nano-conductive material is good, such re-aggregation is unlikely to occur, and as a result, a uniform film with no film thickness unevenness or partial aggregation can be formed, and the adhesion with the electrode is improved. To do.
  • thermoelectric conversion material of the present invention the compound represented by the general formula (1a) or (1b) having a sulfur atom in the cation portion, and the general formula (2a) or (2b) having a phosphorus atom in the cation portion.
  • the empty d orbitals of the cation portion and the nanoconductive material interact electronically, thereby loosening the aggregation state of the nanoconductive material and improving the dispersibility. Since sulfur atoms and phosphorus atoms have a larger atomic radius than oxygen atoms and nitrogen atoms, it is considered that they are relatively easy to interact with nano-conductive materials even when alkyl groups or the like are substituted.
  • the compound represented by the general formula (3a) or (3b) has a nitrogen-containing heterocyclic structure in the cation part, and this interacts electronically with the nano-conductive material, so that The state of aggregation of the conductive material is loosened and the dispersibility is improved.
  • X ⁇ represents a counter anion.
  • R 11 to R 13 each independently represents an alkyl group or a heteroaryl group.
  • R 12 and R 13 may combine with each other to form a ring.
  • n represents an integer of 2 or 3.
  • X p- represents a p-valent counter anion, and p represents an integer of 1 to 3.
  • k represents an integer of 1 to 3.
  • L represents an n-valent linking group or a single bond.
  • R ⁇ 12 > and R ⁇ 13 > are synonymous with General formula (1a).
  • the plurality of R 12 and R 13 may be the same or different.
  • R 11 to R 13 each independently represents an alkyl group or a heteroaryl group, and an alkyl group is preferable.
  • compounds in which R 11 to R 13 are each independently an alkyl group do not have absorption in the visible light region, and thus are not easily decomposed by light. Therefore, the element using the compound for the thermoelectric conversion layer has excellent stability over time with respect to light, and can maintain the initial thermoelectric conversion performance over a long period of time.
  • the alkyl group includes a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group.
  • the alkyl group preferably has 1 to 14 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • the methylene group contained in the alkyl group may be substituted with a divalent linking group.
  • the divalent linking group include —O—, —S—, —COO—, —OCO—, and —OCOO.
  • the hetero atom of the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom.
  • the ring constituting the heteroaryl group is preferably a 5-membered ring or a 6-membered ring, or a condensed ring thereof.
  • alkyl groups or heteroaryl groups may further have a substituent, and examples thereof include the following substituent W.
  • substituent W include a halogen atom (preferably fluorine, chlorine), a linear, branched or cyclic alkyl group (the number of carbon atoms is preferably 1-20, more preferably 4-15), an aryl group, heteroaryl Group, —NH 2 , —NHR b , —NR b R c , —COR b , —COOH, —COOR b , —OCOR b , —OCOOR b , —CONHR b , —CONR b R c , —OCONHR b , — OCONR b R c , —OH, —OR b , SH, —SR b , —O (CH 2 CH 2 O) 1 R b (R b and R c are each independently a linear, branched or cyclic alky
  • R 12 and R 13 may be bonded to each other to form a heterocycle containing a sulfur atom to which R 12 and R 13 are bonded.
  • the formed heterocycle may be an aromatic ring or an aliphatic ring, and is preferably an aliphatic ring. Further, a 5- or 6-membered ring is preferable. Specifically, a tetrahydrothiophene ring and a tetrahydro-2H-thiopyran ring are preferable.
  • a plurality of R 12 and R 13 may be the same or different.
  • X ⁇ and X p ⁇ represent a counter anion.
  • X - or X p-in counter anion represented is not particularly limited, preferably the conjugate base of a strong acid.
  • the strong acid means an acid having an acid dissociation constant pKa of 10 or less in dimethyl sulfoxide (DMSO).
  • Preferred conjugate bases for strong acids are preferably halogen ions, aryl sulfonate anions, perfluoroalkyl sulfonate anions, perhalogenated Lewis acid anions, perfluoroalkyl sulfonimide anions, perhalogenate anions, aryl borate anions, perfluoroaryl borates.
  • a perhalogenated Lewis acid anion a perfluoroalkylsulfonimide anion, a perhalogenate anion, an aryl borate anion, and a perfluoroaryl borate anion are more preferable.
  • halogen ion examples include Cl ⁇ , Br ⁇ and I ⁇ .
  • arylsulfonate anion include p-toluenesulfonate anion, benzenesulfonate anion, naphthalenesulfonate anion, naphthoquinonesulfonate anion, naphthalenedisulfonate anion, and anthraquinonesulfonate anion.
  • the aryl part of the anion may have a substituent, and examples of the substituent include a fluoro group.
  • perfluoroalkylsulfonic acid anion examples include CF 3 SO 3 ⁇ , C 4 F 9 SO 3 ⁇ , and C 8 F 17 SO 3 — .
  • perhalogenated Lewis acid anion examples include PF 6 ⁇ , SbF 6 ⁇ , BF 4 ⁇ , AsF 6 ⁇ and FeCl 4 ⁇ .
  • perfluoroalkylsulfonimide anion examples include CF 3 SO 2 —N —— SO 2 CF 3 and C 4 F 9 SO 2 —N —— SO 2 C 4 F 9 .
  • perhalogenate anion include ClO 4 ⁇ , BrO 4 ⁇ and IO 4 ⁇ .
  • aryl borate anion examples include (C 6 H 5 ) 4 B ⁇ and (p-CH 3 C 6 H 4 ) 4 B — .
  • the aryl part of the anion may have a substituent, and examples of the substituent include a fluoro group.
  • Specific examples of the perfluoroaryl borate anion include (C 6 F 5 ) 4 B — .
  • n is preferably 2.
  • p is preferably 1 or 2, and more preferably 1. More preferably, k is 2 and p is 1.
  • the linking group for L is preferably a divalent or trivalent aliphatic group, and more preferably an alkylene group. L is preferably an alkylene group or a single bond.
  • thermoelectric conversion material of the present invention the compound represented by the general formula (1a) or (1b) may be used alone or in combination of two or more.
  • X ⁇ represents a counter anion.
  • R 21 to R 24 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Any two groups selected from R 21 to R 24 may be bonded to each other to form a ring.
  • n represents an integer of 2 or 3.
  • X p- represents a p-valent counter anion, and p represents an integer of 1 to 3.
  • k represents an integer of 1 to 3.
  • n kp.
  • L represents an n-valent linking group or a single bond.
  • R 22 to R 24 have the same meaning as in general formula (2a). The plurality of R 22 to R 24 may be the same or different.
  • R 21 to R 24 each independently represents an alkyl group, an aryl group, or a heteroaryl group, and an alkyl group is preferable.
  • a compound in which R 21 to R 24 are each independently an alkyl group does not absorb in the visible light region and is not easily decomposed by light. Therefore, the element using the compound for the thermoelectric conversion layer has excellent stability over time with respect to light, and can maintain the initial thermoelectric conversion performance over a long period of time.
  • the alkyl group includes a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group.
  • the alkyl group preferably has 1 to 14 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • the methylene group contained in the alkyl group may be substituted with a divalent linking group. Examples of the divalent linking group include —O—, —S—, —CO—, —COO—, and —OCO. —, —OCOO—, —CH ⁇ CH—, —C ⁇ C—, —NR a — (R a represents an alkyl group having 1 to 6 carbon atoms).
  • the number of carbon atoms of the aryl group is preferably 4 to 50, more preferably 6 to 40.
  • the ring constituting the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an indacene ring, and a fluorene ring, and a benzene ring is preferable.
  • the hetero atom of the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom.
  • the heteroaryl group preferably has 4 to 50 carbon atoms, more preferably 6 to 40 carbon atoms.
  • Specific examples of the ring constituting the heteroaryl ring include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, oxathiazole ring, pyridine ring, pyrazine ring, pyrimidyl ring, pyridazinyl ring, And a benzo condensed ring (for example, benzothiophene) and a dibenzodi condensed ring (for example, dibenzothiophene, carbazole), and a thiophene ring, a furan ring, and a pyrrole ring are preferable.
  • alkyl groups, aryl groups, and heteroaryl groups may have a substituent, and examples of the substituent include the above-described substituent W.
  • Any two groups selected from R 21 to R 24 may be bonded to each other to form a heterocycle containing a phosphorus atom.
  • the formed heterocycle may be an aromatic ring or an aliphatic ring, and is preferably an aliphatic ring. Further, a 5- or 6-membered ring is preferable.
  • a plurality of R 22 to R 24 may be the same or different.
  • X -, X p-, n, k, and p are, X in the general formula (1a) and (1b) -, X p-, n, k, and a p Each is synonymous and the preferable range is also the same.
  • the linking group for L is preferably a divalent or trivalent aliphatic group, and more preferably an alkylene group.
  • L is preferably an alkylene group or a single bond.
  • thermoelectric conversion material of the present invention the compound represented by the general formula (2a) or (2b) may be used alone or in combination of two or more.
  • X ⁇ represents a counter anion.
  • A represents a nitrogen-containing heterocyclic group.
  • R 31 and R 32 each independently represents an alkyl group, an aryl group, or a heteroaryl group. R 31 may combine with A to form a ring.
  • m represents 0 or 1
  • m is 0 when A is a nitrogen-containing aromatic heterocyclic group
  • m is 1 when A is a nitrogen-containing aliphatic heterocyclic group.
  • n represents an integer of 2 or 3.
  • X p- represents a p-valent counter anion, and p represents an integer of 1 to 3.
  • k represents an integer of 1 to 3.
  • n kp.
  • L represents an n-valent linking group or a single bond.
  • A, R 32 and m have the same meanings as in the general formula (3a).
  • a plurality of A and R 32 may be the same or different.
  • A represents a nitrogen-containing heterocyclic group, which may be a nitrogen-containing aromatic heterocyclic ring or a nitrogen-containing aliphatic heterocyclic ring. However, when A is a nitrogen-containing aromatic heterocyclic group, m is 0, and when A is a nitrogen-containing aliphatic heterocyclic group, m is 1. A is preferably a nitrogen-containing aromatic heterocyclic group.
  • the compound in which A is a nitrogen-containing aromatic heterocyclic group has ⁇ electrons, and electronic interaction with the surface of the nanoconductive material ( ⁇ - ⁇ interaction) ) Occurs.
  • the compound represented by the general formula (3a) or (3b) is electronically adsorbed on the surface of the nanoconductive material, so that the structure is not easily oxidized and decomposed by light. Therefore, the element using the compound for the thermoelectric conversion layer has excellent stability over time with respect to light, and can maintain the initial thermoelectric conversion performance over a long period of time.
  • the nitrogen-containing heterocyclic group of A may contain a hetero atom other than a nitrogen atom, and the hetero atom is preferably a sulfur atom or an oxygen atom.
  • the nitrogen-containing heterocyclic group preferably includes a plurality of nitrogen atoms, and more preferably includes two nitrogen atoms.
  • the ring constituting the nitrogen-containing aromatic heterocyclic group for A is preferably a 5-membered ring or a 6-membered ring, or a condensed ring thereof is also preferable.
  • a pyridine ring and an imidazole ring are preferred.
  • the ring constituting the nitrogen-containing aliphatic heterocyclic group of A is preferably a 5-membered ring or a 6-membered ring, or a condensed ring thereof is also preferable.
  • pyrrolidine ring examples include a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a quinuclidine ring, and a benzo condensed ring thereof (for example, dihydroindole), and a pyrrolidine ring and a piperidine ring are preferable.
  • These nitrogen-containing aromatic heterocycle and nitrogen-containing aliphatic heterocycle may have a substituent, and examples of the substituent include the above-described substituent W.
  • R 31 and R 32 each independently represents an alkyl group, an aryl group, or a heteroaryl group, preferably an alkyl group.
  • the alkyl group includes a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group.
  • the alkyl group preferably has 1 to 14 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • the methylene group contained in the alkyl group may be substituted with a divalent linking group. Examples of the divalent linking group include —O—, —S—, —CO—, —COO—, and —OCO. —, —OCOO—, —CH ⁇ CH—, —C ⁇ C—, —NR a — (R a represents an alkyl group having 1 to 6 carbon atoms).
  • the number of carbon atoms of the aryl group is preferably 4 to 50, more preferably 6 to 40.
  • the ring constituting the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, an indacene ring, and a fluorene ring, and a benzene ring is preferable.
  • the hetero atom of the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom.
  • the heteroaryl group preferably has 4 to 50 carbon atoms, more preferably 6 to 40 carbon atoms.
  • Specific examples of the ring constituting the heteroaryl ring include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, oxathiazole ring, pyridine ring, pyrazine ring, pyrimidyl ring, pyridazinyl ring, And a benzo condensed ring (for example, benzothiophene) and a dibenzodi condensed ring (for example, dibenzothiophene, carbazole), and a thiophene ring, a furan ring, and a pyrrole ring are preferable.
  • alkyl groups, aryl groups, and heteroaryl groups may have a substituent, and examples of the substituent include the above-described substituent W.
  • R 31 may combine with A to form a ring.
  • the heterocycle formed is preferably a triethylenediamine ring, an azabicyclo- [4,4,0] decane ring, or an azabicyclo- [2,2,2] octane ring.
  • a plurality of A and R 32 may be the same or different.
  • X -, X p-, n, k, and p are, X in the general formula (1a) and (1b) -, X p-, n, k, and a p
  • X p-, n, k, and a p are synonymous and the preferable range is also the same.
  • the linking group for L is preferably a divalent or trivalent aliphatic group, and more preferably an alkylene group.
  • L is preferably an alkylene group or a single bond.
  • thermoelectric conversion material of the present invention the compound represented by the general formula (3a) or (3b) may be used alone or in combination of two or more.
  • the compounds represented by the general formulas (1a) to (3b) preferably have a melting point of 100 ° C. or lower. From the viewpoint of setting the melting point within the above range, it is preferable that the counter anion of the compounds represented by the general formulas (1a) to (3b) is a conjugate base of the above-mentioned strong acid.
  • the compounds represented by the general formulas (1a) to (3b) are well dissolved in the dispersion medium (described later) during the preparation of the thermoelectric conversion material. The dispersibility of the material is further improved. As a result, the adhesion between the thermoelectric conversion layer formed of the material and the electrode is improved, and the thermoelectric conversion performance is also improved.
  • thermoelectric conversion material of the present invention preferably contains a conjugated polymer in addition to the nano-conductive material and the compounds represented by the general formulas (1a) to (3b). By containing the conjugated polymer, the thermoelectric conversion performance of the device can be further improved.
  • the content of the polymer compound in the thermoelectric conversion material is not particularly limited, but is preferably 10 to 90% by mass in the total solid content of the thermoelectric conversion material, that is, in the thermoelectric conversion layer, from the viewpoint of thermoelectric conversion performance, and 20 to 80% by mass is more preferable, and 30 to 70% by mass is even more preferable.
  • the conjugated polymer is not particularly limited as long as it has a structure in which the main chain is conjugated with a ⁇ electron or a lone pair of lone electrons.
  • Examples of such a conjugated structure include a structure in which a single bond and a double bond are alternately connected in a carbon-carbon bond on the main chain.
  • the conjugated polymer is not necessarily a high molecular weight compound, and may be an oligomer compound.
  • Such conjugated polymers include thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene compounds, p-fluorene compounds.
  • Nylene vinylene compound fluorene compound, aromatic polyamine compound (also referred to as arylamine compound), polyacene compound, polyphenanthrene compound, metal phthalocyanine compound, p-xylylene compound, vinylene sulfide compound, m- At least one selected from the group consisting of phenylene compounds, naphthalene vinylene compounds, p-phenylene oxide compounds, phenylene sulfide compounds, furan compounds, selenophene compounds, azo compounds, and metal complex compounds It includes conjugated polymer containing a repeating structural components that correspond to the compound. When the conjugated polymer is a copolymer, it may be a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or the like.
  • thermoelectric conversion performance thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene compounds, fluorene compounds, and A conjugated polymer containing a constituent component corresponding to at least one compound selected from the group consisting of arylamine compounds as a repeating structure is preferable.
  • the substituent introduced into the above compound is not particularly limited, but the dispersibility of the conjugated polymer in the dispersion medium can be improved in consideration of compatibility with other components and the type of dispersion medium that can be used. It is preferable to select and introduce those appropriately.
  • an organic solvent in addition to a linear, branched or cyclic alkyl group, alkoxy group, thioalkyl group, an alkoxyalkyleneoxy group, an alkoxyalkyleneoxyalkyl group, a crown ether group, an aryl group Etc. can be preferably used. These groups may further have a substituent.
  • the number of carbon atoms of the substituent is not particularly limited, but is preferably 1 to 12, more preferably 4 to 12, particularly a long-chain alkyl group having 6 to 12 carbon atoms, an alkoxy group, a thioalkyl group, An alkoxyalkyleneoxy group and an alkoxyalkyleneoxyalkyl group are preferred.
  • a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, a hydroxyl group, or a phosphoric acid group to the terminal of each monomer or the above substituent.
  • An alkoxy group or the like can be introduced as a substituent, which is preferable.
  • the number of substituents that can be introduced is not particularly limited, and one or more substituents can be appropriately introduced in consideration of dispersibility, compatibility, conductivity, and the like of the conjugated polymer.
  • the conductive polymer described in JP 2012-251132 A can be suitably used as the conjugated polymer.
  • the above conjugated polymers can be used singly or in combination of two or more.
  • thermoelectric conversion material of the present invention contains a dispersion medium, and the nano conductive material is dispersed in the dispersion medium.
  • the dispersion medium only needs to be able to disperse the nanoconductive material, and water, an organic solvent, and a mixed solvent thereof can be used.
  • an organic solvent Preferably an organic solvent, alcohol solvents such as methanol, ethanol, butanol, benzyl alcohol, cyclohexanol, halogen solvents such as chloroform, chlorobenzene, dichlorobenzene, aprotic polar solvents such as DMF, NMP, DMSO, Aromatic solvents such as benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, cumene, ethylbenzene, methylpropylbenzene, methylisopropylbenzene, tetrahydronaphthalene, pyridine, aliphatic solvents such as pentane, hexane, octane, decane, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, 2-butanone,
  • thermoelectric conversion material of the present invention More preferred are halogen solvents such as chloroform and dichlorobenzene, aprotic polar solvents such as DMF and NMP, aromatic solvents such as xylene, tetramethylbenzene and tetrahydronaphthalene, and ether solvents such as THF.
  • halogen solvents such as chloroform and dichlorobenzene
  • aprotic polar solvents such as DMF and NMP
  • aromatic solvents such as xylene, tetramethylbenzene and tetrahydronaphthalene
  • ether solvents such as THF.
  • one type of dispersion medium can be used alone, or two or more types can be used in combination.
  • the dispersion medium is preferably deaerated beforehand.
  • the dissolved oxygen concentration in the dispersion medium is preferably 10 ppm or less.
  • Examples of the degassing method include a method of irradiating ultrasonic waves under reduced pressure, a method of bubbling an inert gas such as argon, and the like.
  • the dispersion medium is preferably dehydrated in advance.
  • the amount of water in the dispersion medium is preferably 1000 ppm or less, and more preferably 100 ppm or less.
  • a method for dehydrating the dispersion medium a known method such as a method using molecular sieve or distillation can be used.
  • the amount of the dispersion medium in the thermoelectric conversion material is preferably 25 to 99.99% by mass, more preferably 30 to 99.95% by mass, and more preferably 30 to 99.99% by mass with respect to the total amount of the thermoelectric conversion material. More preferably, it is 9 mass%.
  • the thermoelectric conversion material of the present invention may contain an antioxidant, a light stabilizer, a heat stabilizer, a plasticizer and the like in addition to the above components.
  • examples of the antioxidant include Irganox 1010 (trade name, manufactured by Nihon Chiga Bigi), Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Examples include Sumilizer GM (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
  • Examples of the light-resistant stabilizer include TINUVIN 234 (trade name, manufactured by BASF), CHIMASSORB 81 (trade name, manufactured by BASF), Siasorb UV-3853 (trade name, manufactured by Sun Chemical), and the like.
  • Examples of the heat stabilizer include IRGANOX 1726 (trade name, manufactured by BASF).
  • Examples of the plasticizer include Adeka Sizer RS (trade name, manufactured by Adeka). The mixing ratio of the other components is preferably 5% by mass or less, more preferably 0 to 2% by mass, based on the total solid content of the preliminary mixture.
  • thermoelectric conversion material of the present invention can be prepared by mixing the above components.
  • the dispersion medium is prepared by mixing the nano conductive material, the compounds represented by the general formulas (1a) to (3b), and optionally other components, and dissolving or dispersing each component.
  • each component in the thermoelectric conversion material is a state in which the nano-conductive material is dispersed, and other components such as the compounds represented by the general formulas (1a) to (3b) and the conjugated polymer are dispersed or dissolved. It is preferable that components other than the nano-conductive material are in a dissolved state.
  • the dispersed state is an aggregate state of molecules having a particle size that does not settle in a solvent even when stored for a long time (generally 1 month or longer), and a dissolved state is in a solvent. A state in which one molecule is solvated.
  • thermoelectric conversion material there is no restriction
  • each component may be prepared by stirring, shaking, kneading and dissolving or dispersing in a solvent. Sonication may be performed to promote dissolution and dispersion.
  • the dispersibility of the nano-conductive material is increased by heating the solvent to a temperature not lower than room temperature and not higher than the boiling point, extending the dispersion time, or increasing the application strength of stirring, soaking, kneading, ultrasonic waves, etc. Can be increased.
  • thermoelectric conversion element has a 1st electrode, a thermoelectric conversion layer, and a 2nd electrode on a base material, This thermoelectric conversion layer is formed using the thermoelectric conversion material mentioned above.
  • thermoelectric conversion element of this invention should just have a 1st electrode, a thermoelectric conversion layer, and a 2nd electrode on a base material, The position of a 1st electrode, a 2nd electrode, and a thermoelectric conversion layer There are no particular limitations on other configurations such as relationships.
  • the thermoelectric conversion layer may be disposed so that at least one surface thereof is in contact with the first electrode and the second electrode.
  • the thermoelectric conversion layer is sandwiched between the first electrode and the second electrode, that is, the thermoelectric conversion element of the present invention has the first electrode, the thermoelectric conversion layer, and the second electrode in this order on the substrate. It may be an embodiment.
  • thermoelectric conversion layer is disposed on one surface so as to be in contact with the first electrode and the second electrode, that is, the thermoelectric conversion element of the present invention is formed on the base material so as to be separated from each other.
  • stacked on the 1st electrode and the 2nd electrode may be sufficient.
  • An example of the structure of the thermoelectric conversion element of the present invention is the structure of the element shown in FIGS. In FIG. 1 and FIG. 2, the arrows indicate the direction of the temperature difference when the thermoelectric conversion element is used.
  • the thermoelectric conversion element 1 shown in FIG. 1 includes a pair of electrodes including a first electrode 13 and a second electrode 15 on a first base 12, and the thermoelectric conversion material of the present invention between the electrodes 13 and 15.
  • thermoelectric conversion layer 14 formed by is provided.
  • a second substrate 16 is disposed on the other surface of the second electrode 15, and the metal plates 11 and 17 face each other outside the first substrate 12 and the second substrate 16. Is arranged.
  • the thermoelectric conversion element of the present invention it is preferable to provide a thermoelectric conversion layer in the form of a film (film) with the thermoelectric conversion material of the present invention on a substrate via an electrode.
  • the first electrode 13 or the second electrode 15 is provided on the surfaces of the two base materials 12 and 16 (the surface on which the thermoelectric conversion layer 14 is formed).
  • a structure having a thermoelectric conversion layer 14 formed of the thermoelectric conversion material of the invention is preferable.
  • thermoelectric conversion element 2 shown in FIG. 2 is provided with a first electrode 23 and a second electrode 25 on a first base material 22, and a thermoelectric conversion formed on the thermoelectric conversion material of the present invention on the first electrode 23 and the second electrode 25.
  • a layer 24 is provided.
  • thermoelectric conversion layer 14 of the thermoelectric conversion element 1 is covered with the first base material 12 via the first electrode 13.
  • the second base material 16 is preferably pressure-bonded to the other surface.
  • the second electrode 15 is preferably interposed between the thermoelectric conversion layer 14 and the base material 16.
  • One surface of the thermoelectric conversion layer 24 of the thermoelectric conversion element 2 is covered with the first electrode 23, the second electrode 25, and the first base material 22.
  • the second base material 26 is pressure-bonded also to the other surface. That is, it is preferable that the second electrode 15 is formed in advance on the surface of the second base material 16 used for the thermoelectric conversion element 1 (the pressure contact surface of the thermoelectric conversion layer 14).
  • the pressure bonding between the electrode and the thermoelectric conversion layer is preferably performed by heating to about 100 ° C. to 200 ° C. from the viewpoint of improving adhesion.
  • the base material of the thermoelectric conversion element of the present invention, the first base material 12 and the second base material 16 in the thermoelectric conversion element 1 may be a base material such as glass, transparent ceramics, metal, or plastic film.
  • the base material has flexibility. Specifically, the flexibility in which the number of bending resistances MIT according to the measurement method specified in ASTM D2176 is 10,000 cycles or more. It is preferable to have.
  • the substrate having such flexibility is preferably a plastic film.
  • polyethylene terephthalate polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), Polyethylene-2,6-naphthalene dicarboxylate, polyester film such as polyester film of bisphenol A and iso and terephthalic acid, ZEONOR film (trade name, manufactured by Zeon Corporation), ARTON film (trade name, manufactured by JSR Corporation), Sumilite Polycycloolefin films such as FS1700 (trade name, manufactured by Sumitomo Bakelite), Kapton (trade name, manufactured by Toray DuPont), Apical (trade name, manufactured by Kaneka), Upilex (trade name, U.S.) Polyimide films such as Kosan Co., Ltd., Pomilan (trade name, manufactured by Arakawa Chemical Co., Ltd.), Polycarbonate films such as Pure Ace (trade name, manufactured by Teijin Chemicals Ltd.), Elmec (trade name, manufactured by Kan
  • polyethylene terephthalate polyethylene naphthalate
  • various polyimides polycarbonate films and the like are preferable from the viewpoints of availability, preferably heat resistance of 100 ° C. or higher, economy and effects.
  • a base material in which an electrode is provided on the pressure-bonding surface with the thermoelectric conversion layer.
  • electrode materials for forming the first electrode and the second electrode provided on the substrate transparent electrodes such as ITO and ZnO, metal electrodes such as silver, copper, gold, and aluminum, and carbon materials such as CNT and graphene
  • An organic material such as PEDOT / PSS, a conductive paste in which conductive fine particles such as silver and carbon are dispersed, and a conductive paste containing metal nanowires such as silver, copper, and aluminum can be used.
  • a metal material is preferable, and aluminum, gold, silver, or copper is more preferable.
  • thermoelectric conversion element 1 is configured in the order of the base material 11, the first electrode 13, the thermoelectric conversion layer 14, and the second electrode 15, and the second base material is disposed outside the second electrode 15. Even if 16 adjoins, the 2nd electrode 15 may be exposed to air as the outermost surface, without providing the 2nd substrate 16.
  • the thermoelectric conversion element 2 includes a base material 22, a first electrode 23 and a second electrode 25, and a thermoelectric conversion layer 24 in this order.
  • a second base material 26 is disposed outside the thermoelectric conversion layer 24. Even if it adjoins, the thermoelectric conversion layer 24 may be exposed to air as the outermost surface, without providing the 2nd base material 26.
  • the thickness of the substrate is preferably from 30 to 3000 ⁇ m, more preferably from 50 to 1000 ⁇ m, still more preferably from 100 to 1000 ⁇ m, particularly preferably from 200 to 800 ⁇ m from the viewpoints of handleability and durability. If the substrate is too thick, the thermal conductivity may decrease, and if it is too thin, the film may be easily damaged by external impact.
  • thermoelectric conversion layer of the thermoelectric conversion element of the present invention is formed of the thermoelectric conversion material of the present invention, and may contain other components such as the conjugated polymer described above in addition to these. These components and contents in the thermoelectric conversion layer are as described above.
  • the layer thickness of the thermoelectric conversion layer is preferably 0.1 to 1000 ⁇ m, more preferably 1 to 100 ⁇ m. If the layer thickness is thin, it is not preferable because it is difficult to provide a temperature difference and the resistance in the layer increases.
  • a thermoelectric conversion element can be easily produced as compared with a photoelectric conversion element such as an organic thin film solar cell element.
  • the thermoelectric conversion material of the present invention when used, it is not necessary to consider the light absorption efficiency as compared with the element for an organic thin film solar cell, so that the film thickness can be increased by about 100 to 1000 times. Chemical stability against moisture is improved.
  • thermoelectric conversion layer is not particularly limited.
  • spin coating extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, ink jet printing, etc.
  • a known coating method can be used.
  • screen printing is preferable from the viewpoint of excellent adhesion of the thermoelectric conversion layer to the electrode.
  • Ink jet printing is also preferable because it is easy to handle the apparatus and has a high degree of freedom in selecting an element pattern shape.
  • the thermoelectric conversion material of the present invention is used for the coating solution. It is preferable that the amount of the dispersion medium is appropriately adjusted so that the coating solution has a solid content concentration and viscosity suitable for the method used. As an example, a case where application is performed by an ink jet printing method is shown below, but the present invention is not limited to this.
  • the total solid content concentration of the inkjet coating liquid is generally 0.05% by mass or more and 30% by mass or less, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more. It is 10 mass% or less.
  • the viscosity of the inkjet coating liquid is generally from 1 mPa ⁇ s to 30 mPa ⁇ s, preferably from 1.5 mPa ⁇ s to 20 mPa ⁇ s, more preferably from 1.5 mPa ⁇ s, from the viewpoint of ejection stability. s to 15 mPa ⁇ s.
  • alcohol solvents benzyl alcohol and cyclohexanol are preferable.
  • halogen solvent chlorobenzene and dichlorobenzene are preferable.
  • aromatic solvent xylene, cumene, trimethylbenzene, tetramethylbenzene, and tetrahydronaphthalene are more preferable.
  • aliphatic solvent octane and decane are preferable.
  • ketone solvent methyl isobutyl ketone and propylene carbonate are preferable.
  • amide solvent N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferable.
  • the said solvent may be used independently and may use 2 or more types together.
  • the inkjet coating solution is prepared by dissolving or dispersing the nano-conductive material, the compounds represented by the general formulas (1a) to (3b), and if necessary, other components in a dispersion medium, followed by filter filtration. It is preferable to do.
  • the pore size (pore size) of the filter used for filter filtration is preferably 2.0 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the filter material is preferably made of polytetrafluoroethylene, polyethylene or nylon.
  • a drying process is performed as necessary to volatilize the solvent.
  • a method of drying in a low-pressure atmosphere using heat drying, hot air drying, a vacuum pump, or the like can be given.
  • the temperature and time of the drying process are not particularly limited as long as the coating solution is dried.
  • the drying temperature is generally 100 ° C. or higher and 200 ° C. or lower, and preferably 120 ° C. or higher and 160 ° C. or lower.
  • the drying time is generally from 1 minute to 120 minutes, preferably from 1 minute to 60 minutes, and more preferably from 1 minute to 25 minutes.
  • thermoelectric conversion layer may be formed thick by repeating the above coating and drying steps a plurality of times.
  • thermoelectric conversion layer also referred to as thermoelectric conversion film
  • thermoelectric conversion element of the present invention are excellent in adhesion between the thermoelectric conversion layer and the electrode and thermoelectric conversion performance. Therefore, the thermoelectric conversion element of the present invention can be suitably used as a power generation element of an article for thermoelectric power generation.
  • power generation elements include power generators such as hot spring thermal generators, solar thermal generators, waste heat generators, wristwatch power supplies, semiconductor drive power supplies, (small) sensor power supplies, and the like.
  • thermoelectric conversion material of the present invention and the thermoelectric conversion layer formed of the thermoelectric conversion material of the present invention are suitably used as the thermoelectric conversion element, the material for thermoelectric power generation element, the film for thermoelectric power generation, or various conductive films of the present invention. Specifically, it is suitably used as the above-described thermoelectric conversion material for a power generation element or a film for thermoelectric power generation.
  • Exemplary compound 201 is described in the literature Tetrahedron Letters, 2007, vol. 48, no. 44, p. Synthesized according to 7774-7777.
  • Exemplary compound 202 is described in the literature Chemical Communications, 2012, vol. 48, no. 26, p. Synthesized according to 3185-3187.
  • Exemplary compound 203 was synthesized according to the following scheme. To a methanol solution (25 mL) of compound A (2.9 g), trifluoromethanesulfonic acid (1.6 g) was added dropwise at room temperature. Furthermore, it stirred at 40 degreeC for 1 hour. Thereafter, methanol was distilled off, and dichloromethane (50 mL) and ion-exchanged water (20 mL) were added thereto, followed by solvent extraction, followed by washing twice with 20 mL of ion-exchanged water.
  • Exemplary compound 204 is described in the literature Journal of the American Chemical Society, 1981, vol. 103, no. 13, p. Synthesized according to 3959-3961.
  • Exemplary compound 205 is described in the literature Journal of Organic Chemistry, 1975, vol. 40, p. Synthesized according to 2801-2806.
  • Example Compound 301 N-butylpyridinium bromide (1 g) was dissolved in 20 mL of ion-exchanged water, lithium bis (trifluoromethanesulfonyl) imide (1.5 g) was added to this aqueous solution, and the mixture was stirred at room temperature for 1 hour.
  • Dichloromethane (50 mL) was added thereto, solvent extraction was performed, and water washing was performed twice with 20 mL of ion-exchanged water. Thereafter, the oil layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain the target compound as an oily substance with a yield of 90%.
  • the target compound was identified by 1 H-NMR.
  • the results of 1 H-NMR are shown below.
  • Exemplified Compound 302 uses an equimolar amount of 1,2-dimethyl-3-butylimidazole bromide instead of N-butylpyridinium bromide in the synthesis of Exemplified Compound 301, and instead of lithium bis (trifluoromethanesulfonyl) imide. The synthesis was performed in the same manner except that an equimolar amount of sodium tetrafluoroborate was used.
  • Exemplified Compound 303 uses equimolar amounts of 1-butyl-3-methylimidazole bromide instead of N-butylpyridinium bromide in the synthesis of Exemplified Compound 301, and equimolar instead of lithium bis (trifluoromethanesulfonyl) imide. The synthesis was performed in the same manner except that an amount of sodium tetraphenylborate was used.
  • Exemplary compound 304 was synthesized according to the document Tetrahedron Letters, 1965, 1817, 1819.
  • Exemplified Compound 305 uses an equimolar amount of 1-butyl-1-methyl-piperidine bromide instead of N-butylpyridinium bromide in the synthesis of Exemplified Compound 301, and instead of Lithium bis (trifluoromethanesulfonyl) imide Synthesis was performed in the same manner except that a molar amount of sodium tetrafluoroborate was used.
  • Example Production of Thermoelectric Conversion Layer and Thermoelectric Conversion Element Example Compound 301 in an amount shown in Table 1-2, and a conjugated polymer in an amount shown in Table 1-2 as needed, 3 mg of CNT (ASP-100F, manufactured by Hanwha Nanotech). Then, it was added to 4.0 ml of orthodichlorobenzene and dispersed in an ultrasonic water bath for 70 minutes to obtain a dispersion 301. Using a glass rod as the thermoelectric conversion material on the electrode surface of a polyethylene terephthalate film (thickness: 125 ⁇ m) having gold (thickness: 20 nm, length: 1 cm, width: 1 cm) as a first electrode on one side surface Bar applied.
  • a glass rod as the thermoelectric conversion material on the electrode surface of a polyethylene terephthalate film (thickness: 125 ⁇ m) having gold (thickness: 20 nm, length: 1 cm, width: 1 cm) as a first electrode
  • thermoelectric conversion layer 301 (film thickness: 1.5 ⁇ m) was formed by drying at 80 ° C. under vacuum for 8 hours. A polyethylene terephthalate film on which gold was vapor-deposited as a second electrode was bonded to the upper part of the thermoelectric conversion layer 301 at 80 ° C. to produce a thermoelectric conversion element 301.
  • thermoelectric conversion elements 101, 201 to 206, and 302 to 305 were produced in the same manner as the thermoelectric conversion element 301 except that the exemplified compounds were changed as shown in Table 1-1 or Table 1-2. 101, 201 to 206, 302 to 305 were produced.
  • thermoelectric conversion elements 306 to 309 were prepared after producing thermoelectric conversion layers 306 to 309 in the same manner as thermoelectric conversion element 301 except that the amount of addition of exemplary compound 301 was changed as shown in Table 1-2 below.
  • thermoelectric conversion elements 207 to 210 were produced after producing thermoelectric conversion layers 207 to 210 in the same manner as thermoelectric conversion element 201 except that the addition amount of exemplary compound 201 was changed as shown in Table 1-1 below.
  • thermoelectric conversion elements 310 to 312 were manufactured after manufacturing thermoelectric conversion layers 310 to 312 in the same manner as thermoelectric conversion element 301 except that a conjugated polymer was added as shown in Table 1-2 below.
  • thermoelectric conversion elements 211 to 213 were manufactured after manufacturing thermoelectric conversion layers 211 to 213 in the same manner as thermoelectric conversion element 201 except that a conjugated polymer was added as shown in Table 1-1 below.
  • a comparative thermoelectric conversion layer c101 was prepared in the same manner as the thermoelectric conversion element 301 except that polystyrene (manufactured by Aldrich, product number 430102) was added instead of the exemplified compound, and then a comparative thermoelectric conversion element c101 was prepared. Next, an attempt was made to produce a comparative thermoelectric conversion layer c102 made only of CNTs to which no exemplary compound was added, and a comparative thermoelectric conversion element c102, but the CNTs could not be dispersed and could not be formed. Also, the following evaluations 1 to 3 could not be performed.
  • thermoelectric conversion layer and thermoelectric conversion element were evaluated by the following methods for adhesion to electrodes, thermoelectric characteristic value (thermoelectromotive force S), and thermoelectric performance over time with respect to light. The results are shown in Tables 1-1 and 1-2.
  • thermoelectric conversion layer The adhesion between the thermoelectric conversion layer and the electrode was evaluated by a tape peeling test. A scotch tape was affixed to the surface of the thermoelectric conversion layer so that bubbles did not enter the surface of the thermoelectric conversion layer, and then the peel test was performed to peel off the tape vigorously. The peel test was evaluated in the following five stages. It can be judged that the smaller the peeled area, the better the adhesion of the thermoelectric conversion layer to the electrode.
  • thermoelectric conversion layer A: No peeling B: Less than 20% of the area of the thermoelectric conversion layer is peeling C: 20% or more and less than 50% of the area of the thermoelectric conversion layer is peeling D: 50% or more and less than 75% of the area of the thermoelectric conversion layer is peeling E : 75% or more of the area of the thermoelectric conversion layer is peeled off
  • thermoelectric characteristic value thermoelectric conversion element
  • thermoelectric conversion performance was evaluated.
  • One electrode of the thermoelectric conversion element was placed on a hot plate maintained at a constant temperature, and a Peltier element for temperature control was placed on the other electrode. While keeping the temperature of the hot plate constant (100 ° C.), the temperature of the Peltier element was lowered to give a temperature difference (over 0K to 4K or less) between both electrodes.
  • thermoelectromotive force ( ⁇ V / K) per unit temperature difference is calculated by dividing the thermoelectromotive force ( ⁇ V) generated between both electrodes by the specific temperature difference (K) generated between both electrodes. This value was used as the thermoelectric characteristic value of the thermoelectric conversion element.
  • the calculated thermoelectric characteristic value is shown as a relative value with respect to 100 as the thermoelectric characteristic value of the comparative thermoelectric conversion element c101.
  • thermoelectric conversion performance to light was evaluated by a light resistance test.
  • a light resistance test device (super xenon weather meter SX120 type (long life xenon lamp), manufactured by Suga Test Instruments Co., Ltd.), irradiance 100 ⁇ 25 W / m 2 (wavelength 310 nm to 400 nm), A light resistance test for 25 hours was carried out in accordance with JIS K 5600-7-5 under the conditions of a test chamber temperature of 35 ⁇ 5 ° C., a black panel temperature of 50 ⁇ 5 ° C., and a relative humidity of 65 ⁇ 15%.
  • thermoelectric conversion element was produced.
  • the above-mentioned evaluation 2. was measured in the same manner. The obtained value is assigned to the corresponding evaluation 2. In comparison with the thermoelectric characteristic value, the following five levels were evaluated. It can be determined that the smaller the rate of change of the thermoelectric characteristic value, the better the light resistance and the higher the temporal stability against light.
  • thermoelectric conversion elements 101, 201-206 using the exemplary compounds 101, 201-206, 301-305 represented by the general formulas (1a) to (3b).
  • 301 to 312 were excellent in the adhesion between the electrode and the thermoelectric conversion layer and showed high thermoelectric property values, as compared with the comparative element c101 using polystyrene.
  • the thermoelectric conversion elements 101, 201 to 206, and 301 to 312 were excellent in stability over time.
  • thermoelectric conversion elements 207 to 210 and 306 to 309 showed particularly excellent temporal stability. Further, from the results of the thermoelectric conversion elements 207 to 210 and 306 to 309, the content ratio of the exemplary compound and the CNT in the thermoelectric conversion layer is within the range of 1: 9 to 9: 1, so that the thermoelectric conversion layer is in close contact with the thermoelectric conversion layer. It was found that the property, thermoelectric characteristic value, and stability over time were further improved. Further, the thermoelectric conversion elements 211 to 213 and 310 to 312 to which the conjugated polymer was added in addition to the exemplified compound and CNT showed high thermoelectric characteristic values. On the other hand, the comparative element c101 using polystyrene had very poor adhesion between the electrode and the thermoelectric conversion layer, and was significantly inferior to the thermoelectric conversion element of the present invention in thermoelectric characteristic values and temporal stability.

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Abstract

La présente invention concerne un élément de conversion thermoélectrique qui comporte une première électrode, une couche de conversion thermoélectrique et une seconde électrode sur une base, la couche de conversion thermoélectrique contenant un nano-matériau conducteur et au moins un composé qui est choisi parmi des composés représentés par la formule générale (1a)-(3b) ; un article pour la génération de puissance thermoélectrique et une alimentation électrique pour des capteurs, chacun d'eux utilisant l'élément de conversion thermoélectrique ; et un matériau de conversion thermoélectrique qui contient au moins un composé qui est choisi parmi les composés représentés par les formules générales (1a)-(3b). Dans la formule générale (1a), X- représente un contre-anion ; chacun de R11-R13 représente indépendamment un groupe alkyle ou un groupe hétéroaryle ; et R12 et R13 peuvent se combiner l'un avec l'autre pour former un cycle. Dans la formule générale (1b), n représente un nombre entier de 2 ou 3 ; Xp- représente un contre-anion de valence p ; p représente un nombre entier de 1 à 3 et k représente un nombre entier de 1 à 3, à condition que n = kp ; L représente un groupe de liaison de valence n ou une liaison simple ; R12 et R13 sont tels que définis pour la formule générale (2a) ; et une pluralité de groupes R12 et R13 peuvent être identiques ou différents les uns des autres. Dans la formule générale (2a), X- représente un contre-anion ; chacun de R21-R24 représente indépendamment un groupe alkyle, un groupe aryle ou un groupe hétéroaryle ; et deux groupes quelconques choisis parmi R21-R24 peuvent se combiner les uns avec les autres pour former un cycle. Dans la formule générale (2b), n représente un nombre entier de 2 ou 3 ; Xp- représente un contre-anion de valence p ; p représente un nombre entier de 1 à 3 et k représente un nombre entier de 1 à 3, à condition que n = kp ; L représente un groupe de liaison de valence n ou une liaison simple ; R22-R24 sont tels que définis pour la formule générale (2a) ; et une pluralité de groupes R22-R24 peuvent être identiques ou différents les uns des autres. Dans la formule générale (3a), X- représente un contre-anion ; A représente un groupe hétérocyclique contenant de l'azote ; chacun de R31 et R32 représente indépendamment un groupe alkyle, un groupe aryle ou un groupe hétéroaryle ; R31 peut se combiner avec A pour former un cycle ; m représente 0 ou 1 ; et dans les cas où A est un groupe hétérocyclique aromatique contenant de l'azote, m est égal à 0, alors que dans les cas où A est un groupe hétérocyclique aliphatique contenant de l'azote, m est égal à 1. Dans la formule générale (3b), n représente un nombre entier de 2 ou 3 ; Xp- représente un contre-anion de valence p ; p représente un nombre entier de 1 à 3 et k représente un nombre entier de 1 à 3, à condition que n = kp ; L représente un groupe de liaison de valence n ou une liaison simple ; A, R32 et m sont tels que définis pour la formule générale (3a) ; et une pluralité de groupes A et R32 peuvent être identiques ou différents les uns des autres. FIG. 1: AA%%%Formule générale
PCT/JP2014/060844 2013-05-02 2014-04-16 Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article pour la génération de puissance thermoélectrique, et alimentation électrique pour capteurs Ceased WO2014178284A1 (fr)

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JPWO2021235526A1 (fr) * 2020-05-21 2021-11-25
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JP7011361B1 (ja) 2021-09-10 2022-01-26 株式会社Ｇｃｅインスティチュート 発電素子の製造方法、発電素子、発電装置、及び電子機器
JP2023062767A (ja) * 2021-10-22 2023-05-09 東洋インキＳｃホールディングス株式会社 熱電変換材料および熱電変換素子

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JP7693822B2 (ja) 2021-10-12 2025-06-17 デンカ株式会社 熱電変換素子及びその製造方法

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