JP6329828B2 - Thermoelectric conversion material and manufacturing method thereof - Google Patents
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Description
本発明は、熱電変換材料及びその製造方法に関する。 The present invention relates to a thermoelectric conversion material and a method for producing the same.
熱電変換はゼーベック効果を利用して熱を直接電気に変換する技術であり、化石燃料を使用した際に生じる廃熱等を電気に変換するエネルギー回収技術として注目されている。 Thermoelectric conversion is a technology that directly converts heat into electricity using the Seebeck effect, and is attracting attention as an energy recovery technology that converts waste heat generated when fossil fuel is used into electricity.
熱電変換の性能を表す指数として、以下の式で表わされるパワーファクター（ＰＦ）や無次元性能指数（ＺＴ）が用いられる。なお、σは導電率（Ｓ／ｍ）、Ｓはゼーベック係数（Ｖ／Ｋ）、κは熱伝導率（Ｗ／ｍ・Ｋ２）、Ｔは絶対温度（Ｋ）を示す。
ＰＦ＝σＳ２
ＺＴ＝σＳ２Ｔ／κ
ＰＦやＺＴが高い程、その材料の熱電変換性能が高いと言える。
As an index representing the performance of thermoelectric conversion, a power factor (PF) or a dimensionless figure of merit (ZT) represented by the following formula is used. Here, σ is conductivity (S / m), S is Seebeck coefficient (V / K), κ is thermal conductivity (W / m · K 2 ), and T is absolute temperature (K).
PF = σS 2
ZT = σS 2 T / κ
It can be said that the higher the PF and ZT, the higher the thermoelectric conversion performance of the material.
ＺＴが高い材料として従来は無機材料が中心に検討されてきたが、曲面への設置が困難である点、希少元素や毒性元素を使用する点、大面積への設置に適さない点等の問題点を抱えていた。 Conventionally, inorganic materials have been studied mainly as materials with high ZT, but problems such as difficulty in installation on curved surfaces, use of rare and toxic elements, and inadequate installation on large areas I had a point.
そこで近年、前述した問題点を解消する熱電変換材料として有機材料が注目されている。 Therefore, in recent years, organic materials have attracted attention as thermoelectric conversion materials that solve the above-described problems.
このような材料としてポリアニリン、ポリ（３，４−エチレンジオキシチオフェン）等の導電性ポリマーや、カーボンナノチューブなどの炭素材料、およびこれらの複合材料が検討されている（例えば、特許文献１〜３）。 As such materials, conductive polymers such as polyaniline and poly (3,4-ethylenedioxythiophene), carbon materials such as carbon nanotubes, and composite materials thereof have been studied (for example, Patent Documents 1 to 3). ).
しかし、上記熱電変換材料は熱電変換の効率は低い、原料が高価である等の理由で工業的に実用化することが難しい。特に炭素材料としてカーボンナノチューブを用いた場合は、原料のカーボンナノチューブが高価であるため、得られる熱電変換材料も著しく高価になる。 However, the thermoelectric conversion material is difficult to put into practical use for reasons such as low thermoelectric conversion efficiency and expensive raw materials. In particular, when carbon nanotubes are used as the carbon material, since the raw carbon nanotubes are expensive, the resulting thermoelectric conversion material is also extremely expensive.
本発明は、安価な炭素原料を用いて製造可能であり、優れた熱電変換特性を有する熱電変換材料を提供することを目的とする。本発明はまた、この熱電変換材料を用いた熱電変換素子及び熱電変換材料の製造方法を提供することを目的とする。 An object of the present invention is to provide a thermoelectric conversion material that can be manufactured using an inexpensive carbon raw material and has excellent thermoelectric conversion characteristics. Another object of the present invention is to provide a thermoelectric conversion element using the thermoelectric conversion material and a method for producing the thermoelectric conversion material.
本発明者らは、上記課題を達成するために鋭意努力した結果、安価な炭素材料であるグラファイトイト又はカーボンブラックを酸化して酸化グラフェン又は酸化カーボンブラックを得、続いてこれら酸化グラフェン又は酸化カーボンブラックを還元することにより得られる炭素材料が、導電性ポリマーと共に優れた熱電変換特性を有する熱電変換材料を形成し得ることを見出し、本発明を完成するに至った。 As a result of diligent efforts to achieve the above-mentioned problems, the inventors of the present invention oxidized graphite or carbon black, which is an inexpensive carbon material, to obtain graphene oxide or carbon black. Subsequently, these graphene oxide or carbon oxide The present inventors have found that a carbon material obtained by reducing black can form a thermoelectric conversion material having excellent thermoelectric conversion characteristics together with a conductive polymer, and completed the present invention.
すなわち、本発明の一態様は、以下のとおりである。
［１］炭素材料と導電性ポリマーとを含み、上記炭素材料が、酸化グラフェン及び酸化カーボンブラックからなる群より選択される炭素原料の還元物を含有する、熱電変換材料に関する。
［２］前記還元物が、前記炭素原料を電気化学反応により還元したものである、［１］に記載の熱電変換材料。
［３］前記導電性ポリマーが、電解重合可能なモノマーの重合物を含有する、［１］又は［２］に記載の熱電変換材料。
［４］前記モノマーが、アニリン類、チオフェン類及びピロール類からなる群より選択される少なくとも一種である、請求項［３］に記載の熱電変換材料。
［５］前記還元物が、前記炭素原料を電気化学反応により還元したものであり、前記導電性ポリマーが、電解重合可能なモノマーの重合物を含有し、前記電気化学反応に供された前記炭素原料の量が、前記炭素原料及び前記モノマーの総量基準で５０〜９９質量％である、［１］〜［４］のいずれかに記載の熱電変換材料。
［６］前記炭素材料を含む層と前記導電性ポリマーを含む層とが交互に積層された構造を有する、［１］〜［５］のいずれかに記載の熱電変換材料。
［７］導電率が０．０１〜１０００Ｓ／ｃｍである、［１］〜［６］のいずれかに記載の熱電変換材料。
［８］ゼーベック係数が３〜２００μＶ／Ｋである、［１］〜［７］のいずれかに記載の熱電変換材料。
［９］熱伝導率が０．０１〜０．５Ｗ／ｍＫである、［１］〜［８］のいずれかに記載の熱電変換材料。
［１０］［１］〜［９］のいずれかに記載の熱電変換材料を製造する方法であって、前記炭素原料及び電解重合可能なモノマーを含む混合液に浸漬された導電性基板に、正の電圧及び負の電圧を交互に印加して、該導電性基板上に前記炭素材料及び前記導電性ポリマーを含む前記熱電変換材料を形成する工程を有する、熱電変換材料の製造方法。
［１１］前記導電性基板が、スズドープ酸化インジウム、フッ素ドープ酸化スズ及びステンレス鋼からなる群より選択される少なくとも一種の導電材料を含む、［１０］に記載の製造方法。
［１２］［１］〜［９］のいずれか一項に記載の熱電変換材料を製造する方法であって、前記炭素原料及び電解重合可能なモノマーを含む混合液が一方面上に塗布された２つの導電性基板を、電解液を含浸させたセパレータを介して前記混合液が塗布された面同士が対向するように配置する工程と、前記導電性基板の一方に、他方の導電性基板に対する正の電圧及び負の電圧を交互に印加して、前記導電性基板上に前記炭素材料及び前記導電性ポリマーを含む前記熱電変換材料を形成する工程と、を有する、熱電変換材料の製造方法。
［１３］前記導電性基板のうち少なくとも一方が、スズドープ酸化インジウム、フッ素ドープ酸化スズ及びステンレス鋼からなる群より選択される少なくとも一種の導電材料を含む、［１２］に記載の製造方法。
［１４］前記電解液が、ｐＨが５以下の硫酸水溶液である、［１２］又は［１３］に記載の製造方法。
［１５］［１］〜［９］のいずれかに記載の熱電変換材料を含む、熱電変換素子。
That is, one embodiment of the present invention is as follows.
[1] A thermoelectric conversion material comprising a carbon material and a conductive polymer, wherein the carbon material contains a reduced product of a carbon raw material selected from the group consisting of graphene oxide and carbon black oxide.
[2] The thermoelectric conversion material according to [1], wherein the reduced product is obtained by reducing the carbon raw material by an electrochemical reaction.
[3] The thermoelectric conversion material according to [1] or [2], wherein the conductive polymer contains a polymer of a monomer capable of electrolytic polymerization.
[4] The thermoelectric conversion material according to [3], wherein the monomer is at least one selected from the group consisting of anilines, thiophenes, and pyrroles.
[5] The reduced product is obtained by reducing the carbon raw material by an electrochemical reaction, and the conductive polymer contains a polymer of a monomer capable of electrolytic polymerization, and the carbon subjected to the electrochemical reaction. The thermoelectric conversion material according to any one of [1] to [4], wherein the amount of the raw material is 50 to 99% by mass based on the total amount of the carbon raw material and the monomer.
[6] The thermoelectric conversion material according to any one of [1] to [5], which has a structure in which layers including the carbon material and layers including the conductive polymer are alternately stacked.
[7] The thermoelectric conversion material according to any one of [1] to [6], wherein the electrical conductivity is 0.01 to 1000 S / cm.
[8] The thermoelectric conversion material according to any one of [1] to [7], which has a Seebeck coefficient of 3 to 200 μV / K.
[9] The thermoelectric conversion material according to any one of [1] to [8], which has a thermal conductivity of 0.01 to 0.5 W / mK.
[10] A method for producing the thermoelectric conversion material according to any one of [1] to [9], wherein a positive electrode is applied to a conductive substrate immersed in a mixed solution containing the carbon raw material and an electropolymerizable monomer. A method for producing a thermoelectric conversion material, comprising alternately applying a negative voltage and a negative voltage to form the thermoelectric conversion material containing the carbon material and the conductive polymer on the conductive substrate.
[11] The manufacturing method according to [10], wherein the conductive substrate includes at least one conductive material selected from the group consisting of tin-doped indium oxide, fluorine-doped tin oxide, and stainless steel.
[12] A method for producing the thermoelectric conversion material according to any one of [1] to [9], wherein a mixed liquid containing the carbon raw material and an electropolymerizable monomer is applied on one surface. A step of arranging two conductive substrates such that the surfaces coated with the mixed solution are opposed to each other through a separator impregnated with an electrolytic solution, and one of the conductive substrates with respect to the other conductive substrate Forming a thermoelectric conversion material containing the carbon material and the conductive polymer on the conductive substrate by alternately applying a positive voltage and a negative voltage.
[13] The manufacturing method according to [12], wherein at least one of the conductive substrates includes at least one conductive material selected from the group consisting of tin-doped indium oxide, fluorine-doped tin oxide, and stainless steel.
[14] The production method according to [12] or [13], wherein the electrolytic solution is an aqueous sulfuric acid solution having a pH of 5 or less.
[15] A thermoelectric conversion element comprising the thermoelectric conversion material according to any one of [1] to [9].
本発明によれば、安価な炭素原料を用いて製造可能であり、優れた熱電変換特性を有する熱電変換材料を提供することができる。また、本発明によれば、上記熱電変換材料を用いた熱電変換素子、及び上記熱電変換の製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it can manufacture using an inexpensive carbon raw material and can provide the thermoelectric conversion material which has the outstanding thermoelectric conversion characteristic. Moreover, according to this invention, the manufacturing method of the thermoelectric conversion element using the said thermoelectric conversion material and the said thermoelectric conversion can be provided.
本発明の好適な実施形態について以下に説明する。 A preferred embodiment of the present invention will be described below.
本実施形態に係る熱電変換材料は、炭素材料と導電性ポリマーを含み、本実施形態において、上記炭素材料は、酸化グラフェン及び酸化カーボンブラックからなる群より選択される炭素原料の還元物を含有する。 The thermoelectric conversion material according to the present embodiment includes a carbon material and a conductive polymer. In the present embodiment, the carbon material includes a reduction product of a carbon raw material selected from the group consisting of graphene oxide and oxidized carbon black. .
上記熱電変換材料は、安価な炭素材料から製造可能であり、優れた熱電変換特性を有する。このため、上記熱電変換材料によれば、良好な熱電変換特性を有する熱電変換素子を安価に製造することができる。 The thermoelectric conversion material can be manufactured from an inexpensive carbon material and has excellent thermoelectric conversion characteristics. For this reason, according to the said thermoelectric conversion material, the thermoelectric conversion element which has a favorable thermoelectric conversion characteristic can be manufactured cheaply.
グラフェンは、グラファイトの単分子膜であり、酸化グラフェンは、グラファイトを酸化処理することによって安価に、且つ容易に得ることができる。グラファイトの酸化方法は特に制限されないが、例えば、過マンガン酸カリウム、硫酸等の酸化剤を用いて水中でグラファイトを酸化する方法が挙げられる。具体例として、例えば、Ｘ．Ｊｉａｎｇら、Ｃａｒｂｏｎ，Ｖｏｌ．６７，ｐ．６６２−６７２に記載の方法に従って、グラファイトを水中で硫酸、ペルオキソ二硫酸カリウム及び五酸化二リンと反応させた後に、さらに過マンガン酸カリウムと反応させることで、酸化グラフェンを得ることができる。 Graphene is a monomolecular film of graphite, and graphene oxide can be obtained inexpensively and easily by oxidizing graphite. The method for oxidizing graphite is not particularly limited, and examples thereof include a method for oxidizing graphite in water using an oxidizing agent such as potassium permanganate and sulfuric acid. As a specific example, for example, X. Jiang et al., Carbon, Vol. 67, p. According to the method described in 662-672, graphene oxide can be obtained by reacting graphite with sulfuric acid, potassium peroxodisulfate and diphosphorus pentoxide in water and further reacting with potassium permanganate.
カーボンブラックは、炭素主体の微粒子であり、例えば、炭化水素を熱分解温度以上の高温場（好ましくは１８００〜２２００℃）で燃焼させて得ることができる。カーボンブラックの原料の炭化水素としては、例えば、メタン、エタン、プロパン、ブタン等の飽和炭化水素；エチレン、プロピレン、ブテン、ブタジエン等の二重結合を有する不飽和炭化水素；アセチレン、プロピン、ブチン等の三重結合を有する不飽和炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素；などを用いることができる。これらのうち、エチレン、アセチレン及びブタジエンは、自己発熱分解反応を生じるため反応炉の中心部分でも高温を維持できるため好ましく、アセチレンが特に好ましい。 Carbon black is carbon-based fine particles, and can be obtained, for example, by burning hydrocarbons in a high-temperature field (preferably 1800 to 2200 ° C.) higher than the thermal decomposition temperature. Examples of hydrocarbons used as the raw material for carbon black include saturated hydrocarbons such as methane, ethane, propane, and butane; unsaturated hydrocarbons having double bonds such as ethylene, propylene, butene, and butadiene; acetylene, propyne, and butyne. Or an unsaturated hydrocarbon having a triple bond, such as benzene, toluene, xylene, or the like. Among these, ethylene, acetylene, and butadiene are preferable because they cause a self-exothermic decomposition reaction and can maintain a high temperature even in the central portion of the reaction furnace, and acetylene is particularly preferable.
酸化カーボンブラックは、カーボンブラックを酸化処理することによって安価に、且つ容易に得ることができる。カーボンブラックの酸化方法は特に制限されないが、例えば、過マンガン酸カリウム、硫酸等の酸化剤を用いて水中でカーボンブラックを酸化する方法が挙げられる。具体例として、例えば、Ｘ．Ｊｉａｎｇら、Ｃａｒｂｏｎ，Ｖｏｌ．６７，ｐ．６６２−６７２に記載の方法に従って、カーボンブラックを水中で硫酸、ペルオキソ二硫酸カリウム及び五酸化二リンと反応させた後に、さらに過マンガン酸カリウムと反応させることで、酸化カーボンブラックを得ることができる。 Oxidized carbon black can be obtained inexpensively and easily by oxidizing carbon black. The method for oxidizing carbon black is not particularly limited, and examples thereof include a method for oxidizing carbon black in water using an oxidizing agent such as potassium permanganate and sulfuric acid. As a specific example, for example, X. Jiang et al., Carbon, Vol. 67, p. After reacting carbon black with sulfuric acid, potassium peroxodisulfate and diphosphorus pentoxide in water according to the method described in 662-672, oxidized carbon black can be obtained by further reacting with potassium permanganate. .
酸化グラフェン及び酸化カーボンブラックは、酸化処理によって生じたヒドロキシル基、カルボキシル基、カルボニル基、エポキシ基等の酸素官能基を有し、グラフェン及びカーボンブラックと比較して親水性に優れる。本実施形態において、酸化グラフェンとしては酸素濃度が４５〜７５質量％であるものが好ましく、酸化カーボンブラックとしては酸素濃度が３〜３０質量％であるものが好ましい。なお、本明細書中、酸素濃度は、炭素原子及び酸素原子の総数に対する酸素原子数の割合であり、紫外光電子分光スペクトルから求められる値を示す。 Graphene oxide and carbon black oxide have an oxygen functional group such as a hydroxyl group, a carboxyl group, a carbonyl group, and an epoxy group generated by an oxidation treatment, and are superior in hydrophilicity to graphene and carbon black. In the present embodiment, the graphene oxide preferably has an oxygen concentration of 45 to 75% by mass, and the oxidized carbon black preferably has an oxygen concentration of 3 to 30% by mass. In the present specification, the oxygen concentration is a ratio of the number of oxygen atoms to the total number of carbon atoms and oxygen atoms, and indicates a value obtained from an ultraviolet photoelectron spectroscopy spectrum.
上記還元物は、酸化グラフェン及び酸化カーボンブラックからなる群より選択される炭素原料を還元して得られるものであり、炭素原料が有する上記酸素官能基の少なくとも一部が還元されたものである。炭素原料の還元方法は特に制限されないが、ヒドラジンなどの還元剤により化学的に還元する方法、ｎ−メチルピロリドンやエチレングリコールなどの水混和性溶媒を添加して加熱することで熱的に還元する方法、電気化学反応により還元する方法などが挙げられる。この中では安全性やコスト面、導電性高分子との複合体の製造が容易である点から電気化学反応により還元することが好ましい。 The reduced product is obtained by reducing a carbon raw material selected from the group consisting of graphene oxide and carbon black oxide, and is obtained by reducing at least a part of the oxygen functional group of the carbon raw material. The method for reducing the carbon raw material is not particularly limited, but is a method in which it is chemically reduced with a reducing agent such as hydrazine, or it is thermally reduced by adding a water-miscible solvent such as n-methylpyrrolidone or ethylene glycol and heating. The method, the method of reducing by an electrochemical reaction, etc. are mentioned. Of these, reduction by an electrochemical reaction is preferable from the viewpoint of safety, cost, and ease of producing a complex with a conductive polymer.
酸化グラフェンの還元物（還元型酸化グラフェン、reduced graphene oxideともいう。）は、酸化グラフェンの酸素官能基の少なくとも一部が還元されたものであり、必ずしも全ての酸素官能基が還元除去されている必要はなく、酸素官能基に由来する酸素原子を有していてよい。また、酸化グラフェンの還元物は、グラァイトより格子欠陥が多い傾向にあるが、優れた導電性を有する。本実施形態において、酸化グラフェンの還元物は、還元前の酸化グラフェンより低い酸素濃度を有し、好ましくは酸素濃度が０〜４０質量％であり、より好ましくは０〜３５質量％である。 A graphene oxide reduction product (also referred to as reduced graphene oxide or reduced graphene oxide) is obtained by reducing at least a part of oxygen functional groups of graphene oxide, and all oxygen functional groups are necessarily reduced and removed. It is not necessary and may have an oxygen atom derived from an oxygen functional group. Further, a reduced product of graphene oxide tends to have more lattice defects than graphite, but has excellent conductivity. In this embodiment, the reduced product of graphene oxide has a lower oxygen concentration than that of graphene oxide before reduction, preferably the oxygen concentration is 0 to 40% by mass, more preferably 0 to 35% by mass.
酸化カーボンブラックの還元物は、酸化カーボンブラックの酸素官能基の少なくとも一部が還元されたものであり、必ずしも全ての酸素官能基が還元除去されている必要はなく、酸素官能基に由来する酸素原子を有していてよい。また、酸化カーボンブラックの還元物は、優れた導電性を有する。本実施形態において、酸化カーボンブラックの還元物は、還元前の酸化カーボンブラックより低い酸素濃度を有する。 The reduced product of oxidized carbon black is obtained by reducing at least a part of the oxygen functional group of oxidized carbon black, and it is not always necessary to reduce and remove all oxygen functional groups. It may have atoms. Further, the reduced product of oxidized carbon black has excellent conductivity. In this embodiment, the reduced product of oxidized carbon black has a lower oxygen concentration than the oxidized carbon black before reduction.
上記炭素材料は、上記炭素原料の還元物を含有する。炭素材料は、当該還元物以外の炭素材料を含有していてもよく、例えば、グラフェン、カーボンブラック、グラファイト等を更に含有していてもよい。炭素材料は、その主成分が、上記炭素原料の還元物であることが好ましく、炭素材料の総量に対して６０質量％以上が上記炭素原料の還元物であることが好ましく、８０質量％以上が上記炭素原料の還元物であることがより好ましい。また、炭素材料は、上記炭素原料の還元物であってよい。 The carbon material contains a reduced product of the carbon raw material. The carbon material may contain a carbon material other than the reduced product, and may further contain, for example, graphene, carbon black, graphite or the like. The main component of the carbon material is preferably a reduction product of the carbon raw material, and 60% by mass or more is preferably a reduction product of the carbon raw material with respect to the total amount of the carbon material, and 80% by mass or more. More preferred is a reduced product of the carbon raw material. The carbon material may be a reduced product of the carbon raw material.
上記導電性ポリマーは、炭素材料と協働して熱電変換機能を奏する。導電性ポリマーとしては、公知の種々の導電性ポリマーを用いることができる。 The conductive polymer has a thermoelectric conversion function in cooperation with the carbon material. Various known conductive polymers can be used as the conductive polymer.
本実施形態において、上記導電性ポリマーは、電解重合可能なモノマーの重合物を含有することが好ましい。このような重合物は、上記還元物と共に電気化学反応によって合成することができる。 In the present embodiment, the conductive polymer preferably contains a polymer of a monomer that can be electropolymerized. Such a polymer can be synthesized by an electrochemical reaction together with the reduced product.
電解重合可能なモノマーとしては、例えば、アニリン類、チオフェン類、ピロール類、フラン類、セレノフェン類等挙げられ、これらのうち、アニリン類、チオフェン類及びピロール類からなる群より選択される化合物を好適に用いることができる。なお、電気重合可能なモノマーとしては、一種を単独で用いても、二種以上を組合わせて用いてもよい。 Examples of the electropolymerizable monomer include anilines, thiophenes, pyrroles, furans, and selenophenes. Among these, a compound selected from the group consisting of anilines, thiophenes, and pyrroles is preferable. Can be used. As the electropolymerizable monomer, one kind may be used alone, or two or more kinds may be used in combination.
アニリン類は、アニリン及びアニリンの水素原子の一部が置換された置換アニリンを含み、これらのうち電解重合可能な化合物を好適に用いることができる。アニリン類としては、例えば、アニリン；２−メチルアニリン、３−イソブチルアニリン等のアルキル置換アニリン；２−アニリンスルホン酸、３−アニリンスルホン酸等のアニリンスルホン酸類；等が挙げられる。 The anilines include aniline and substituted anilines in which a part of the hydrogen atoms of aniline are substituted, and among these, an electropolymerizable compound can be suitably used. Examples of anilines include aniline; alkyl-substituted anilines such as 2-methylaniline and 3-isobutylaniline; aniline sulfonic acids such as 2-aniline sulfonic acid and 3-aniline sulfonic acid; and the like.
チオフェン類は、チオフェン及びチオフェンの水素原子の一部が置換された置換チオフェンを含み、これらのうち電解重合可能な化合物を好適に用いることができる。チオフェン類としては、例えば、チオフェン；３−メチルチオフェン、３−エチルチオフェン、３−プロピルチオフェン、３−ブチルチオフェン、３−ヘキシルチオフェン、３−ヘプチルチオフェン、３−シクロヘキシルチオフェン、３−ドデシルチオフェン等のアルキル置換チオフェン；３−メトキシチオフェン、３−エトキシチオフェン、３−ブトキシチオフェン、３−ヘキシルオキシチオフェン、３，４−エチレンジオキシチオフェン、３，４−プロピレンジオキシチオフェン等のアルコキシ置換チオフェン；３−メトキシ−４−メチルチオフェン、３−メトキシ−４−エチルチオフェン等の３−アルコキシ−４−アルキル置換チオフェン；３−チオヘキシルチオフェン、３−チオオクチルチオフェン等のチオアルキルチオフェン類；３−カルボキシチオフェン等のカルボキシルチオフェン類；等が挙げられる。 Thiophenes include thiophene and substituted thiophenes in which a part of the hydrogen atoms of thiophene are substituted, and among these, an electropolymerizable compound can be suitably used. Examples of thiophenes include thiophene; 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-cyclohexylthiophene, 3-dodecylthiophene, etc. Alkyl-substituted thiophene; alkoxy-substituted thiophene such as 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene; 3-alkoxy-4-alkyl-substituted thiophenes such as methoxy-4-methylthiophene and 3-methoxy-4-ethylthiophene; thioalkylthiophenes such as 3-thiohexylthiophene and 3-thiooctylthiophene; - carboxyl thiophenes such as carboxymethyl thiophene; and the like.
ピロール類は、ピロール及びピロールの水素原子の一部が置換された置換ピロールを含み、これらのうち電解重合可能な化合物を好適に用いることができる。ピロール類としては、例えば、ピロール、Ｎ−メチルピロール、３−メチルピロール、３−エチルピロール、３−ｎ−プロピルピロール、３−ブチルピロール、３−オクチルピロール、３，４−ジメチルピロール等のアルキル置換ピロール；３−カルボキシピロール、３−メチル−４−カルボキシピロール等のカルボキシルピロール類；３−メトキシピロール、３−エトキシピロール、３−ブトキシピロール等のアルコキシ置換ピロール；等が挙げられる。 Pyrrole includes pyrrole and substituted pyrrole in which part of hydrogen atoms of pyrrole is substituted, and among these, a compound that can be electropolymerized can be preferably used. Examples of pyrroles include alkyls such as pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, and 3,4-dimethylpyrrole. Substituted pyrrole; carboxyl pyrroles such as 3-carboxypyrrole and 3-methyl-4-carboxypyrrole; alkoxy-substituted pyrrole such as 3-methoxypyrrole, 3-ethoxypyrrole and 3-butoxypyrrole;
一態様において、熱電変換材料は、炭素原料を電気化学反応により還元して得られた上記還元物と、電解重合可能なモノマーを電解重合により重合して得られた導電性ポリマーと、を含むものであってよい。 In one aspect, a thermoelectric conversion material includes the reduced product obtained by reducing a carbon raw material by an electrochemical reaction, and a conductive polymer obtained by polymerizing an electropolymerizable monomer by electrolytic polymerization. It may be.
上記態様において、電気化学反応に供された炭素原料の量は、当該炭素原料及び電解重合に供されたモノマーの総量基準で、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。炭素原料の量が５０質量％以上であると、熱電変換材料の導電率がより向上する傾向がある。 In the above aspect, the amount of the carbon raw material subjected to the electrochemical reaction is preferably 50% by mass or more, and preferably 70% by mass or more, based on the total amount of the carbon raw material and the monomer subjected to electrolytic polymerization. Is more preferable, and it is still more preferable that it is 90 mass% or more. There exists a tendency for the electrical conductivity of a thermoelectric conversion material to improve that the quantity of a carbon raw material is 50 mass% or more.
また、上記態様において、電気化学反応に供された炭素原料の量は、当該炭素原料及び電解重合に供されたモノマーの総量基準で、９９質量％以下であることが好ましく、９７質量％以下であることがより好ましい。炭素原料の量を９９質量％以下とすることで、熱電変換材料の耐久性が向上する傾向がある。 Moreover, in the said aspect, it is preferable that the quantity of the carbon raw material provided to the electrochemical reaction is 99 mass% or less on the basis of the total amount of the said carbon raw material and the monomer provided to the electropolymerization, and 97 mass% or less. More preferably. When the amount of the carbon raw material is 99% by mass or less, the durability of the thermoelectric conversion material tends to be improved.
上記態様において、電解重合に供されたモノマーの量は、当該モノマー及び電気化学反応に供された炭素原料の総量基準で、１質量％以上であることが好ましく、３質量％以上であることがより好ましい。モノマーの量を１質量％以上とすることで、熱電変換材料の耐久性が向上する傾向がある。 In the above aspect, the amount of the monomer subjected to electrolytic polymerization is preferably 1% by mass or more, preferably 3% by mass or more, based on the total amount of the monomer and the carbon raw material subjected to electrochemical reaction. More preferred. By setting the amount of the monomer to 1% by mass or more, the durability of the thermoelectric conversion material tends to be improved.
また、上記態様において、電解重合に供されたモノマーの量は、当該モノマー及び電気化学反応に供された炭素原料の総量基準で、５０質量％以下であることが好ましく、３０質量％以下であることがより好ましく、１０質量％以下であることがさらに好ましい。モノマーの量を５０質量％以下とすることで、熱電変換材料の導電率がより向上する傾向がある。 Moreover, in the said aspect, it is preferable that the quantity of the monomer provided to the electropolymerization is 50 mass% or less on the basis of the total amount of the carbon raw material provided to the said monomer and electrochemical reaction, and is 30 mass% or less. More preferred is 10% by mass or less. There exists a tendency for the electrical conductivity of a thermoelectric conversion material to improve more because the quantity of a monomer shall be 50 mass% or less.
本実施形態に係る熱電変換材料は、上記炭素材料及び導電性ポリマーを含み、優れた熱電変換特性を有する。 The thermoelectric conversion material according to the present embodiment includes the carbon material and the conductive polymer, and has excellent thermoelectric conversion characteristics.
熱電変換材料の導電率は、好ましくは０．０１Ｓ／ｃｍ以上であり、より好ましくは５Ｓ／ｃｍ以上である。また、熱電変換材料の導電率は、１０００Ｓ／ｃｍ以下であってよく、１００Ｓ／ｃｍ以下であってもよい。 The electrical conductivity of the thermoelectric conversion material is preferably 0.01 S / cm or more, more preferably 5 S / cm or more. Moreover, the electrical conductivity of the thermoelectric conversion material may be 1000 S / cm or less, and may be 100 S / cm or less.
熱電変換材料のゼーベック係数は、好ましくは３μＶ／Ｋ以上であり、より好ましくは５μＶ／Ｋ以上である。また、熱電変換材料のゼーベック係数は、２００μＶ／Ｋ以下であってよく、３０μＶ／Ｋ以下であってもよい。 The Seebeck coefficient of the thermoelectric conversion material is preferably 3 μV / K or more, more preferably 5 μV / K or more. Further, the Seebeck coefficient of the thermoelectric conversion material may be 200 μV / K or less, or 30 μV / K or less.
熱電変換材料の熱伝導率は、好ましくは０．５Ｗ／ｍ・Ｋ以下であり、より好ましくは０．３Ｗ／ｍＫ以下である。また、熱電変換材料の熱伝導率は、０．０１Ｗ／ｍ・Ｋ以上であってよく、０．０５Ｗ／ｍ・Ｋ以上であってもよい。 The thermal conductivity of the thermoelectric conversion material is preferably 0.5 W / m · K or less, more preferably 0.3 W / mK or less. Further, the thermal conductivity of the thermoelectric conversion material may be 0.01 W / m · K or more, or 0.05 W / m · K or more.
熱電変換材料は、本発明の効果が有効に得られる範囲で、炭素材料及び導電性ポリマー以外の成分を含んでいてもよい。 The thermoelectric conversion material may contain components other than the carbon material and the conductive polymer as long as the effects of the present invention are effectively obtained.
熱電変換材料は、フィルム状又は板状に成形することができ、その厚みは、例えば５μｍ以上とすることができ、１０μｍ以上とすることもできる。厚みを５μｍ以上とすることで、熱電変換材料の機械的強度が向上し、取り扱いが容易になる傾向がある。また、熱電変換材料の厚みは３０μｍ以下としてもよく、２０μｍ以下としてもよい。厚みが３０μｍ以下の熱電変換材料は、後述する電気化学反応を利用した製造方法で容易に、短時間で製造することができる。 The thermoelectric conversion material can be formed into a film shape or a plate shape, and the thickness thereof can be, for example, 5 μm or more, and can be 10 μm or more. By setting the thickness to 5 μm or more, the mechanical strength of the thermoelectric conversion material is improved and the handling tends to be easy. The thickness of the thermoelectric conversion material may be 30 μm or less, or 20 μm or less. A thermoelectric conversion material having a thickness of 30 μm or less can be easily manufactured in a short time by a manufacturing method using an electrochemical reaction described later.
一態様において、熱電変換材料は、炭素材料を含む層と導電性ポリマーを含む層とが交互に積層された構造を有していてよい。各層の積層数は特に制限されず、例えば１０以上であってよく、２０以上であってもよい。また積層数は、１０００以下であってよく、９００以下であってもよい。 In one embodiment, the thermoelectric conversion material may have a structure in which layers including a carbon material and layers including a conductive polymer are alternately stacked. The number of stacked layers is not particularly limited, and may be, for example, 10 or more, or 20 or more. The number of layers may be 1000 or less, or 900 or less.
積層方法は特に制限されず、例えば炭素材料を含む層と導電性ポリマーを含む層とをそれぞれ作製して積層してもよい。また、後述する電気化学反応を利用した製造方法によっても積層構造が形成されると考えられる。 The lamination method is not particularly limited, and for example, a layer containing a carbon material and a layer containing a conductive polymer may be prepared and laminated. Moreover, it is thought that a laminated structure is formed also by the manufacturing method using the electrochemical reaction mentioned later.
（熱電変換材料の製造方法１：基板浸漬法による製造方法）
本実施形態に係る熱電変換材料の製造方法の好適な一態様について以下に説明する。
(Manufacturing method of thermoelectric conversion material 1: manufacturing method by substrate immersion method)
A preferred aspect of the method for producing a thermoelectric conversion material according to the present embodiment will be described below.
本態様に係る製造方法は、炭素原料及び電解重合可能なモノマーを含む混合液に浸漬された導電性基板に、正の電圧及び負の電圧を交互に印加して、該導電性基板上に炭素材料及び導電性ポリマーを含む前記熱電変換材料を形成する工程を有する。 In the manufacturing method according to this aspect, a positive voltage and a negative voltage are alternately applied to a conductive substrate immersed in a liquid mixture containing a carbon raw material and an electropolymerizable monomer, and carbon is formed on the conductive substrate. Forming the thermoelectric conversion material including the material and a conductive polymer.
上記製造方法では、導電性基板に正の電圧を印加したとき、上記モノマーが電解重合して導電性ポリマーが形成される。また、導電性基板に負の電圧を印加したとき、上記炭素原料が還元されて炭素原料の還元物が形成される。すなわち、上記製造方法では、導電性基板に正の電圧及び負の電圧を交互に印加することで、導電性基板上に導電性ポリマー及び炭素原料の還元物が交互に形成される。 In the manufacturing method, when a positive voltage is applied to the conductive substrate, the monomer is electrolytically polymerized to form a conductive polymer. Moreover, when a negative voltage is applied to the conductive substrate, the carbon raw material is reduced to form a reduced carbon raw material. That is, in the manufacturing method described above, a positive polymer and a negative voltage are alternately applied to the conductive substrate, whereby the conductive polymer and the reduced product of the carbon raw material are alternately formed on the conductive substrate.
上記混合液は、炭素原料及びモノマーを分散又は溶解可能な溶媒を含むことが望ましく、該溶媒としては、水が好適に用いられる。すなわち、上記混合液としては、炭素原料及びモノマーが水中に分散又は溶解した混合液を好適に用いることができる。 The mixed solution desirably contains a solvent capable of dispersing or dissolving the carbon raw material and the monomer, and water is preferably used as the solvent. That is, as the mixed solution, a mixed solution in which a carbon raw material and a monomer are dispersed or dissolved in water can be suitably used.
上記混合液中の炭素原料の量は、炭素原料及びモノマーの総量基準で、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましく、好ましくは９９質量％以下であり、より好ましくは９７質量％以下である。 The amount of the carbon raw material in the mixed liquid is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more based on the total amount of the carbon raw material and the monomer. Preferably, it is 99 mass% or less, More preferably, it is 97 mass% or less.
上記混合液中のモノマーの量は、炭素原料及びモノマーの総量基準で、１質量％以上であることが好ましく、３質量％以上であることがより好ましく、好ましくは５０質量％以下であり、より好ましくは３０質量％以下であり、さらに好ましくは１０質量％以下である。 The amount of the monomer in the mixed liquid is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 50% by mass or less, based on the total amount of the carbon raw material and the monomer. Preferably it is 30 mass% or less, More preferably, it is 10 mass% or less.
上記混合液中の炭素原料の濃度は、混合液の総量基準で、１質量％以下であることが好ましく、０．５質量％以下であることがより好ましい。濃度が１質量％を超えると混合液の粘度が上昇し、取り扱いが困難になる可能性がある。 The concentration of the carbon raw material in the mixed solution is preferably 1% by mass or less, and more preferably 0.5% by mass or less, based on the total amount of the mixed solution. If the concentration exceeds 1% by mass, the viscosity of the mixed solution increases, which may make handling difficult.
上記混合液は、炭素原料及びモノマー以外の成分を含んでいてもよく、例えば硫酸、塩酸、酢酸、過塩素酸等を含んでいてもよい。 The mixed liquid may contain components other than the carbon raw material and the monomer, and may contain, for example, sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, and the like.
上記製造方法では、導電性基板上に熱電変換材料が形成される。熱電変換材料は、導電性基板上から剥離して熱電変換素子に利用してもよく、導電性基板上に設けられた状態で導電性基板と共に熱電変換素子に適用してもよい。 In the manufacturing method, the thermoelectric conversion material is formed on the conductive substrate. The thermoelectric conversion material may be peeled off from the conductive substrate and used for the thermoelectric conversion element, or may be applied to the thermoelectric conversion element together with the conductive substrate in a state of being provided on the conductive substrate.
導電性基板としては、公知の種々の導電性基板を用いることができる。腐食・溶出しにくいという観点から、導電性基板は、スズドープ酸化インジウム（ＩＴＯ）、フッ素ドープ酸化スズ（ＦＴＯ）及びステンレス鋼からなる群より選択される少なくとも一種の導電材料を含むことが好ましく、ＦＴＯ及びステンレス鋼からなる群より選択される少なくとも一種の導電材料を含むことがより好ましい。また、導電性基板は上記導電材料からなる基板であってもよい。 Various known conductive substrates can be used as the conductive substrate. From the viewpoint of being resistant to corrosion and elution, the conductive substrate preferably contains at least one conductive material selected from the group consisting of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), and stainless steel. And at least one conductive material selected from the group consisting of stainless steel. The conductive substrate may be a substrate made of the conductive material.
上記工程において、電圧印加時の混合液の温度は、使用する炭素原料及びモノマーに応じて適宜調整でき、１０〜５０℃とすることが好ましい。 In the said process, the temperature of the liquid mixture at the time of voltage application can be suitably adjusted according to the carbon raw material and monomer to be used, and it is preferable to set it as 10-50 degreeC.
上記工程において、導電性基板に印加する正の電圧は、使用するモノマーに応じて適宜調整できるが、＋１．０〜＋２．０Ｖの範囲とすることが好ましい。このような正の電圧を印加することで、導電性基板上に、熱電変換材料として好適な導電性ポリマーを容易に形成することができる。 In the above step, the positive voltage applied to the conductive substrate can be appropriately adjusted according to the monomer used, but is preferably in the range of +1.0 to + 2.0V. By applying such a positive voltage, a conductive polymer suitable as a thermoelectric conversion material can be easily formed on the conductive substrate.
上記工程において、導電性基板に印加する負の電圧は、使用する炭素原料に応じて適宜調整できるが、−０．５〜−１．５Ｖの範囲とすることが好ましい。このような負の電圧を印加することで、導電性基板上に、熱電変換材料として好適な炭素材料を容易に形成することができる。 In the above step, the negative voltage applied to the conductive substrate can be appropriately adjusted according to the carbon raw material to be used, but is preferably in the range of −0.5 to −1.5V. By applying such a negative voltage, a carbon material suitable as a thermoelectric conversion material can be easily formed on the conductive substrate.
電圧印加のサイクルは、所望する熱電変換材料の厚さ、層構造等に応じて適宜選択することができ、例えば１０〜１０００回とすることができる。 The cycle of voltage application can be appropriately selected according to the desired thickness of the thermoelectric conversion material, the layer structure, etc., and can be 10 to 1000 times, for example.
電圧印加の一回のサイクル中、導電性基板には正の電圧及び負の電圧がそれぞれ所定の時間印加される。正の電圧を印加する時間は、例えば１秒〜１０分とすることができ、１０秒〜１分とすることが好ましい。負の電圧を印加する時間は、例えば５秒〜３０分とすることができ、３０秒〜５分とすることが好ましい。 During one cycle of voltage application, a positive voltage and a negative voltage are respectively applied to the conductive substrate for a predetermined time. The time for applying the positive voltage can be, for example, 1 second to 10 minutes, and preferably 10 seconds to 1 minute. The time for applying the negative voltage can be, for example, 5 seconds to 30 minutes, and preferably 30 seconds to 5 minutes.
上記工程を実施する装置は、導電性基板に正の電圧及び負の電圧を印加できる装置であればよい。例えば、上記工程は、作用極に導電性基板、対極に白金、参照極に銀−塩化銀電極を使用した三電極系を用いて実施することができる。 The apparatus for performing the above steps may be any apparatus that can apply a positive voltage and a negative voltage to the conductive substrate. For example, the above process can be performed using a three-electrode system using a conductive substrate as a working electrode, platinum as a counter electrode, and a silver-silver chloride electrode as a reference electrode.
本態様に係る製造方法は、グラファイト及び／又はカーボンブラックを酸化処理して上記炭素原料を得る酸化工程を更に有していてもよい。 The production method according to this aspect may further include an oxidation step of obtaining the carbon raw material by oxidizing graphite and / or carbon black.
酸化処理の方法は特に制限されないが、例えば、過マンガン酸カリウム、硫酸等の酸化剤を用いて水中でグラファイト及び／又はカーボンブラックを酸化する方法を適用することができる。このとき、酸化剤の量は、グラファイト及びカーボンブラックの総量１００質量部に対して、１０００〜２００００質量部とすることが好ましく、５０００〜１００００質量部とすることがより好ましい。 Although the method of oxidation treatment is not particularly limited, for example, a method of oxidizing graphite and / or carbon black in water using an oxidizing agent such as potassium permanganate or sulfuric acid can be applied. At this time, the amount of the oxidizing agent is preferably 1000 to 20000 parts by mass, and more preferably 5000 to 10,000 parts by mass with respect to 100 parts by mass of the total amount of graphite and carbon black.
酸化処理の方法としては、例えば、Ｘ．Ｊｉａｎｇら、Ｃａｒｂｏｎ，Ｖｏｌ．６７，ｐ．６６２−６７２に記載の方法に従って、グラファイト及び／又はカーボンブラックを水中で硫酸、ペルオキソ二硫酸カリウム及び五酸化二リンを用いて反応させた後に、さらに過マンガン酸カリウムと反応させることで、上記酸化工程を実施することもできる。 Examples of the oxidation treatment method include X. Jiang et al., Carbon, Vol. 67, p. According to the method described in 662-672, graphite and / or carbon black is reacted in water with sulfuric acid, potassium peroxodisulfate, and diphosphorus pentoxide, and then further reacted with potassium permanganate, whereby the oxidation is performed. A process can also be carried out.
上記方法において、グラファイト及びカーボンブラックの総量１００質量部に対し、硫酸の使用量は１０００〜２００００質量部とすることが好ましく、ペルオキソ二硫酸カリウムの使用量は１０〜２００質量部とすることが好ましく、五酸化二リンの使用量は１０〜２００質量部とすることが好ましく、過マンガン酸カリウムの使用量は１００〜１０００質量部とすることが好ましい。 In the above method, the amount of sulfuric acid used is preferably 1000-20000 parts by mass and the amount of potassium peroxodisulfate is preferably 10-200 parts by mass with respect to 100 parts by mass of the total amount of graphite and carbon black. The amount of diphosphorus pentoxide is preferably 10 to 200 parts by mass, and the amount of potassium permanganate is preferably 100 to 1000 parts by mass.
（熱電変換材料の製造方法２：基板塗布法による製造方法）
本実施形態に係る熱電変換材料の製造方法の好適な他の一態様について以下に説明する。
(Manufacturing method 2 of thermoelectric conversion material: manufacturing method by substrate coating method)
Another preferred aspect of the method for producing a thermoelectric conversion material according to this embodiment will be described below.
本態様に係る製造方法は、炭素原料及び電解重合可能なモノマーを含む混合液が一方面上に塗布された２つの導電性基板を、電解液を含浸させたセパレータを介して混合液が塗布された面同士が対向するように配置する工程（配置工程）と、導電性基板の一方（以下、「第一の導電性基板」という。）に、他方の導電性基板（以下、「第二の導電性基板」という。）に対する正の電圧及び負の電圧を交互に印加して、導電性基板上に炭素材料及び導電性ポリマーを含む熱電変換材料を形成する工程（電圧印加工程）と、を有する。 In the manufacturing method according to this aspect, the mixed liquid is applied to the two conductive substrates coated on one surface with the mixed liquid containing the carbon raw material and the electropolymerizable monomer via the separator impregnated with the electrolytic solution. One of the conductive substrates (hereinafter referred to as the “first conductive substrate”) and the other conductive substrate (hereinafter referred to as the “second conductive substrate”). A step of forming a thermoelectric conversion material containing a carbon material and a conductive polymer on the conductive substrate by alternately applying a positive voltage and a negative voltage to the conductive substrate ()) (voltage applying step). Have.
上記製造方法では、第一の導電性基板に、第二の導電性基板に対して正の電圧を印加したとき、第一の導電性基板上で上記モノマーが電解重合して導電性ポリマーが形成され、第二の導電性基板上で上記炭素原料が還元されて炭素原料の還元物が形成される。また、第一の導電性基板に、第二の導電性基板に対して負の電圧を印加したとき、第一の導電性基板上で上記炭素原料が還元されて炭素原料の還元物が形成され、第二の導電性基板上で上記モノマーが電解重合して導電性ポリマーが形成される。すなわち、上記製造方法では、第一の導電性基板及び第二の導電性基板の両方の導電性基板上で、モノマーの電解重合と炭素原料の還元とが交互に生じ、導電性ポリマー及び炭素原料の還元物が交互に形成される。 In the manufacturing method, when a positive voltage is applied to the first conductive substrate with respect to the second conductive substrate, the monomer is electrolytically polymerized on the first conductive substrate to form a conductive polymer. The carbon raw material is reduced on the second conductive substrate to form a reduced product of the carbon raw material. Further, when a negative voltage is applied to the first conductive substrate with respect to the second conductive substrate, the carbon raw material is reduced on the first conductive substrate to form a reduced carbon raw material. The monomer is electrolytically polymerized on the second conductive substrate to form a conductive polymer. That is, in the above manufacturing method, the electrolytic polymerization of the monomer and the reduction of the carbon raw material are alternately generated on the conductive substrates of both the first conductive substrate and the second conductive substrate, and the conductive polymer and the carbon raw material are produced. Are formed alternately.
配置工程では、上記混合液が一方面上に塗布された第一の導電性基板及び第二の導電性基板を、電解液を含浸させたセパレータを介して混合液が塗布された面同士が対向するように配置する。 In the arranging step, the first conductive substrate and the second conductive substrate coated with the mixed liquid on one side face each other with the mixed liquid applied through a separator impregnated with an electrolytic solution. Arrange to do.
上記混合液としては、炭素原料及びモノマーが均一に分散又は溶解していることが望ましい。このため、上記混合液は、炭素原料及びモノマーを分散又は溶解可能な溶媒を含むことが望ましく、該溶媒としては、水が好適に用いられる。 As the liquid mixture, it is desirable that the carbon raw material and the monomer are uniformly dispersed or dissolved. For this reason, it is desirable that the mixed solution contains a solvent capable of dispersing or dissolving the carbon raw material and the monomer, and water is preferably used as the solvent.
上記混合液中の炭素原料の量は、炭素原料及びモノマーの総量基準で、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましく、好ましくは９９質量％以下であり、より好ましくは９７質量％以下である。 The amount of the carbon raw material in the mixed liquid is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more based on the total amount of the carbon raw material and the monomer. Preferably, it is 99 mass% or less, More preferably, it is 97 mass% or less.
上記混合液中のモノマーの量は、炭素原料及びモノマーの総量基準で、１質量％以上であることが好ましく、３質量％以上であることがより好ましく、好ましくは５０質量％以下であり、より好ましくは３０質量％以下であり、さらに好ましくは１０質量％以下である。 The amount of the monomer in the mixed liquid is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 50% by mass or less, based on the total amount of the carbon raw material and the monomer. Preferably it is 30 mass% or less, More preferably, it is 10 mass% or less.
上記混合液中の炭素原料及びモノマーの濃度は特に制限されず、導電性基板上に均一に塗布可能な濃度であればよい。 The concentration of the carbon raw material and the monomer in the mixed solution is not particularly limited as long as it can be uniformly applied on the conductive substrate.
上記混合液は、炭素原料及びモノマー以外の成分を含んでいてもよく、例えば塩酸、硫酸、酢酸、過塩素酸等を含んでいてもよい。 The mixed liquid may contain components other than the carbon raw material and the monomer, and may contain, for example, hydrochloric acid, sulfuric acid, acetic acid, perchloric acid, and the like.
上記混合液は、導電性基板上に塗布された後、配置工程で導電性基板上から炭素原料及びモノマーが流出することを避けるため、必要に応じて適宜、溶媒の一部（又は全部）を揮発させてよい。溶媒を揮発させるため、例えば、５０℃で１０分間加熱するという方法を実施することができる。 After the liquid mixture is applied on the conductive substrate, a part (or all) of the solvent is appropriately added as necessary in order to prevent the carbon raw material and the monomer from flowing out from the conductive substrate in the arranging step. It can be volatilized. In order to volatilize the solvent, for example, a method of heating at 50 ° C. for 10 minutes can be performed.
上記電解液としては、例えば、塩酸、硫酸、酢酸、過塩素酸等の酸を含む酸性水溶液を用いることができ、これらのうち、硫酸水溶液を特に好適に用いることができる。酸性水溶液のｐＨは好ましくは５以下である。 As the electrolytic solution, for example, an acidic aqueous solution containing an acid such as hydrochloric acid, sulfuric acid, acetic acid, and perchloric acid can be used, and among these, a sulfuric acid aqueous solution can be particularly preferably used. The pH of the acidic aqueous solution is preferably 5 or less.
上記セパレータは、導電性基板間で電解液を保持できるものであればよい。セパレータとしては、例えば、ろ紙やリチウムイオン二次電池用のセパレータなどを好適に用いることができる。 The said separator should just be what can hold | maintain electrolyte solution between electroconductive substrates. As the separator, for example, a filter paper or a separator for a lithium ion secondary battery can be suitably used.
第一の導電性基板及び第二の導電性基板としては、公知の種々の導電性基板を用いることができる。腐食・溶出しにくいという観点から、導電性基板は、スズドープ酸化インジウム（ＩＴＯ）、フッ素ドープ酸化スズ（ＦＴＯ）及びステンレス鋼からなる群より選択される少なくとも一種の導電材料を含むことが好ましく、ＦＴＯ及びステンレス鋼からなる群より選択される少なくとも一種の導電材料を含むことがより好ましい。また、導電性基板は上記導電材料からなる基板であってもよい。 Various known conductive substrates can be used as the first conductive substrate and the second conductive substrate. From the viewpoint of being resistant to corrosion and elution, the conductive substrate preferably contains at least one conductive material selected from the group consisting of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), and stainless steel. And at least one conductive material selected from the group consisting of stainless steel. The conductive substrate may be a substrate made of the conductive material.
電圧印加工程では、第一の導電性基板に、第二の導電性基板に対する正の電圧及び負の電圧を交互に印加して、導電性基板上に炭素材料及び導電性ポリマーを含む熱電変換材料を形成する。 In the voltage application step, a positive voltage and a negative voltage with respect to the second conductive substrate are alternately applied to the first conductive substrate, and the thermoelectric conversion material including the carbon material and the conductive polymer on the conductive substrate. Form.
第一の導電性基板及び第二の導電性基板の両方に、同特性の熱電変換材料を形成する観点からは、第二の導電性基板との電圧の絶対値が等しくなるように、第一の導電性基板に正の電圧及び負の電圧を印加することが好ましい。 From the viewpoint of forming a thermoelectric conversion material having the same characteristics on both the first conductive substrate and the second conductive substrate, the first conductive substrate and the second conductive substrate have the same voltage so that the absolute values of the voltages are the same. It is preferable to apply a positive voltage and a negative voltage to the conductive substrate.
また電圧印加工程では、印加される電圧の絶対値の最大が１〜３Ｖの範囲内となるように、第一の導電性基板に正の電圧及び負の電圧を印加することが好ましい。このように電圧を印加することで、第一の導電性基板上に、熱電変換材料として好適な炭素材料及び導電性ポリマーを容易に形成することができる。 In the voltage application step, it is preferable to apply a positive voltage and a negative voltage to the first conductive substrate so that the maximum absolute value of the applied voltage is within a range of 1 to 3V. By applying a voltage in this way, a carbon material and a conductive polymer suitable as a thermoelectric conversion material can be easily formed on the first conductive substrate.
電圧印加のサイクルは、所望する熱電変換材料の厚さ等に応じて適宜選択することができ、例えば１０〜１０００回とすることができる。 The cycle of voltage application can be appropriately selected according to the desired thickness of the thermoelectric conversion material, and can be, for example, 10 to 1000 times.
電圧印加の一回のサイクル中、第一の導電性基板には正の電圧及び負の電圧がそれぞれ所定の時間印加される。正の電圧及び負の電圧を印加する時間は、例えば１秒〜１０分とすることができ、１０秒〜１分とすることが好ましい。 During one cycle of voltage application, a positive voltage and a negative voltage are respectively applied to the first conductive substrate for a predetermined time. The time for applying the positive voltage and the negative voltage can be, for example, 1 second to 10 minutes, and preferably 10 seconds to 1 minute.
また、本態様に係る製造方法では、第一の導電性基板の電圧を正の方向及び負の方向に交互に掃引して、電圧印加工程を実施することもできる。電圧掃引速度は、例えば１〜１０００ｍＶ／ｓｅｃとすることができ、好ましくは１０〜５００ｍＶ／ｓｅｃ、より好ましくは２０〜２００ｍＶ／ｓｅｃである。 In the manufacturing method according to this aspect, the voltage application step can be performed by alternately sweeping the voltage of the first conductive substrate in the positive direction and the negative direction. The voltage sweep rate can be set to, for example, 1 to 1000 mV / sec, preferably 10 to 500 mV / sec, and more preferably 20 to 200 mV / sec.
本態様に係る製造方法は、グラファイト及び／又はカーボンブラックを酸化処理して上記炭素原料を得る酸化工程を更に有していてもよい。酸化工程としては、上記製造方法１に記載の工程と同じ工程が挙げられる。 The production method according to this aspect may further include an oxidation step of obtaining the carbon raw material by oxidizing graphite and / or carbon black. Examples of the oxidation step include the same steps as those described in Production Method 1.
（熱電変換素子）
本実施形態に係る熱電変換材料は、安価な炭素原料を用いて製造可能であり、優れた熱電変換特性を有する。このため、本実施形態に係る熱電変換材料によれば、優れた熱電変換特性を有する熱電変換素子を安価に製造することができる。
(Thermoelectric conversion element)
The thermoelectric conversion material according to the present embodiment can be manufactured using an inexpensive carbon raw material and has excellent thermoelectric conversion characteristics. For this reason, according to the thermoelectric conversion material which concerns on this embodiment, the thermoelectric conversion element which has the outstanding thermoelectric conversion characteristic can be manufactured at low cost.
以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。 The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.
以下、本発明を実施例及び比較例により具体的に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to this.
［実施例１］
（酸化グラフェン分散液の調製）
天然グラファイト（ＳＥＣカーボン社製「ＳＮＯ−１０」）２ｇ、硫酸９．２ｇ、ペルオキソ二硫酸カリウム１ｇ、及び五酸化二リン１ｇを仕込み、８０℃で５時間反応させた。その後、室温まで徐冷しイオン交換水２００ｇで反応液を希釈し、一晩静置した。反応液をブフナー漏斗で濾過し、得られた固形分のイオン交換水による洗浄を、洗浄後のイオン交換水が中性になるまで行った。洗浄後の固形分を室温で一晩真空乾燥した後、０℃の硫酸１４７．２ｇと混合した。混合液を撹拌しながら過マンガン酸カリウム８ｇを、混合液の温度を２０℃以下に保ちながら３０分かけて徐々に添加し、混合液の温度を３５℃に保ちながら２時間撹拌した。得られた混合液を５０℃以下になるように冷却しながらイオン交換水１００ｇで徐々に希釈し、２時間撹拌した。撹拌後の混合液に濃度３０質量％の過酸化水素水１１．１ｇを含むイオン交換水４００ｇを添加して酸化反応を停止させ、黄色の反応液を得た。
[Example 1]
(Preparation of graphene oxide dispersion)
2 g of natural graphite (“SNO-10” manufactured by SEC Carbon Co.), 9.2 g of sulfuric acid, 1 g of potassium peroxodisulfate, and 1 g of diphosphorus pentoxide were charged and reacted at 80 ° C. for 5 hours. Thereafter, the mixture was gradually cooled to room temperature, diluted with 200 g of ion exchange water, and allowed to stand overnight. The reaction solution was filtered through a Buchner funnel, and the resulting solid content was washed with ion exchange water until the ion exchange water after washing became neutral. The solid content after washing was vacuum-dried overnight at room temperature, and then mixed with 147.2 g of sulfuric acid at 0 ° C. While stirring the mixed solution, 8 g of potassium permanganate was gradually added over 30 minutes while maintaining the temperature of the mixed solution at 20 ° C. or lower, and stirred for 2 hours while maintaining the temperature of the mixed solution at 35 ° C. While cooling the obtained mixed liquid to 50 ° C. or lower, it was gradually diluted with 100 g of ion-exchanged water and stirred for 2 hours. 400 g of ion-exchanged water containing 11.1 g of hydrogen peroxide solution having a concentration of 30% by mass was added to the mixed solution after stirring to stop the oxidation reaction, thereby obtaining a yellow reaction solution.
反応液をブフナー漏斗で濾過し、得られた固形分から金属イオンを除去する為に３％の塩酸５０７．５ｇで洗浄し、粘調な反応物を得た。反応物を透析膜で包んでイオン交換水中に一週間静置して透析を行い、残留している金属イオンと塩酸を除去した。その後３０分間超音波処理を行い、黄茶色の粘調な反応物を得た。得られた反応物をイオン交換水で希釈して酸化グラフェン分散液を調製した。酸化グラフェン分散液１０００ｍｇ中には５ｍｇの酸化グラフェンが含まれていた。なお、酸化グラフェン分散液中の酸化グラフェン量は、酸化グラフェン分散液を６０℃で２時間真空乾燥させて得られる固形分量から求めた。 The reaction solution was filtered with a Buchner funnel, and washed with 507.5 g of 3% hydrochloric acid to remove metal ions from the obtained solid, to obtain a viscous reaction product. The reaction product was wrapped with a dialysis membrane and allowed to stand in ion-exchanged water for one week for dialysis to remove residual metal ions and hydrochloric acid. Thereafter, ultrasonic treatment was performed for 30 minutes to obtain a yellowish brown viscous reaction product. The obtained reaction product was diluted with ion exchange water to prepare a graphene oxide dispersion. In 1000 mg of the graphene oxide dispersion, 5 mg of graphene oxide was contained. The amount of graphene oxide in the graphene oxide dispersion was determined from the solid content obtained by vacuum drying the graphene oxide dispersion at 60 ° C. for 2 hours.
なお、得られた反応物の光電子スペクトルを測定し、２８７ｅＶ付近の炭素−酸素結合に由来するピークを観測することにより、反応物が酸化物（すなわち、酸化グラフェン）であることを確認した。光電子スペクトルの測定結果は、図１に示すとおりであった。 Note that the photoelectron spectrum of the obtained reaction product was measured, and a peak derived from a carbon-oxygen bond near 287 eV was observed to confirm that the reaction product was an oxide (ie, graphene oxide). The measurement result of the photoelectron spectrum was as shown in FIG.
（熱電変換材料の製造）
上記と同様の方法により、酸化グラフェン分散液１０００ｇを調製した。
酸化グラフェン分散液１０００ｇ（酸化グラフェン含有量：５ｇ）にアニリン２．５ｇを加えて１０分間超音波処理を行い、酸化グラフェン６７質量％及びアニリン３３質量％を含む混合液からなる熱電変換材料前駆体を調製した。得られた混合液を電解液とし、作用極にＦＴＯ、対極に白金、参照極に銀―塩化銀電極を使用して三極セルを組み立てた。北斗電工社製ポテンショ―ガルバノスタットＨＺ−３０００を用いて−０．９Ｖの定電圧条件で電気化学還元を２分間行い、その後＋１．４Ｖの定電圧条件で電気化学酸化を３０秒間行った。この還元及び酸化を１サイクルとして、５０サイクル行った。
(Manufacture of thermoelectric conversion materials)
By the same method as described above, 1000 g of graphene oxide dispersion was prepared.
Thermoelectric conversion material precursor comprising a mixed solution containing 67% by mass of graphene oxide and 33% by mass of aniline by adding 2.5 g of aniline to 1000 g of graphene oxide dispersion (graphene oxide content: 5g) and performing ultrasonic treatment for 10 minutes. Was prepared. The obtained mixed solution was used as an electrolytic solution, and a triode cell was assembled using FTO as a working electrode, platinum as a counter electrode, and a silver-silver chloride electrode as a reference electrode. Using a potentio-galvanostat HZ-3000 manufactured by Hokuto Denko, electrochemical reduction was performed for 2 minutes under a constant voltage condition of -0.9V, and then electrochemical oxidation was performed for 30 seconds under a constant voltage condition of + 1.4V. This reduction and oxidation was performed as one cycle, and 50 cycles were performed.
作用極板上の生成物を作用極から剥離し、厚み１０μｍの熱電変換材料を得た。熱電変換材料の厚みはマイクロメーターで測定した。得られた熱電変換材料の光電子スペクトルの測定結果を図２に示す。図２において、図１と比較して２８７ｅＶ付近のピーク強度が弱くなっていることから、酸化グラフェンが還元されていることが確認できる。 The product on the working electrode plate was peeled from the working electrode to obtain a thermoelectric conversion material having a thickness of 10 μm. The thickness of the thermoelectric conversion material was measured with a micrometer. The measurement result of the photoelectron spectrum of the obtained thermoelectric conversion material is shown in FIG. In FIG. 2, since the peak intensity near 287 eV is weaker than that in FIG. 1, it can be confirmed that graphene oxide is reduced.
また、得られた熱電変換材料について、下記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は１１Ｓ／ｃｍ、熱伝導率は０．１５Ｗ／ｍ・Ｋ、ゼーベック係数は１５μＶ／Ｋ、２５℃におけるＰＦは０．２５μＷ／ｍ・Ｋ２、ＺＴは５×１０−４であった。 In addition, for the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the following methods. The conductivity is 11 S / cm, the thermal conductivity is 0.15 W / m · K, the Seebeck coefficient is 15 μV / K, the PF at 25 ° C. is 0.25 μW / m · K 2 , and the ZT is 5 × 10 −4. It was.
（１）導電率
得られた熱電変換材料を２０ｍｍ×１０ｍｍに切り出して試験片とし、温度２５℃で四端子法にて（三菱化学アナリテック社製抵抗率計ロレスタＧＰ ＭＣＰ−Ｔ６１０型、プローブ：ＱＰＰを使用）、熱電変換材料の導電率を測定した。
(1) Conductivity The obtained thermoelectric conversion material was cut into 20 mm × 10 mm to make a test piece, and the temperature was measured at 25 ° C. by a four-terminal method (Mitsubishi Chemical Analytech Corp. resistivity meter Loresta GP MCP-T610, probe: QPP was used), and the electric conductivity of the thermoelectric conversion material was measured.
（２）熱伝導率
得られた熱電変換材料を１０ｍｍ×１０ｍｍに切り出して試験片とし、熱拡散率、比熱及び密度を測定し、以下の式より熱伝導率を算出した。
（熱伝導率）＝（熱拡散率）×（比熱）×（密度）
なお、熱拡散率と比熱はレーザーフラッシュ法により測定し、密度はアルキメデス法により測定した。すべての測定は２５℃にて実施した。
(2) Thermal conductivity The obtained thermoelectric conversion material was cut out into 10 mm x 10 mm, it was set as the test piece, the thermal diffusivity, the specific heat, and the density were measured, and the thermal conductivity was computed from the following formula | equation.
(Thermal conductivity) = (thermal diffusivity) x (specific heat) x (density)
The thermal diffusivity and specific heat were measured by the laser flash method, and the density was measured by the Archimedes method. All measurements were performed at 25 ° C.
（３）ゼーベック係数
得られた熱電変換材料を２０ｍｍ×１０ｍｍに切り出して試験片とし、試験片の一端を加熱し、両端に生じる温度差と電圧をアルメル―クロメル熱電対で計測することでゼーベック係数を算出した。具体的には、温度と電圧を測定する試料の両端間距離を１５ｍｍとして、片側を２５℃に固定し、もう一端を３０℃まで加熱して、その間の温度と電圧を測定して、温度差と電圧の傾きからゼーベック係数を算出した。
(3) Seebeck coefficient The obtained thermoelectric conversion material was cut into 20 mm x 10 mm to form a test piece, one end of the test piece was heated, and the temperature difference and voltage generated at both ends were measured with an alumel-chromel thermocouple to see the Seebeck coefficient. Was calculated. Specifically, the distance between both ends of the sample for measuring temperature and voltage is 15 mm, one side is fixed at 25 ° C., the other end is heated to 30 ° C., the temperature and voltage between them are measured, and the temperature difference is measured. The Seebeck coefficient was calculated from the voltage slope.
（４）パワーファクター（ＰＦ）
パワーファクター（ＰＦ）は、以下の式により求めた。
ＰＦ＝Ｓ２σ
（Ｓ：ゼーベック係数（Ｖ／Ｋ）、σ：導電率（Ｓ／ｍ））
(4) Power factor (PF)
The power factor (PF) was determined by the following formula.
PF = S 2 σ
(S: Seebeck coefficient (V / K), σ: conductivity (S / m))
（５）無次元性能指数（ＺＴ）
無次元性能指数（ＺＴ）は、以下の式により求めた。
ＺＴ＝Ｓ２σＴ／κ
（（Ｓ：ゼーベック係数（Ｖ／Ｋ）、σ：導電率（Ｓ／ｍ）、Ｔ：絶対温度（Ｋ）、κ：熱伝導率（Ｗ／ｍ・Ｋ））
(5) Dimensionless figure of merit (ZT)
The dimensionless figure of merit (ZT) was determined by the following formula.
ZT = S2σT / κ
((S: Seebeck coefficient (V / K), σ: conductivity (S / m), T: absolute temperature (K), κ: thermal conductivity (W / m · K))
［実施例２］
アニリンの仕込量を２．５ｇから０．５ｇに変更して、熱電変換材料前駆体を、酸化グラフェン９１質量％及びアニリン９質量％の混合液としたこと以外は、実施例１と同様の操作を行い、厚み１０μｍの熱電変換材料を得た。
[Example 2]
The same operation as in Example 1 except that the amount of charged aniline was changed from 2.5 g to 0.5 g and the thermoelectric conversion material precursor was a mixed liquid of 91% by mass of graphene oxide and 9% by mass of aniline. To obtain a thermoelectric conversion material having a thickness of 10 μm.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は２４Ｓ／ｃｍ、熱伝導率は０．１８Ｗ／ｍ・Ｋ、ゼーベック係数は１４μＶ／Ｋ、２５℃におけるＰＦは０．４６μＷ／ｍ・Ｋ２、ＺＴは８×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 24 S / cm, the thermal conductivity was 0.18 W / m · K, the Seebeck coefficient was 14 μV / K, the PF at 25 ° C. was 0.46 μW / m · K 2 , and the ZT was 8 × 10 −4 .
［実施例３］
アニリンの仕込量を２．５ｇから０．２５ｇに変更して、熱電変換材料前駆体を、酸化グラフェン９５質量％及びアニリン５質量％の混合液としたこと以外は、実施例１と同様の操作を行い、厚み１０μｍの熱電変換材料を得た。
[Example 3]
The same operation as in Example 1 except that the amount of charged aniline was changed from 2.5 g to 0.25 g and the thermoelectric conversion material precursor was a mixed liquid of 95% by mass of graphene oxide and 5% by mass of aniline. And a thermoelectric conversion material having a thickness of 10 μm was obtained.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は５５Ｓ／ｃｍ、熱伝導率は０．２Ｗ／ｍ・Ｋ、ゼーベック係数は１７μＶ／Ｋ、２５℃におけるＰＦは１．６０μＷ／ｍ・Ｋ２、ＺＴは２４×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 55 S / cm, the thermal conductivity was 0.2 W / m · K, the Seebeck coefficient was 17 μV / K, the PF at 25 ° C. was 1.60 μW / m · K 2 , and the ZT was 24 × 10 −4 .
［実施例４］
アニリンの仕込量を２．５ｇから０．１６７ｇに変更して、熱電変換材料前駆体を、酸化グラフェン９７質量％及びアニリン３質量％の混合液としたこと以外は、実施例１と同様の操作を行い、厚み１０μｍの熱電変換材料を得た。
[Example 4]
The same operation as in Example 1 except that the amount of aniline charged was changed from 2.5 g to 0.167 g and the thermoelectric conversion material precursor was a mixed liquid of 97% by mass of graphene oxide and 3% by mass of aniline. And a thermoelectric conversion material having a thickness of 10 μm was obtained.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は６５Ｓ／ｃｍ、熱伝導率は０．２１Ｗ／ｍ・Ｋ、ゼーベック係数は１４μＶ／Ｋ、２５℃におけるＰＦは１．３３μＷ／ｍ・Ｋ２、ＺＴは１９×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 65 S / cm, the thermal conductivity was 0.21 W / m · K, the Seebeck coefficient was 14 μV / K, the PF at 25 ° C. was 1.33 μW / m · K 2 , and the ZT was 19 × 10 −4 .
［実施例５］
アニリンの仕込量を２．５ｇから０．１２５ｇに変更して、熱電変換材料前駆体を、酸化グラフェン９８質量％及びアニリン２質量％の混合液としたこと以外は、実施例１と同様の操作を行い、厚み１０μｍの熱電変換材料を得た。
[Example 5]
The same operation as in Example 1 except that the charged amount of aniline was changed from 2.5 g to 0.125 g, and the thermoelectric conversion material precursor was a mixed liquid of 98% by mass of graphene oxide and 2% by mass of aniline. And a thermoelectric conversion material having a thickness of 10 μm was obtained.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は２０Ｓ／ｃｍ、熱伝導率は０．２１Ｗ／ｍ・Ｋ、ゼーベック係数は１４μＶ／Ｋ、２５℃におけるＰＦは０．４２μＷ／ｍ・Ｋ２、ＺＴは６×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 20 S / cm, the thermal conductivity was 0.21 W / m · K, the Seebeck coefficient was 14 μV / K, the PF at 25 ° C. was 0.42 μW / m · K 2 , and the ZT was 6 × 10 −4 .
［実施例６］
（酸化カーボンブラック分散液の調製）
天然グラファイト２ｇに替えてカーボンブラック（電気化学工業社製「ＨＳ−１００」）１ｇを用いたこと以外は、実施例１の「酸化グラフェンの分散液の調製」と同様の操作を行い、酸化カーボンブラック分散液を調製した。酸化カーボンブラック分散液１０００ｍｇ中には５ｍｇの酸化カーボンブラックが含まれていた。なお、酸化カーボンブラック分散液中の酸化カーボンブラックの量は、酸化カーボンブラック分散液を６０℃で２４時間真空乾燥することで得られる固形分量から求めた。
[Example 6]
(Preparation of oxidized carbon black dispersion)
Except that 1 g of carbon black (“HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd.) was used instead of 2 g of natural graphite, the same operation as in “Preparation of Graphene Oxide Dispersion” in Example 1 was performed, and carbon oxide A black dispersion was prepared. In 1000 mg of the oxidized carbon black dispersion, 5 mg of oxidized carbon black was contained. The amount of oxidized carbon black in the oxidized carbon black dispersion was determined from the solid content obtained by vacuum drying the oxidized carbon black dispersion at 60 ° C. for 24 hours.
（熱電変換材料の作製）
上記と同様の方法により、酸化カーボンブラック分散液１０００ｇを調製した。
酸化グラフェン分散液１０００ｇに替えて酸化カーボンブラック分散液１０００ｇ（酸化カーボンブラック含有量：５ｇ）を用いたこと以外は、実施例１の「熱電変換材料の製造」と同様の操作を行い、厚み１０μｍの熱電変換材料を得た。
(Production of thermoelectric conversion material)
1000 g of oxidized carbon black dispersion was prepared by the same method as above.
Except for using 1000 g of oxidized carbon black dispersion (oxidized carbon black content: 5 g) instead of 1000 g of graphene oxide dispersion, the same operation as in “Production of thermoelectric conversion material” in Example 1 was performed, and the thickness was 10 μm. A thermoelectric conversion material was obtained.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は１５Ｓ／ｃｍ、熱伝導率は０．１６Ｗ／ｍ・Ｋ、ゼーベック係数は１６μＶ／Ｋ、２５℃におけるＰＦは０．３８μＷ／ｍ・Ｋ２、ＺＴは７×１０−４あった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 15 S / cm, the thermal conductivity was 0.16 W / m · K, the Seebeck coefficient was 16 μV / K, the PF at 25 ° C. was 0.38 μW / m · K 2 , and the ZT was 7 × 10 −4 .
［実施例７］
アニリン２．５ｇに替えてピロール２．５ｇを用いて、熱電変換材料前駆体を、酸化グラフェン６７質量％及びピロール３３質量％の混合液としたこと以外は、実施例１と同様の操作を行い、厚み１０μｍの熱電変換材料を得た。
[Example 7]
The same operation as in Example 1 was performed except that 2.5 g of pyrrole was used instead of 2.5 g of aniline, and the thermoelectric conversion material precursor was a mixed liquid of 67% by mass of graphene oxide and 33% by mass of pyrrole. A thermoelectric conversion material having a thickness of 10 μm was obtained.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は５Ｓ／ｃｍ、熱伝導率は０．２Ｗ／ｍ・Ｋ、ゼーベック係数は２０μＶ／Ｋ、２５℃におけるＰＦは０．２μＷ／ｍ・Ｋ２、ＺＴは２×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 5 S / cm, the thermal conductivity was 0.2 W / m · K, the Seebeck coefficient was 20 μV / K, the PF at 25 ° C. was 0.2 μW / m · K 2 , and the ZT was 2 × 10 −4 .
［実施例８］
電気化学反応におけるサイクル数を２５サイクルとしたこと以外は、実施例７と同様の操作を行い、厚み５μｍの熱電変換材料を得た。
[Example 8]
A thermoelectric conversion material having a thickness of 5 μm was obtained by performing the same operation as in Example 7 except that the number of cycles in the electrochemical reaction was 25.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は１２Ｓ／ｃｍ、熱伝導率は０．３Ｗ／ｍ・Ｋ、ゼーベック係数は１５μＶ／Ｋ、２５℃におけるＰＦは０．３μＷ／ｍ・Ｋ２、ＺＴは３×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 12 S / cm, the thermal conductivity was 0.3 W / m · K, the Seebeck coefficient was 15 μV / K, the PF at 25 ° C. was 0.3 μW / m · K 2 , and the ZT was 3 × 10 −4 .
［実施例９］
実施例１と同様の方法により、酸化グラフェン分散液１０００ｇ（酸化グラフェン含有量：５ｇ）を調製した。
酸化グラフェン分散液１０００ｇにアニリン２．５ｇを加え、１０分間超音波処理を行い、酸化グラフェン６７質量％及びアニリン３３質量％の混合液からなる熱電変換材料前駆体を調製した。得られた混合液０．１３４ｇを、幅１５ｍｍ、長さ２５ｍｍ、厚さ３．１ｍｍのＦＴＯ基板上に塗布し、４０℃で２時間放置した。この混合液が塗布されたＦＴＯ基板を２枚作製した。濃度２Ｍの硫酸水溶液に浸漬した濾紙を、混合液が塗布された部分が濾紙と接触するように２枚のＦＴＯ基板で挟み、二極セルを組み立てた。
[Example 9]
In the same manner as in Example 1, 1000 g of graphene oxide dispersion (graphene oxide content: 5 g) was prepared.
2.5 g of aniline was added to 1000 g of the graphene oxide dispersion and subjected to ultrasonic treatment for 10 minutes to prepare a thermoelectric conversion material precursor composed of a mixed liquid of 67% by mass of graphene oxide and 33% by mass of aniline. 0.134 g of the obtained mixed solution was applied onto an FTO substrate having a width of 15 mm, a length of 25 mm, and a thickness of 3.1 mm, and left at 40 ° C. for 2 hours. Two FTO substrates coated with this mixed solution were produced. A filter paper immersed in a sulfuric acid aqueous solution having a concentration of 2 M was sandwiched between two FTO substrates so that a portion where the mixed solution was applied was in contact with the filter paper, and a bipolar cell was assembled.
ＦＴＯ基板の一方の電圧を−１．４Ｖから＋１．４Ｖまで１００ｍＶ／ｓｅｃで掃引し、電圧が１．４Ｖに到達したのちに−１．４Ｖまで１００ｍＶ／ｓｅｃで掃引した。これを１サイクルとして１５０サイクル行った。ＦＴＯ基板上の生成物を剥離し、厚み１６μｍの熱電変換材料を得た。 One voltage of the FTO substrate was swept from −1.4 V to +1.4 V at 100 mV / sec, and after the voltage reached 1.4 V, it was swept to −1.4 V at 100 mV / sec. This was performed as 150 cycles. The product on the FTO substrate was peeled off to obtain a thermoelectric conversion material having a thickness of 16 μm.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は５０Ｓ／ｃｍ、熱伝導率は０．１４Ｗ／ｍ・Ｋ、ゼーベック係数は１５μＶ／Ｋ、２５℃におけるＰＦは１．１３μＷ／ｍ・Ｋ２、ＺＴは２３×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 50 S / cm, the thermal conductivity was 0.14 W / m · K, the Seebeck coefficient was 15 μV / K, the PF at 25 ° C. was 1.13 μW / m · K 2 , and the ZT was 23 × 10 −4 .
［実施例１０］
アニリンの仕込量を２．５ｇから１．２５ｇに変更して、酸化グラフェン８０質量％及びアニリン２０質量％の混合液を調製した。得られた混合液０．１６ｇを、幅１５ｍｍ、長さ２５ｍｍ、厚さ３．１ｍｍのＦＴＯ基板上に塗布し、４０℃で２時間放置した。この混合液が塗布されたＦＴＯ基板を２枚作製した。このＦＴＯ基板を用い、サイクル数を３００としたこと以外は、実施例９と同様の操作を行い、厚み１６μｍの熱電変換材料を得た。
[Example 10]
The mixed amount of graphene oxide 80% by mass and aniline 20% by mass was prepared by changing the charged amount of aniline from 2.5 g to 1.25 g. 0.16 g of the obtained mixed solution was applied onto an FTO substrate having a width of 15 mm, a length of 25 mm, and a thickness of 3.1 mm, and left at 40 ° C. for 2 hours. Two FTO substrates coated with this mixed solution were produced. A thermoelectric conversion material having a thickness of 16 μm was obtained by using this FTO substrate and performing the same operation as in Example 9 except that the number of cycles was set to 300.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は６８Ｓ／ｃｍ、熱伝導率は０．１６Ｗ／ｍ・Ｋ、ゼーベック係数は１８μＶ／Ｋ、２５℃におけるＰＦは２．２μＷ／ｍ・Ｋ２、ＺＴは４１×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 68 S / cm, the thermal conductivity was 0.16 W / m · K, the Seebeck coefficient was 18 μV / K, the PF at 25 ° C. was 2.2 μW / m · K 2 , and the ZT was 41 × 10 −4 .
［実施例１１］
アニリンの仕込量を２．５ｇから０．６２５ｇに変更して、酸化グラフェン８９質量％及びアニリン１１質量％の混合液を調製した。得られた混合液０．１７８ｇを、幅１５ｍｍ、長さ２５ｍｍ、厚さ３．１ｍｍのＦＴＯ基板上に塗布し、４０℃で２時間放置した。この混合液が塗布されたＦＴＯ基板を２枚作製した。このＦＴＯ基板を用い、サイクル数を３５０としたこと以外は、実施例９と同様の操作を行い、厚み１６μｍの熱電変換材料を得た。
[Example 11]
The amount of charged aniline was changed from 2.5 g to 0.625 g to prepare a mixed solution of 89% by mass of graphene oxide and 11% by mass of aniline. 0.178 g of the obtained mixed solution was applied onto an FTO substrate having a width of 15 mm, a length of 25 mm, and a thickness of 3.1 mm, and left at 40 ° C. for 2 hours. Two FTO substrates coated with this mixed solution were produced. A thermoelectric conversion material having a thickness of 16 μm was obtained by using this FTO substrate and performing the same operation as in Example 9 except that the number of cycles was 350.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は７２Ｓ／ｃｍ、熱伝導率は０．１８Ｗ／ｍ・Ｋ、ゼーベック係数は２０μＶ／Ｋ、２５℃におけるＰＦは２．８８μＷ／ｍ・Ｋ２、ＺＴは４８×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 72 S / cm, the thermal conductivity was 0.18 W / m · K, the Seebeck coefficient was 20 μV / K, the PF at 25 ° C. was 2.88 μW / m · K 2 , and the ZT was 48 × 10 −4 .
［実施例１２］
アニリンの仕込量を２．５ｇから０．３１２５ｇに変更して、酸化グラフェン９４質量％及びアニリン６質量％の混合液を調製した。得られた混合液０．１８８ｇを、幅１５ｍｍ、長さ２５ｍｍ、厚さ３．１ｍｍのＦＴＯ基板上に塗布し、４０℃で２時間放置した。この混合液が塗布されたＦＴＯ基板を２枚作製した。このＦＴＯ基板を用い、サイクル数を４００としたこと以外は、実施例９と同様の操作を行い、厚み１６μｍの熱電変換材料を得た。
[Example 12]
The charged amount of aniline was changed from 2.5 g to 0.3125 g to prepare a mixed solution of 94% by mass of graphene oxide and 6% by mass of aniline. 0.188 g of the obtained mixed solution was applied on an FTO substrate having a width of 15 mm, a length of 25 mm, and a thickness of 3.1 mm, and left at 40 ° C. for 2 hours. Two FTO substrates coated with this mixed solution were produced. A thermoelectric conversion material having a thickness of 16 μm was obtained by using this FTO substrate and performing the same operation as in Example 9 except that the number of cycles was set to 400.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は８０Ｓ／ｃｍ、熱伝導率は０．１８Ｗ／ｍ・Ｋ、ゼーベック係数は１９μＶ／Ｋ、２５℃におけるＰＦは２．８９μＷ／ｍ・Ｋ２、ＺＴは４８×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 80 S / cm, the thermal conductivity was 0.18 W / m · K, the Seebeck coefficient was 19 μV / K, the PF at 25 ° C. was 2.89 μW / m · K 2 , and the ZT was 48 × 10 −4 .
［実施例１３］
実施例６と同様の方法により、酸化カーボンブラック分散液１０００ｇ（酸化カーボンブラック含有量：５ｇ）を調製した。
酸化グラフェン分散液に替えて酸化カーボンブラック分散液を用いたこと以外は、実施例９と同様の操作を行い、厚み１６μｍの熱電変換材料を得た。
[Example 13]
In the same manner as in Example 6, 1000 g of oxidized carbon black dispersion (oxidized carbon black content: 5 g) was prepared.
A thermoelectric conversion material having a thickness of 16 μm was obtained by performing the same operation as in Example 9 except that an oxidized carbon black dispersion was used instead of the graphene oxide dispersion.
得られた熱電変換材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は６５Ｓ／ｃｍ、熱伝導率は０．１９Ｗ／ｍ・Ｋ、ゼーベック係数は１９μＶ／Ｋ、２５℃におけるＰＦは２．３５μＷ／ｍ・Ｋ２、ＺＴは３７×１０−４であった。 For the obtained thermoelectric conversion material, the electrical conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) were determined by the above method. The rate was 65 S / cm, the thermal conductivity was 0.19 W / m · K, the Seebeck coefficient was 19 μV / K, the PF at 25 ° C. was 2.35 μW / m · K 2 , and the ZT was 37 × 10 −4 .
［比較例１］
実施例１と同様の方法により調製した酸化グラフェン分散液０．２ｇをステンレス基板上に塗布し、５０℃で１０分間放置した。濃度２Ｍの硫酸水溶液１．６８ｇにアニリン０．０１５３ｇを加えた混合液を含浸させたろ紙を、酸化グラフェン分散液が塗布されたスンレス基板上に配置し、更にろ紙の上にステンレス基板を配置した。酸化グラフェン分散液を塗布したステンレス基板の電圧を−１．４Ｖとして、定電圧条件で還元を２時間行った。ステンレス基板上の生成物を剥離し、酸化グラフェンの還元物からなる厚み２０μｍの導電性材料を得た。
[Comparative Example 1]
0.2 g of graphene oxide dispersion prepared by the same method as in Example 1 was applied on a stainless steel substrate and allowed to stand at 50 ° C. for 10 minutes. A filter paper impregnated with a mixed solution obtained by adding 0.0153 g of aniline to 1.68 g of a 2M sulfuric acid aqueous solution was placed on a stainless steel substrate coated with graphene oxide dispersion, and a stainless steel substrate was placed on the filter paper. . The voltage of the stainless steel substrate coated with the graphene oxide dispersion was −1.4 V, and reduction was performed for 2 hours under constant voltage conditions. The product on the stainless steel substrate was peeled off to obtain a conductive material having a thickness of 20 μm made of a reduced product of graphene oxide.
得られた導電性材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は３７Ｓ／ｃｍ、熱伝導率は１０Ｗ／ｍ・Ｋ、ゼーベック係数は１６μＶ／Ｋ、２５℃におけるＰＦは０．９０μＷ／ｍ・Ｋ２、ＺＴは０．３×１０−４あった。 The obtained conductive material was measured for conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) by the above method. The rate was 37 S / cm, the thermal conductivity was 10 W / m · K, the Seebeck coefficient was 16 μV / K, the PF at 25 ° C. was 0.90 μW / m · K 2 , and the ZT was 0.3 × 10 −4 .
［比較例２］
２Ｍの硫酸水溶液１６８ｇにアニリン１．５３ｇを加えた混合物を電解液とし、作用極にＦＴＯ、対極に白金ワイヤー、参照極に銀―塩化銀電極を使用して三極セルを組み立てた。０．９Ｖの定電圧条件で２時間電気化学酸化を行い、作用極上の生成物を剥離して、導電性ポリマーからなる厚み１６μｍの導電性材料を得た。
[Comparative Example 2]
A mixture of 168 g of 2M aqueous sulfuric acid and 1.53 g of aniline was used as the electrolyte, and a triode cell was assembled using FTO as the working electrode, platinum wire as the counter electrode, and silver-silver chloride electrode as the reference electrode. Electrochemical oxidation was performed for 2 hours under a constant voltage condition of 0.9 V, and the product on the working electrode was peeled off to obtain a conductive material having a thickness of 16 μm made of a conductive polymer.
得られた導電性材料について、上記の方法で導電率（σ）、熱伝導率（κ）、ゼーベック係数（Ｓ）、パワーファクター（ＰＦ）、無次元性能指数（ＺＴ）を求めたところ、導電率は７Ｓ／ｃｍ、熱伝導率は０．２Ｗ／ｍ・Ｋ、ゼーベック係数は２μＶ／Ｋ、２５℃におけるＰＦは０．００３μＷ／ｍ・Ｋ２、ＺＴは１×１０−４であった。 The obtained conductive material was measured for conductivity (σ), thermal conductivity (κ), Seebeck coefficient (S), power factor (PF), and dimensionless figure of merit (ZT) by the above method. The rate was 7 S / cm, the thermal conductivity was 0.2 W / m · K, the Seebeck coefficient was 2 μV / K, the PF at 25 ° C. was 0.003 μW / m · K 2 , and the ZT was 1 × 10 −4 .
基材浸漬法によって熱電変換材料を製造した実施例１〜８の結果を表１に、基板塗布法によって熱電変換材料を製造した実施例９〜１３の結果を表２に示す。また、比較例１及び２の結果を表２に示す。 The result of Examples 1-8 which manufactured the thermoelectric conversion material by the base material immersion method is shown in Table 1, and the result of Examples 9-13 which manufactured the thermoelectric conversion material by the board | substrate coating method is shown in Table 2. The results of Comparative Examples 1 and 2 are shown in Table 2.
本発明に係る熱電変換材料は、安価に製造でき、且つ熱電変換特性に優れるため、熱電変換素子（熱電変換モジュール、熱電変換セル等）に好適に使用することができる。
Since the thermoelectric conversion material according to the present invention can be produced at low cost and has excellent thermoelectric conversion characteristics, it can be suitably used for thermoelectric conversion elements (thermoelectric conversion modules, thermoelectric conversion cells, etc.).
Claims (14)
前記炭素材料が、酸化グラフェン及び酸化カーボンブラックからなる群より選択される炭素原料の還元物を含有し、
前記炭素材料を含む層と前記導電性ポリマーを含む層とが交互に積層された構造を有する、熱電変換材料。 Including a carbon material and a conductive polymer;
The carbon material contains a reduced product of a carbon raw material selected from the group consisting of graphene oxide and carbon black oxide ,
And a layer to have a stacked structure alternately comprising the conductive polymer and a layer containing the carbon material, the thermoelectric conversion material.
前記導電性ポリマーが、電解重合可能なモノマーの重合物を含有し、
前記電気化学反応に供された前記炭素原料の量が、前記炭素原料及び前記モノマーの総量基準で５０〜９９質量％である、請求項１〜４のいずれか一項に記載の熱電変換材料。 The reduced product is obtained by reducing the carbon raw material by an electrochemical reaction,
The conductive polymer contains a polymerized monomer that can be electropolymerized,
The thermoelectric conversion material according to any one of claims 1 to 4, wherein an amount of the carbon raw material subjected to the electrochemical reaction is 50 to 99 mass% based on a total amount of the carbon raw material and the monomer.
前記炭素原料及び電解重合可能なモノマーを含む混合液に浸漬された導電性基板に、正の電圧及び負の電圧を交互に印加して、該導電性基板上に前記炭素材料及び前記導電性ポリマーを含む前記熱電変換材料を形成する工程を有する、熱電変換材料の製造方法。 A method for producing the thermoelectric conversion material according to any one of claims 1 to 8 ,
A positive voltage and a negative voltage are alternately applied to a conductive substrate immersed in a liquid mixture containing the carbon raw material and an electropolymerizable monomer so that the carbon material and the conductive polymer are formed on the conductive substrate. The manufacturing method of the thermoelectric conversion material which has the process of forming the said thermoelectric conversion material containing.
前記炭素原料及び電解重合可能なモノマーを含む混合液が一方面上に塗布された２つの導電性基板を、電解液を含浸させたセパレータを介して前記混合液が塗布された面同士が対向するように配置する工程と、
前記導電性基板の一方に、他方の導電性基板に対する正の電圧及び負の電圧を交互に印加して、前記導電性基板上に前記炭素材料及び前記導電性ポリマーを含む前記熱電変換材料を形成する工程と、
を有する、熱電変換材料の製造方法。 A method for producing the thermoelectric conversion material according to any one of claims 1 to 8 ,
Two conductive substrates coated on one surface with a mixed liquid containing the carbon raw material and an electropolymerizable monomer face each other on the surfaces coated with the mixed liquid through a separator impregnated with the electrolytic solution. The step of arranging
While the of the conductive substrate, a positive voltage 及 beauty negative voltage to the other of the conductive substrate by applying alternately, the thermoelectric conversion material comprising the carbon material and the conductive polymer on the conductive substrate Forming, and
A method for producing a thermoelectric conversion material.
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