JP2012119657A - Photothermal power generation element and photothermal power generation method using the same - Google Patents
Photothermal power generation element and photothermal power generation method using the same Download PDFInfo
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本発明は、光熱発電素子及び該光熱発電素子を用いた光熱発電方法に関する。 The present invention relates to a photothermal power generation element and a photothermal power generation method using the photothermal power generation element.
近年、新たな電力源として、熱電効果を利用した発電機構の開発が行われるようになってきている。熱電効果は、電気伝導体や半導体などの金属中において、熱流の熱エネルギーと電流の電気エネルギーが相互に及ぼし合う効果の総称であり、ゼーベック効果、ペルティエ効果、トムソン効果の３つの効果をいう。このうち、ゼーベック効果は物体の温度差が電圧に直接変換される現象であり、電圧を温度差に変換するペルティエ効果とはちょうど逆の関係にある。 In recent years, power generation mechanisms using the thermoelectric effect have been developed as new power sources. The thermoelectric effect is a general term for effects in which heat energy of heat flow and electric energy of electric current interact with each other in a metal such as an electric conductor or a semiconductor, and refers to three effects: Seebeck effect, Peltier effect, and Thomson effect. Of these, the Seebeck effect is a phenomenon in which the temperature difference of an object is directly converted into a voltage, and is just opposite to the Peltier effect that converts a voltage into a temperature difference.
ゼーベック効果によれば、温度差を電圧に変換することができ、これを利用して電気を発生させることができる。このような熱電発電システムを実現する熱電モジュールについては、これまでに様々な開発がなされてきている（例えば非特許文献１参照）。 According to the Seebeck effect, a temperature difference can be converted into a voltage, and electricity can be generated using this. Various developments have been made so far for the thermoelectric module that realizes such a thermoelectric power generation system (see, for example, Non-Patent Document 1).
このような熱を電気に変換するシステムにおいては、熱を供給すれば発電し、熱の供給を止めれば発電も停止することとなり、熱の供給の有無を発電のスイッチとして用いることができる。 In such a system that converts heat into electricity, power is generated when heat is supplied, and power generation is stopped when the supply of heat is stopped, and the presence or absence of the supply of heat can be used as a switch for power generation.
そこで、効率よく短時間で熱することが可能な素材を加熱して熱源として用いることで、このようなスイッチ機能を実現できると考えられるが、そのような研究はほとんどなされていない。 Therefore, it is considered that such a switch function can be realized by heating a material that can be heated efficiently and in a short time and using it as a heat source, but such research has hardly been conducted.
特許文献１は、カーボンナノチューブを含む熱電モジュールを開示しているが、その光熱発電効率において改善が求められていた。
本発明は、効率よく短時間で熱することが可能な素材を光により加熱して熱源として用い、光照射により発電可能な光熱発電素子を提供することを目的とする。 An object of the present invention is to provide a photothermal power generation element capable of generating power by light irradiation using a material that can be efficiently heated in a short time as a heat source.
本発明者らは、驚くべきことに、カーボンナノチューブとポリ(3-ヘキシルチオフェン)（P3HT）の複合体をポリジメチルシロキサン（PDMS）中に分散させたコンポジットに光を吸収させて熱源とすれば、高効率で光発電可能な光熱発電素子を提供できることを見出し本発明を完成させるに至った。 Surprisingly, the inventors have absorbed light into a composite in which a composite of carbon nanotubes and poly (3-hexylthiophene) (P3HT) is dispersed in polydimethylsiloxane (PDMS) and used as a heat source. The present inventors have found that a photothermal power generation element capable of photovoltaic power generation with high efficiency can be provided and have completed the present invention.
すなわち、本発明は例えば以下の光熱発電素子及び該光熱発電素子を用いた光熱発電方法に係るものである。
項１．光発熱体により熱電モジュールを被覆した光熱発電素子であって、前記光発熱体がカーボンナノチューブ(CNT)とポリ(3-ヘキシルチオフェン)（P3HT）の複合体をポリジメチルシロキサン（PDMS）中に含むコンポジットから構成される、光熱発電素子。
項２．項１に記載の光熱発電素子の光発熱体に光を吸収させ、前記熱電モジュールで発電する、光熱発電方法。
That is, the present invention relates to, for example, the following photothermal power generation element and a photothermal power generation method using the photothermal power generation element.
本発明は、ポリ(3-ヘキシルチオフェン)（P3HT）をカーボンナノチューブ表面に吸着させて複合体を形成し、PDMS中に均一に分散したコンポジットを光発熱体として用いることで、優れた変換効率を有する光熱発電素子を得ることができた。本発明のコンポジットは、カーボンナノチューブの分散性に非常に優れているので、黒色でありながら高い透明性を保つことができ、良好な光吸収性と、光熱変換効率を有している。 In the present invention, poly (3-hexylthiophene) (P3HT) is adsorbed on the surface of a carbon nanotube to form a composite, and a composite that is uniformly dispersed in PDMS is used as a light heating element. It was possible to obtain a photothermal power generation element having the same. Since the composite of the present invention is very excellent in dispersibility of carbon nanotubes, it can maintain high transparency while being black, and has good light absorption and photothermal conversion efficiency.
本発明では、カーボンナノチューブとP3HTの複合体を均一分散したPDMSにより熱電変換モジュールを被覆し、当該PDMS(光発熱体)に光を照射することで発電が可能であることを確認した。光照射による発電の際の発熱は少なく、生体内に埋め込んでも発熱による損傷はなく、安全に繰り返し発電させることができる。また、光熱耐久性は極めて高い。 In the present invention, it was confirmed that power generation is possible by coating a thermoelectric conversion module with PDMS in which a composite of carbon nanotubes and P3HT is uniformly dispersed, and irradiating the PDMS (light heating element) with light. There is little heat generation during power generation due to light irradiation, and even if it is embedded in a living body, there is no damage due to heat generation, and power generation can be repeated safely. Moreover, the photothermal durability is extremely high.
例えば当該素子を生体内に埋め込み、光として生体の透過性が高い近赤外領域の光を使用することで、心筋の拍動や運動神経の動的制御、ペースメーカーなどに応用できる。 For example, by embedding the element in a living body and using light in the near-infrared region, which is highly permeable to the living body, it can be applied to cardiac pulsation, dynamic control of motor nerves, pacemakers and the like.
本発明の光熱発電素子は、発電が望まれる時には光の照射を行い、発電が望まれない時には光の照射を行わないようにすることで、発電の有無を短時間で簡便に切り替えることができる。また、光照射により発電可能であるから、例えば危険な領域で作業を行うロボット等（宇宙空間での作業用ロボット、災害救助用ロボットなど）の遠隔操作等にも有用である。 The photothermal power generation element of the present invention can easily switch the presence or absence of power generation in a short time by irradiating light when power generation is desired and not irradiating light when power generation is not desired. . Further, since power generation is possible by light irradiation, it is useful for remote control of a robot or the like (for example, a robot for working in outer space or a robot for disaster rescue) that performs work in a dangerous area.
熱電モジュールは、公知の熱電モジュールを広く利用することができる。例えば熱電モジュールは、熱電素子と１対のリード線を有し、電力消費機器をリード線と接続することで、熱電モジュールで発電された電気を利用して該電力消費機器を作動させることができる。 As the thermoelectric module, known thermoelectric modules can be widely used. For example, a thermoelectric module has a thermoelectric element and a pair of lead wires, and the power consuming device can be operated using electricity generated by the thermoelectric module by connecting the power consuming device to the lead wire. .
熱電素子としては、公知のものが広く用いられ、特に限定されないが、例えば絶縁層を介してあるいは接触することなく交互に配置された複数のｐ型熱電素子及びｎ型熱電素子が挙げられ、前記リード線（接続電極）はｐ型熱電素子及びｎ型熱電素子を接続する。 Known thermoelectric elements are widely used, and are not particularly limited. For example, a plurality of p-type thermoelectric elements and n-type thermoelectric elements that are alternately arranged via an insulating layer or without contact may be mentioned. The lead wire (connection electrode) connects the p-type thermoelectric element and the n-type thermoelectric element.
ｐ型熱電素子及びｎ型熱電素子の材料としては、熱電モジュールに用い得るものであれば特に制限されるものではなく、例えばｐ型熱電素子材料として(BiSb)2Te3が、ｎ型熱電素子材料としてBi2(TeSe)3が例示できる。 The material of the p-type thermoelectric element and the n-type thermoelectric element is not particularly limited as long as it can be used for the thermoelectric module. For example, (BiSb) 2 Te 3 is used as the p-type thermoelectric element material. Bi 2 (TeSe) 3 can be exemplified as the material.
本発明で用いられるカーボンナノチューブは特に制限されるものではなく、多層のもの（多層カーボンナノチューブ、「ＭＷＮＴ」と呼ばれる）から単層のもの（単層カーボンナノチューブ、「ＳＷＮＴ」と呼ばれる）まで使用することができる。好ましくは、単層ウォール・カーボンナノチューブが用いられる。用いるＳＷＮＴの製造方法としては、特に制限されるものではなく、触媒を用いる熱分解法（気相成長法と類似の方法）、アーク放電法、レーザー蒸発法、ＨｉＰｃｏ法（High-pressure carbon monoxide process）及びCVD法（Chemical Vapor Deposition）等、公知のいずれの製造方法を用いても構わない。 The carbon nanotubes used in the present invention are not particularly limited, and are used from multi-walled ones (multi-walled carbon nanotubes, called “MWNT”) to single-walled ones (single-walled carbon nanotubes, called “SWNT”). be able to. Preferably, single-walled carbon nanotubes are used. The SWNT production method to be used is not particularly limited, and a thermal decomposition method using a catalyst (a method similar to the vapor phase growth method), an arc discharge method, a laser evaporation method, a HiPco method (High-pressure carbon monoxide process). ) And CVD (Chemical Vapor Deposition), etc., any known manufacturing method may be used.
カーボンナノチューブとポリ(3-ヘキシルチオフェン)（P3HT）の複合体（以下、「ＣＮＴ複合体」と称することがある）をポリジメチルシロキサン（PDMS）中に含むコンポジットは、前記複合体がPDMS中に分散したものである。分散の度合いはできるだけ均一であることが好ましく、少なくとも目視によってカーボンナノチューブ濃度に偏りがあることが確認できないことが必要である。分散の度合いが低いと、光の吸収効率が低下、熱電変換デバイスとして機能しないため、好ましくない。 A composite containing a composite of carbon nanotubes and poly (3-hexylthiophene) (P3HT) (hereinafter sometimes referred to as “CNT composite”) in polydimethylsiloxane (PDMS), the composite is included in PDMS. It is distributed. It is preferable that the degree of dispersion be as uniform as possible, and it is necessary that it is not possible to at least visually confirm that the carbon nanotube concentration is uneven. If the degree of dispersion is low, the light absorption efficiency is lowered, and the device does not function as a thermoelectric conversion device.
ＣＮＴ複合体は、ジメチルシロキサン(DMS)への分散性が高く、カーボンナノチューブをPDMSに分散させたコンポジットの製造に適している。このようなコンポジットは、例えばジメチルシロキサン(DMS)中にＣＮＴ複合体と必要に応じて架橋剤（例えばSylgard 184; Dow Corning）を分散させて、必要に応じて水、酸或いは塩基などの触媒を用い、室温若しくは加熱下に重合（硬化）することで、ＣＮＴ複合体が均一に分散したポリジメチルシロキサン(PDMS)を得ることができる。ＣＮＴ複合体はジメチルシロキサン(DMS)との相溶性が高く、均一な溶液を得ることができる。架橋剤としては、トリメトキシメチルシラン、トリエトキシフェニルシラン、テトラメトキシシラン、テトラエトキシシラン、テトラ−ｎ−プロボキシシラン、テトラブトキシシラン等が挙げられ、具体的にはSylgard 184（Dow Corning）などが使用できる。架橋剤は、DMS100重量部に対し、5〜10重量部、好ましくは9〜10重量部使用することができる。 The CNT composite has high dispersibility in dimethylsiloxane (DMS) and is suitable for producing a composite in which carbon nanotubes are dispersed in PDMS. Such a composite is prepared by, for example, dispersing a CNT complex and a cross-linking agent (for example, Sylgard 184; Dow Corning) in dimethylsiloxane (DMS), if necessary, and adding a catalyst such as water, acid or base as necessary. By using and polymerizing (curing) at room temperature or under heating, polydimethylsiloxane (PDMS) in which the CNT composite is uniformly dispersed can be obtained. The CNT composite is highly compatible with dimethylsiloxane (DMS), and a uniform solution can be obtained. Examples of the cross-linking agent include trimethoxymethyl silane, triethoxyphenyl silane, tetramethoxy silane, tetraethoxy silane, tetra-n-propoxy silane, tetrabutoxy silane, and the like. Specifically, Sylgard 184 (Dow Corning) is used. it can. The crosslinking agent can be used in an amount of 5 to 10 parts by weight, preferably 9 to 10 parts by weight, based on 100 parts by weight of DMS.
本発明のコンポジットは、PDMS中においてCNT量として0.001〜1重量%、好ましくは0.005〜0.5重量%、より好ましくは0.01〜0.1重量%、特に0.01〜0.08重量%程度分散することができる。 The composite of the present invention can be dispersed in the PDMS as a CNT amount of 0.001 to 1% by weight, preferably 0.005 to 0.5% by weight, more preferably 0.01 to 0.1% by weight, and particularly 0.01 to 0.08% by weight.
本発明のCNT-P3HT複合体におけるカーボンナノチューブ(CNT)とP3HTの比率は、カーボンナノチューブ100重量部に対し、P3HTを100〜1000重量部、好ましくは500〜650重量部程度含む。PDMS硬化の条件は特に限定されないが、70〜80℃で、１〜１２時間程度反応させればよい。 The ratio of carbon nanotubes (CNT) to P3HT in the CNT-P3HT composite of the present invention includes 100 to 1000 parts by weight, preferably about 500 to 650 parts by weight of P3HT with respect to 100 parts by weight of carbon nanotubes. PDMS curing conditions are not particularly limited, but may be reacted at 70 to 80 ° C. for about 1 to 12 hours.
本発明の光熱発電素子は、例えば図８に示すようにCNT複合体(P3HT-SWNT)をDMSに分散させて重合して、P3HT-SWNT-PDMSからなる底面を形成し、１対の電極(リード線)を有する熱電モジュールをその上に置き、さらにCNT複合体(P3HT-SWNT)のDMS分散液を注いで、１対の電極以外の熱電モジュールを分散液で覆い、硬化(curing)することで、P3HT-SWNT-PDMSにより熱電モジュールを被覆した本発明の光熱発電素子を得ることができる。 For example, as shown in FIG. 8, the photothermal power generation device of the present invention is formed by dispersing and polymerizing a CNT composite (P3HT-SWNT) in DMS to form a bottom surface made of P3HT-SWNT-PDMS. Place a thermoelectric module with a lead wire on it, and then pour a DMS dispersion of CNT composite (P3HT-SWNT), cover the thermoelectric module other than one pair of electrodes with the dispersion, and cure Thus, the photothermal power generation element of the present invention in which the thermoelectric module is coated with P3HT-SWNT-PDMS can be obtained.
本発明の光発熱体として使用するP3HT-CNT-PDMSコンポジットの概念図を図1(a)に示す。 FIG. 1 (a) shows a conceptual diagram of a P3HT-CNT-PDMS composite used as a light heating element of the present invention.
熱電モジュールを被覆する光発熱体（P3HT-SWNT-PDMS）の厚さは、例えば０．１ｍｍ〜５．０ｍｍ程度、好ましくは０．２〜３ｍｍ、より好ましくは０．３〜２ｍｍ、特に好ましくは０．５〜１．５ｍｍである。 The thickness of the light heating element (P3HT-SWNT-PDMS) covering the thermoelectric module is, for example, about 0.1 mm to 5.0 mm, preferably 0.2 to 3 mm, more preferably 0.3 to 2 mm, particularly preferably. 0.5 to 1.5 mm.
このようにして製造される光熱発電素子は、カーボンナノチューブが分散したコンポジットが光を吸収し、発熱することによって発電する。 The photothermal power generation device manufactured in this way generates power when the composite in which the carbon nanotubes are dispersed absorbs light and generates heat.
該コンポジットに照射する光の種類は、可視〜近赤外領域の波長（400〜1100ｎｍ）を有する光であれば、特に限定されない。さらに、該コンポジットは、１１００ｎｍ以上の波長の光も吸収して発熱する。また、レーザーは指向性が極めて高いため遠隔操作が可能なことから、レーザーを用いるのが好適である。光熱発電素子を生体内の深部に埋め込んだ場合、生体に対する透過性の高い近赤外領域の光を照射するのが好ましい。 The type of light applied to the composite is not particularly limited as long as it is light having a wavelength in the visible to near infrared region (400 to 1100 nm). Further, the composite absorbs light having a wavelength of 1100 nm or more and generates heat. In addition, since the laser has extremely high directivity and can be remotely controlled, it is preferable to use a laser. When the photothermal power generation element is embedded in the deep part of the living body, it is preferable to irradiate light in the near infrared region that is highly permeable to the living body.
照射する光の強さは、コンポジットが溶解しない限り、特に制限されるものではない。本発明のコンポジットは〜1Ｗ程度のレーザー出力にも十分耐えることができる。 The intensity of light to be irradiated is not particularly limited as long as the composite is not dissolved. The composite of the present invention can sufficiently withstand a laser output of about 1 W.
以下、本発明を具体的に説明するが、本発明は下記の例に限定されるものではない。
本明細書において、以下の略号を用いる。
CNT：カーボンナノチューブ、P3HT：ポリ(3-ヘキシルチオフェン)、SWNT：単層カーボンナノチューブ、PDMS：ポリジメチルシロキサン
Hereinafter, the present invention will be specifically described, but the present invention is not limited to the following examples.
In this specification, the following abbreviations are used.
CNT: carbon nanotube, P3HT: poly (3-hexylthiophene), SWNT: single-walled carbon nanotube, PDMS: polydimethylsiloxane
実施例１
P3HT-SWNT-PDMSコンポジット及びP3HT-MWNT-PDMSコンポジットの合成
P3HT-SWNT-PDMSコンポジットは、次の方法により作製した。SWNT（5 mg）［high-pressure carbon monoxide（Hipco）super-purified SWNTs（purity > 95%）; Carbon Nanotechnologies］とP3HT（2.5 mg）（regioregular; Ardrich）をクロロホルム（40 mL）に添加し、15 min間、氷冷下（> 8℃）で超音波処理（USD-2R; AS ONE）を施した。得られたP3HT-SWNT複合体溶液を遠心分離（11,000 rpm, 15 min, 4°C）（1720; Kubota）に掛け、上澄みを注意深く回収した。回収した本上澄み溶液（30 mL）をPDMS（30 g）（Sylgard 184; Dow Corning）に添加し、氷冷下、超音波処理を1 min施した。ロータリー真空エバポレーター（EYELA Auto Jack NAJ; Tokyo Rikakikai）によりクロロホルムを90℃で完全に除去した。室温に戻した後、本溶液に架橋剤（Sylgard 184; Dow Corning）を（架橋剤:PDMS = 1:10）の割合で添加し、5 minほど良く混合した。30 min間、真空乾燥させることで気泡を取り除いた。最後に、P3HT-SWNT/PDMS/架橋剤を容器に注ぎ、オーブン（70℃、45 min）に入れ、硬化させた。その他のカーボン材料を封入したPDMSコンポジットに関しては、基本的には、P3HT-SWNT-PDMSコンポジットと同様の手法により作製した。なお、C60-PDMSコンポジットに関しては、溶媒にトルエンを用いた。P3HT-MWNT-PDMSコンポジットについては、SMNTに代えてMWNTを使用した以外はP3HT-SWNT-PDMSコンポジットと同様の手法により作製した。PDMS中のSWNTおよびMWNT濃度は、それぞれ80 μg/mL、12 μg/mLである。クロロホルム及びPDMSコンポジット中のP3HT-SWNT複合体の分散性評価は、顕微レーザーラマン（波長: 532 nm）（NRS-3100; JASCO）とUV-Vis-NIR分光光度計（UV-3100PC; Shimadzu）を用いて行った。光熱発電素子は、3種類のビスマス-テルル系熱電変換素子（Type 1 (OTT-8-1.3-0.4): 大きさ = 2.0 mm × 2.0 mm × 2.4 mm, Seebeck係数 (Z)約2.22 × 10-3, Ri約2.7 Ω, Type 2 (1MD04-017-12): 大きさ = 3.8 mm × 3.8 mm × 2.3 mm, Z約2.55 × 10-3, Ri約2.7 Ω, Type 3 (TEFC1-03112): size = 8.3 mm × 8.3 mm × 2.4 mm, Z約2.07 × 10-3, Ri約2.7 Ω（Japan Tecmo）の表面に各種カーボン材料-PDMSコンポジットを硬化させることで作製した（図８）。
Example 1
Synthesis of P3HT-SWNT-PDMS composite and P3HT-MWNT-PDMS composite
The P3HT-SWNT-PDMS composite was produced by the following method. SWNT (5 mg) [high-pressure carbon monoxide (Hipco) super-purified SWNTs (purity>95%); Carbon Nanotechnologies] and P3HT (2.5 mg) (regioregular; Ardrich) are added to chloroform (40 mL), 15 During min, sonication (USD-2R; AS ONE) was performed under ice cooling (> 8 ° C.). The obtained P3HT-SWNT complex solution was centrifuged (11,000 rpm, 15 min, 4 ° C) (1720; Kubota), and the supernatant was carefully collected. The recovered supernatant solution (30 mL) was added to PDMS (30 g) (Sylgard 184; Dow Corning) and sonicated for 1 min under ice cooling. Chloroform was completely removed at 90 ° C. using a rotary vacuum evaporator (EYELA Auto Jack NAJ; Tokyo Rikakikai). After returning to room temperature, a crosslinking agent (Sylgard 184; Dow Corning) was added to this solution at a ratio of (crosslinking agent: PDMS = 1: 10) and mixed well for about 5 min. Bubbles were removed by vacuum drying for 30 min. Finally, P3HT-SWNT / PDMS / crosslinking agent was poured into a container and placed in an oven (70 ° C., 45 min) to cure. The PDMS composite encapsulating other carbon materials was basically produced by the same method as the P3HT-SWNT-PDMS composite. For the C 60 -PDMS composite, toluene was used as the solvent. The P3HT-MWNT-PDMS composite was prepared in the same manner as the P3HT-SWNT-PDMS composite except that MWNT was used instead of SMNT. The concentrations of SWNT and MWNT in PDMS are 80 μg / mL and 12 μg / mL, respectively. Dispersibility evaluation of P3HT-SWNT composites in chloroform and PDMS composites was performed using a microscopic laser Raman (wavelength: 532 nm) (NRS-3100; JASCO) and a UV-Vis-NIR spectrophotometer (UV-3100PC; Shimadzu). Used. Photothermal power generating element, three bismuth - telluride thermoelectric elements (Type 1 (OTT-8-1.3-0.4) : size = 2.0 mm × 2.0 mm × 2.4 mm, Seebeck coefficient (Z) approximately 2.22 × 10 - 3 , R i approx.2.7 Ω, Type 2 (1MD04-017-12): Size = 3.8 mm × 3.8 mm × 2.3 mm, Z approx.2.55 × 10 -3 , R i approx.2.7 Ω, Type 3 (TEFC1-03112 ): Size = 8.3 mm × 8.3 mm × 2.4 mm, Z approx. 2.07 × 10 -3 , R i approx. 2.7 Ω (Japan Tecmo) The surface was prepared by curing various carbon materials-PDMS composites (Fig. 8) .
温度アッセイ
様々な出力（50, 150, 300, 1000 mW）に設定した670 nm（レーザー径約5 mm）（BWF-670-300E; B&W Tek）、785 nm（レーザー径 約4 mm）(BRM-785-1.0-100-0.22-SMA; B&W Tek)、1064 nm（レーザー径 約 2 mm）（BL106-C; Spectra Physics）のレーザーをカーボン材料-PDMSコンポジットに照射することで温度アッセイを行った（図７）。熱電対（CT-280WR; Custom）を用いて30 sec毎に温度を測定した。なお、レーザービームが、熱電対に直接当たらないようにした。
電圧測定
様々な出力（25, 50, 150, 300, 500, 700 and 1000 mW）に設定した670 nm、785 nm、1064 nmのレーザーを作製した各種コンポジットを搭載した光熱発電素子に照射した。当該発電素子に電圧計（SK-6500; Kaise）を接続することで、開放電圧を測定した。
Voltage measurement Photothermal power generation elements equipped with various composites made with lasers of 670 nm, 785 nm, and 1064 nm set to various outputs (25, 50, 150, 300, 500, 700 and 1000 mW) were irradiated. An open voltage was measured by connecting a voltmeter (SK-6500; Kaise) to the power generation element.
CNTコンポジットフィルムのキャラクタリゼーション
CNT(図１ではSWNT)表面を導電性ポリマーであるP3HTによってラッピングすることでPDMS中に均一かつ高濃度に分散化することができる。特開2009-196877では、PDMS中にCNT複合体を最大で0.01 wt%分散化可能であったが、本発明では0.06 wt%まで分散化することができる。CNTの高濃度分散化により、光発熱の効率を高めることができる。
Characterization of CNT composite film
By lapping the surface of CNT (SWNT in Fig. 1) with P3HT, which is a conductive polymer, it can be dispersed uniformly and at a high concentration in PDMS. In JP-A-2009-196877, it was possible to disperse a CNT complex in PDMS at a maximum of 0.01 wt%, but in the present invention, it can be dispersed to 0.06 wt%. By increasing the concentration of CNTs, the efficiency of light heat generation can be increased.
本発明のP3HT-CNT-PDMSフィルムは、濃度を濃くしていくと（(i) 0 mg/mL, (ii) 0.15 mg/mL, 0.3 mg/mL, (iV) 0.6 mg/mL）黒色が濃くなるが透明なフィルムであり(図1b左)、このフィルムは高いフレキシビリティーを有し、棒状の物体等に巻きつけることも可能である(図1b右)。 When the concentration of the P3HT-CNT-PDMS film of the present invention is increased ((i) 0 mg / mL, (ii) 0.15 mg / mL, 0.3 mg / mL, (iV) 0.6 mg / mL) It is a thick but transparent film (left side of FIG. 1b). This film has high flexibility and can be wrapped around a rod-like object or the like (right side of FIG. 1b).
P3HT-SWNT-PDMSは、SWNTがフィルム中に均一に分散化しているため、SWNTに由来する黒い凝集物は見られない。一方、P3HT未修飾のSWNTは、PDMSに全く分散化できないため、SWNTに由来する黒い凝集物がフィルム中のいたるところで観察される（図1c右：SWNT-PDMSフィルムの光学顕微鏡写真)。 In P3HT-SWNT-PDMS, since SWNTs are uniformly dispersed in the film, black aggregates derived from SWNTs are not observed. On the other hand, SW3 unmodified with P3HT cannot be dispersed in PDMS at all, so black aggregates derived from SWNT are observed everywhere in the film (FIG. 1c right: optical micrograph of SWNT-PDMS film).
P3HT-SWNT複合体を内包したPDMSフィルム（1）からはSWNT(4)と同様のラマンスペクトルが得られ、当該領域にカーボンナノチューブがよく分散していることが裏付けられた。また、未修飾SWNTを内包したPDMSフィルムには、SWNTが凝集している部分(2)と全くSWNTが存在しない部分(3)があることがわかった(図1ｄ)。図1ｄ中、1: Fig. 1左の矢印1、2: Fig. 1右の矢印1、3: Fig. 1右の矢印3、4: SWNT粉末のラマンスペクトル、5: PDMSのラマンスペクトルを各々示す。
From the PDMS film (1) encapsulating the P3HT-SWNT complex, a Raman spectrum similar to that of SWNT (4) was obtained, confirming that the carbon nanotubes were well dispersed in this region. Further, it was found that the PDMS film encapsulating unmodified SWNT had a part (2) where SWNTs aggregated and a part (3) where no SWNTs existed (FIG. 1d). In Fig. 1d: 1: Fig. 1 left
P3HT-SWNT複合体を分散化させたクロロホルムおよびPDMSは、波長約500〜800nmにおいてピークが複数観測され、溶液中にカーボンナノチューブが均一に溶解していることが確認できた(図1e)。なお図1eにおいて、(i)クロロホルム中のP3HT-SWNTのUV-vis-NIR吸収スペクトル解析、(ii)PDMS中のP3HT-SWNTのUV-vis-NIR吸収スペクトル解析を各々示す。
各種コンポジットへのレーザー照射 (785 nm、1 W)における温度上昇の経時変化を測定し、結果を図１(f)に示した。とりわけP3HT-SWNT-PDMS（●）において高い温度上昇が確認できた。その他の材料は温度上昇がほとんど見られなかった。
In chloroform and PDMS in which the P3HT-SWNT complex was dispersed, a plurality of peaks were observed at a wavelength of about 500 to 800 nm, and it was confirmed that the carbon nanotubes were uniformly dissolved in the solution (FIG. 1e). In FIG. 1e, (i) UV-vis-NIR absorption spectrum analysis of P3HT-SWNT in chloroform and (ii) UV-vis-NIR absorption spectrum analysis of P3HT-SWNT in PDMS are shown.
The time-dependent change in temperature rise during laser irradiation (785 nm, 1 W) on various composites was measured, and the results are shown in FIG. 1 (f). In particular, a high temperature rise was confirmed in P3HT-SWNT-PDMS (●). The other materials showed almost no increase in temperature.
各種コンポジットの各レーザー出力(50, 150, 300, 500, 700, 1000 mW)に対する光発熱挙動（温度差測定）を測定し、結果を図１(g)に示した。特にP3HT-SWNT-PDMS(vii)において高い温度差が得られた。その他の材料はほとんど温度差が得られなかった。また、未修飾SWNT(v)およびグラファイト(iii)において温度上昇が見られたが、P3HT-SWNT-PDMSに比較して得られる温度差は小さかった。これは、P3HT-SWNT-PDMS(vii)においてSWNTが均一に分散化しているため光発熱特性を大きく引き出すことができたためと考えられる。P3HT-MWNT-PDMS(vi)もまたPDMS中にMWNTが均一に分散化しているが、P3HT-SWNT-PDMS(vii)に比較してPDMS中のMWNT含有濃度が低いため、光発熱作用が小さいと考えられる（図５）。 The photothermal behavior (temperature difference measurement) of each composite for each laser output (50, 150, 300, 500, 700, 1000 mW) was measured, and the result is shown in FIG. 1 (g). In particular, a high temperature difference was obtained in P3HT-SWNT-PDMS (vii). For the other materials, almost no temperature difference was obtained. Moreover, although temperature rise was seen in unmodified SWNT (v) and graphite (iii), the temperature difference obtained compared with P3HT-SWNT-PDMS was small. This is thought to be due to the fact that photothermal characteristics could be greatly extracted because SWNTs were uniformly dispersed in P3HT-SWNT-PDMS (vii). P3HT-MWNT-PDMS (vi) also has a uniform dispersion of MWNT in PDMS, but its photothermal action is small because the concentration of MWNT in PDMS is low compared to P3HT-SWNT-PDMS (vii) (Fig. 5).
光発熱特性と熱電変換
P3HT-SWNT-PDMSを搭載した熱電変換素子のデジカメ写真を図2(a)に示す。
Photothermal characteristics and thermoelectric conversion
Fig. 2 (a) shows a digital camera photograph of a thermoelectric conversion element equipped with P3HT-SWNT-PDMS.
また、各種コンポジットへのレーザー照射 (1064 nm、1 W)における温度上昇の経時変化を図2bに示す。図2bにおいて、P3HT-SWNT-PDMS（●）、SWNT-PDMS（▲）、C60-PDMS(×)、グラファイト-PDMS（■）、PDMS（◇）である。 In addition, Fig. 2b shows the changes over time in the temperature rise of each composite with laser irradiation (1064 nm, 1 W). In FIG. 2b, they are P3HT-SWNT-PDMS (●), SWNT-PDMS (▲), C 60 -PDMS (×), graphite-PDMS (■), and PDMS (で).
とりわけP3HT-SWNT-PDMSにおいて高い温度上昇が確認できた。その他の材料は温度上昇がほとんど見られなかった。 In particular, a high temperature rise was confirmed in P3HT-SWNT-PDMS. The other materials showed almost no increase in temperature.
各種コンポジットの各レーザー出力(50, 150, 300, 1000 mW)に対する光発熱挙動（温度差測定）を図2cに示す。図2cにおいて、(i) PDMS、(ii) C60-PDMS、(iii) グラファイト-PDMS、(iV) SWNT-PDMS、(V) P3HT-SWNT-PDMSを各々示す。*N. D.は温度変化が全くないことを示す。特にP3HT-SWNT-PDMSにおいて高い温度差が得られた。その他の材料はほとんど温度差が得られなかった。また、未修飾SWNTおよびグラファイトにおいて温度上昇が見られたが、P3HT-SWNT-PDMSに比較して得られる温度差は小さかった。これは、P3HT-SWNT-PDMSにおいてSWNTが均一に分散化しているため光発熱特性を大きく引き出すことができたためと考えられる。 Fig. 2c shows the photothermal behavior (temperature difference measurement) of each composite for each laser power (50, 150, 300, 1000 mW). FIG. 2c shows (i) PDMS, (ii) C 60 -PDMS, (iii) graphite-PDMS, (iV) SWNT-PDMS, and (V) P3HT-SWNT-PDMS, respectively. * ND indicates no temperature change. Especially high temperature difference was obtained in P3HT-SWNT-PDMS. For the other materials, almost no temperature difference was obtained. Moreover, although the temperature rise was seen in unmodified SWNT and graphite, the temperature difference obtained compared with P3HT-SWNT-PDMS was small. This is thought to be due to the fact that photothermal characteristics could be greatly extracted because SWNTs were uniformly dispersed in P3HT-SWNT-PDMS.
次に、各出力（25, 50, 150, 300, 1000 mW）のレーザーを照射したときの熱電変換挙動を図2dに示す。図2dにおいて、(i) PDMS、(ii) C60-PDMS、(iii) グラファイト-PDMS、(iV) SWNT-PDMS、(V) P3HT-SWNT-PDMS、*N. D.: 全く発電しない。 Next, Fig. 2d shows the thermoelectric conversion behavior when irradiated with laser of each power (25, 50, 150, 300, 1000 mW). In FIG. 2d, (i) PDMS, ( ii) C 60 -PDMS, (iii) a graphite -PDMS, (iV) SWNT-PDMS , (V) P3HT-SWNT-PDMS, * ND: not at all power.
全てのレーザー出力においてP3HT-SWNT-PDMSで高い電圧値が得られることがわかった（最大起電力：約1 mW）。その他の材料に関しては、得られる電圧値にほとんど差が見られなかった。これは、P3HT-SWNT-PDMSは、SWNTが均一に分散化しているため光発熱特性を大きく引き出すことができ、結果として高い熱電変換作用を示したと考えられる。 It was found that high voltage values were obtained with P3HT-SWNT-PDMS at all laser outputs (maximum electromotive force: approximately 1 mW). For the other materials, there was almost no difference in the voltage values obtained. This is probably because P3HT-SWNT-PDMS was able to bring out a large amount of photothermal properties because SWNTs were uniformly dispersed, and as a result, showed high thermoelectric conversion.
次に、図２(a2)の熱電変換素子において、各出力（25, 50, 100, 150, 200, 250, 300, 500, 700, 1000 mW）のレーザーを照射したときの熱電変換挙動を図２(e)に示す。図２(e)において、 (i) PDMS、(ii) C60-PDMS、(iii) グラファイト-PDMS、(iV) MWNT-PDMS、(V) SWNT-PDMS、(Vi) P3HT-MWNT-PDMS、(Vii) P3HT-SWNT-PDMS＞*N. D.: 全く発電しない。全てのレーザー出力においてP3HT-SWNT-PDMS(Vii)で高い電圧値が得られることがわかった（最大起電力：約3.2 mW）。その他の材料に関しては、得られる電圧値にほとんど差が見られなかった。これは、P3HT-SWNT-PDMS(Vii)は、SWNTが均一に分散化しているため光発熱特性を大きく引き出すことができ、結果として高い熱電変換作用を示したと考えられる。 Next, in the thermoelectric conversion element of Fig. 2 (a2), the graph shows the thermoelectric conversion behavior when each output (25, 50, 100, 150, 200, 250, 300, 500, 700, 1000 mW) laser is irradiated. Shown in 2 (e). In FIG. 2 (e), (i) PDMS, (ii) C 60 -PDMS, (iii) Graphite-PDMS, (iV) MWNT-PDMS, (V) SWNT-PDMS, (Vi) P3HT-MWNT-PDMS, (Vii) P3HT-SWNT-PDMS> * ND: No power generation. It was found that high voltage values were obtained with P3HT-SWNT-PDMS (Vii) at all laser powers (maximum electromotive force: about 3.2 mW). For the other materials, there was almost no difference in the voltage values obtained. This is probably because P3HT-SWNT-PDMS (Vii) was able to bring out a large amount of photothermal properties because SWNTs were uniformly dispersed, and as a result, showed high thermoelectric conversion.
CNTの光発熱特性を利用した熱電変換メカニズムを図２(f)に示す。 Fig. 2 (f) shows the thermoelectric conversion mechanism using the photothermal characteristics of CNTs.
動物実験
まず、ゼブラフィッシュ（Danio rerio）（AB）の実験は、酸化処理により先端を尖らせたタングステン製のマイクロニードル（直径 = 0.2 mm, Nilaco）をマイクロマニピュレータ（MM-3; Narishige）によって心室に突き刺した。次に、1064 nmレーザー（1 W）を光熱発電素子に約1 min連続照射しながら、連続的に電気刺激を行った(図３a,b)。一方、アフリカツメガエル（Xenopus Laevis）（♂, Hamamatsu Seibutsu Kyozai）の実験に関しては、1064 nmレーザー（1 W）を光熱発電素子に約1 min連続照射しながら、リード線を断続的に接触させることで電気刺激を行った(図３c,d)。ラット（10週齢、♂）（Jcl:Wistar; CLEA Japan）の実験では、光熱発電素子をラット背面に埋め込み、各出力（25, 50, 150, 300 mW）の670 nmレーザーを埋め込み部位に向かって3 min間照射し、電圧計により開放電圧を測定した。このとき、熱電対（AD-5601A; A & D）を手術した小さな切開部位から挿入し、光熱発電素子の下部に置くことで、生体内温度を測定した。また、赤外線サーモグラフィカメラ（b40; FLIR）により、生体表面温度を測定した(図４)。デバイスの生体適合性評価は、次のように行った。リード線を除去した最も小型のデバイス（Type 1）をラット（10週齢、♂）（Jcl:Wistar; CLEA Japan）背面に埋め込んだ。8日後、32日後に腹腔動脈から採血し、本血液サンプルのCBC（Complete blood cell count）と生化学検査を実施した（表1）。また、デバイス埋め込み部位および摘出したデバイスを入念に観察した。
Animal experiment First, the experiment of zebrafish (Danio rerio) (AB) was performed by using a micromanipulator (MM-3; Narishige) to insert a tungsten microneedle (diameter = 0.2 mm, Nilaco) with a sharpened tip. Pierced. Next, electrical stimulation was continuously performed while continuously irradiating the photothermal power generation element with a 1064 nm laser (1 W) for about 1 min (FIGS. 3a and 3b). On the other hand, for the experiment of Xenopus Laevis (Hamamatsu Seibutsu Kyozai), the lead wire was intermittently contacted while continuously irradiating the photovoltaic element with a 1064 nm laser (1 W) for about 1 min. Electrical stimulation was performed (FIGS. 3c and d). In an experiment with rats (10 weeks old, pupa) (Jcl: Wistar; CLEA Japan), a photothermal power generation device was implanted in the back of the rat, and a 670 nm laser with each output (25, 50, 150, 300 mW) was directed toward the implantation site. For 3 min and the open voltage was measured with a voltmeter. At this time, a thermocouple (AD-5601A; A & D) was inserted from a small surgical incision site and placed under the photothermal power generation device, and the in-vivo temperature was measured. Moreover, the living body surface temperature was measured with the infrared thermography camera (b40; FLIR) (FIG. 4). The biocompatibility evaluation of the device was performed as follows. The smallest device (Type 1) from which the lead wire was removed was embedded in the back of a rat (10 weeks old, rabbit) (Jcl: Wistar; CLEA Japan). After 8 and 32 days, blood was collected from the celiac artery, and CBC (Complete blood cell count) and biochemical examination of this blood sample were performed (Table 1). Also, the device implantation site and the removed device were carefully observed.
デバイスの埋め込み有無に関わらず、CBCと生化学検査に大きな違いは見られなかった。とりわけ、炎症性マーカーであるCRPに変化が見られないことから本デバイスは生体適合性が高いと考えられる。 There was no significant difference between CBC and biochemical tests, regardless of whether the device was embedded. In particular, this device is considered to be highly biocompatible since no change is seen in CRP, which is an inflammatory marker.
各種コンポジットとPDMS中の分散化状態
各種コンポジットのデジカメ写真を図5aに示す。図５において、(i) PDMS, (ii) C60-PDMS, (iii) graphite-PDMS, (iv) MWNT-PDMS, (v) P3HT-MWNT-PDMS, (vi) SWNT-PDMS, (vii) P3HT-SWNT-PDMSである。
Various composites and dispersion state in PDMS Figure 5a shows digital camera photographs of various composites. In FIG. 5, (i) PDMS, (ii) C 60 -PDMS, (iii) graphite-PDMS, (iv) MWNT-PDMS, (v) P3HT-MWNT-PDMS, (vi) SWNT-PDMS, (vii) P3HT-SWNT-PDMS.
各種コンポジットの光学顕微鏡写真を図5bに示す。図5bにおいて、((i) PDMS, (ii) C60-PDMS, (iii) graphite-PDMS, (iv) MWNT-PDMS, (v) P3HT-MWNT-PDMS, (vi) SWNT-PDMS, (vii) P3HT-SWNT-PDMSである。C60、P3HT-MWNT複合体、P3HT-SWNT複合体はPDMS中に均一に分散化しているが、グラファイト、未修飾SWNT、未修飾MWNTは、大きな凝集物がたくさん観察され、全く分散化できていないことがわかる。 Optical microscope photographs of various composites are shown in FIG. 5b. In Figure 5b, ((i) PDMS, (ii) C 60 -PDMS, (iii) graphite-PDMS, (iv) MWNT-PDMS, (v) P3HT-MWNT-PDMS, (vi) SWNT-PDMS, (vii ) P3HT-SWNT-PDMS C 60 , P3HT-MWNT complex and P3HT-SWNT complex are uniformly dispersed in PDMS, but graphite, unmodified SWNT, and unmodified MWNT have large aggregates. Many are observed and it can be seen that they are not dispersed at all.
各種コンポジットを搭載した熱電変換素子
各種コンポジットを搭載した熱電変換素子のデジカメ写真を図6aに示す。図6a中、(i) PDMS、(ii) C60-PDMS、(iii) グラファイト-PDMS、(iV) SWNT-PDMS、(V) P3HT-SWNT-PDMSである。図6bは、1064 nmレーザー（1 W）を照射したP3HT-SWNT-PDMSデバイスのデジカメ写真である。図6bにおいて、本発明のデバイス(V)は、レーザー照射前と照射後で全く変化が見られないことから、レーザーによる光熱耐久性が極めて高いことがわかった。
Fig. 6a shows a digital camera photograph of thermoelectric conversion elements equipped with various composites. In FIG. 6a, (i) PDMS, (ii) C 60 -PDMS, (iii) graphite-PDMS, (iV) SWNT-PDMS, (V) P3HT-SWNT-PDMS. FIG. 6b is a digital camera photograph of a P3HT-SWNT-PDMS device irradiated with a 1064 nm laser (1 W). In FIG. 6b, since the device (V) of the present invention shows no change before and after the laser irradiation, it was found that the photothermal durability by the laser is extremely high.
本発明により製造されるカーボンナノチューブが有機溶媒に均一に分散した分散液を用いることで、触媒、ナノエレクトロニクスデバイス、ドラッグデリバリーシステム等への応用が可能である。また、本発明により製造される、カーボンナノチューブが均一に分散したポリマー樹脂は、超高強度繊維、エレクトロニクス素子、アクチュエータ素子、燃料電池、医療用材料等への応用が考えられる。さらに、本発明に係る発電素子によれば、レーザー光線を利用した生体内における遠隔発電が可能であり、心臓ペースメーカー等の様々な体内埋め込み型医療機器への光熱による安定した電力供給システムに利用できるものと考えられる。 By using a dispersion in which the carbon nanotubes produced according to the present invention are uniformly dispersed in an organic solvent, application to catalysts, nanoelectronic devices, drug delivery systems, and the like is possible. In addition, the polymer resin produced by the present invention in which carbon nanotubes are uniformly dispersed can be applied to ultra-high strength fibers, electronics elements, actuator elements, fuel cells, medical materials, and the like. Furthermore, according to the power generating element of the present invention, remote power generation in a living body using a laser beam is possible, and the power generating element can be used for a stable power supply system by photothermal to various implantable medical devices such as a cardiac pacemaker. it is conceivable that.
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