JP2009231224A - Photoelectric conversion element, and manufacturing method thereof - Google Patents

Photoelectric conversion element, and manufacturing method thereof Download PDF

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JP2009231224A
JP2009231224A JP2008078267A JP2008078267A JP2009231224A JP 2009231224 A JP2009231224 A JP 2009231224A JP 2008078267 A JP2008078267 A JP 2008078267A JP 2008078267 A JP2008078267 A JP 2008078267A JP 2009231224 A JP2009231224 A JP 2009231224A
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solid electrolyte
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JP5339756B2 (en
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Takeshi Sugio
剛 杉生
Tetsuya Inoue
鉄也 井上
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Hitachi Zosen Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element with high photoelectric conversion efficiency even though it has a solidified solid electrolyte, and to provide a manufacturing method thereof. <P>SOLUTION: A photocatalyst film 3 and a gelled solid electrolyte sheet 12 are interposed between an electrode 1 as a negative electrode and a counter electrode 2 as a positive electrode, and then, they are heated by heaters 13, 14. The gelled solid electrolyte sheet 12 is melted by heating, and adhesion among a photocatalyst film 3, a solid electrolyte layer, and the counter electrode 2 is raised by being solidified after it is cooled. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、太陽電池のような光電変換素子に関し、さらにその製造方法に関するものである。   The present invention relates to a photoelectric conversion element such as a solar cell, and further relates to a manufacturing method thereof.

一般に、色素増感型太陽電池などの光電変換素子は、ガラス板などの透明基板上に透明導電膜を形成し、これを光増感色素で染色してなる電極と、対極用基板上に透明導電膜を形成してなる対極と、両電極間に介在されたヨウ素系の固体電解質液とからなる。   In general, a photoelectric conversion element such as a dye-sensitized solar cell is formed by forming a transparent conductive film on a transparent substrate such as a glass plate and dyeing this with a photosensitizing dye, and transparent on a counter electrode substrate. It consists of a counter electrode formed with a conductive film and an iodine-based solid electrolyte solution interposed between both electrodes.

前記固体電解質液に用いられるヨウ素は、腐蝕性を有するため、安全性や機器の耐久性の面から使用することの問題が指摘されており、その対策として、固体電解質液部分を固体化する研究が進められている（特許文献１）。
特開２００５−７１６８８ Since iodine used in the solid electrolyte solution is corrosive, it has been pointed out that it may be used from the viewpoint of safety and durability of equipment. (Patent Document 1).
JP-A-2005-71688

上記のように、固体電解質液部分を固体化すると、固体電解質を含んだ光増感色素で染色してなる電極上に、例えば白金板上に透明導電膜を形成してなる対極を組み合わせることになる。   As described above, when the solid electrolyte solution part is solidified, for example, a counter electrode formed by forming a transparent conductive film on a platinum plate is combined with an electrode dyed with a photosensitizing dye containing a solid electrolyte. Become.

この場合、電極及び対極の表面は互いに固体化したもの同士の接触となるため、密着性が十分でなく、光電変換効率が低下するという問題があった。   In this case, since the surfaces of the electrode and the counter electrode are in contact with each other, the adhesion is not sufficient, and the photoelectric conversion efficiency is lowered.

そこで、本発明では、固体化された固体電解質でありながら光電変換効率が高い光電変換素子およびその製造方法を提供する。   Therefore, the present invention provides a photoelectric conversion element having high photoelectric conversion efficiency while being a solidified solid electrolyte, and a method for producing the same.

本発明による光電変換素子は、透明な電極とこれに対向する対極とを有する光電変換素子において、前記対極は、対極用基板の片面上に固体電解質層を形成した構造であり、電極の周縁部を除いた部分と対極の周縁部を除いた部分との間に、光増感色素で染色された光触媒膜および天然高分子またはその誘導体により固体化されたゲル状固体電解質シートが挟まれるとともに、電極の周縁部が対極の周縁部に加熱接着されていることを特徴とする。   The photoelectric conversion element according to the present invention is a photoelectric conversion element having a transparent electrode and a counter electrode opposed to the transparent electrode, wherein the counter electrode has a structure in which a solid electrolyte layer is formed on one side of a counter electrode substrate, and the peripheral portion of the electrode Between the part excluding the peripheral part of the counter electrode and the part excluding the peripheral part of the counter electrode, a photocatalytic film dyed with a photosensitizing dye and a gel-like solid electrolyte sheet solidified by a natural polymer or a derivative thereof are sandwiched, The peripheral portion of the electrode is heat bonded to the peripheral portion of the counter electrode.

電極は、合成樹脂板、ガラス板などの透明基板上に透明導電膜を形成したものとされる。電極用透明基板は、加熱接着性を上げるために、熱可塑性材料とされることが好ましく、例えば、ポリエチレン・ナフタレート、ポリエチレン・テレフタレート、ポリエステル、ポリカーボネート、ポリオレフィンなどの熱可塑性樹脂製とされることがある。   The electrode is formed by forming a transparent conductive film on a transparent substrate such as a synthetic resin plate or a glass plate. The transparent substrate for electrodes is preferably made of a thermoplastic material in order to increase heat adhesion, for example, made of a thermoplastic resin such as polyethylene naphthalate, polyethylene terephthalate, polyester, polycarbonate, polyolefin. is there.

透明導電膜は、スズ添加酸化インジウム［Indium Tin Oxide（ＩＴＯ）］、フッ素添加酸化スズ［Fluorine doped Tin Oxide（ＦＴＯ）］、酸化スズ［ＳｎＯ２］などの導電性金属酸化物を含む薄膜とされる。 The transparent conductive film is a thin film containing a conductive metal oxide such as tin-doped indium oxide (Indium Tin Oxide (ITO)), fluorine-doped tin oxide (Fluorine doped Tin Oxide (FTO)), or tin oxide [SnO 2 ]. The

ゲル状固体電解質シートは、ＤＭＰＩｍＩ（ジメチルプロピルイミダゾリウムヨウ化物）のような固体電解質に微粒子を混ぜて作成することができ、また、多孔質体（例えば不織布）にゲル状固体電解質を含浸させることで得ることもできる。    The gel-like solid electrolyte sheet can be prepared by mixing fine particles with a solid electrolyte such as DMPImI (dimethylpropylimidazolium iodide), and impregnating the porous solid body (for example, non-woven fabric) with the gel-like solid electrolyte. Can also be obtained.

固体電解質としては、例えば、ＤＭＰＩｍＩが例示され、このほか、ＬｉＩ、ＮａＩ、ＫＩ、ＣｓＩ、ＣａＩ２などの金属ヨウ化物、およびテトラアルキルアンモニウムヨーダイドなど４級アンモニウム化合物のヨウ素塩などのヨウ化物とＩ２とを組み合わせたもの；ＬｉＢｒ、ＮａＢｒ、ＫＢｒ、ＣｓＢｒ、ＣａＢｒ２などの金属臭化物、およびテトラアルキルアンモニウムブロマイドなど４級アンモニウム化合物の臭素塩などの臭化物とＢｒ２とを組み合わせたものなどを適宜使用することができる。 The solid electrolyte, for example, DMPImI are exemplified, in addition, LiI, NaI, KI, CsI, and an iodide such as iodine salt of CaI metal iodide such as 2, and tetraalkylammonium iodide and quaternary ammonium compounds combinations of the I 2; LiBr, NaBr, KBr , CsBr, metal bromide such as CaBr 2, and a combination of a bromide and Br 2, such as bromine salts such as quaternary ammonium compounds tetraalkylammonium bromide as appropriate Can be used.

天然高分子またはその誘導体としては、例えば、ゼラチンが例示され、カラゲニン（カラジーナン）、アガロース、寒天、キチン、キトサン、セルロース、デンプン、アミロース、アミロペクチン、コンドロイチン、コンドロイチン硫酸、マンナン、グルコマンナンなどの多糖類やその誘導体；ゼラチンのほか、コラーゲン、カゼイン、アルブミン、フィブロイン、ケラチン、グロブリン、などのタンパク質やその誘導体などが挙げられる。   Examples of natural polymers or derivatives thereof include gelatin, and polysaccharides such as carrageenan (carrageenan), agarose, agar, chitin, chitosan, cellulose, starch, amylose, amylopectin, chondroitin, chondroitin sulfate, mannan and glucomannan. In addition to gelatin, proteins such as collagen, casein, albumin, fibroin, keratin, and globulin, and derivatives thereof may be mentioned.

光増感色素で染色された光触媒膜を形成するには、例えば、光増感色素と光触媒粒子とを含むペーストを塗布し、乾燥により、色素で染色された光触媒粒子を担持するようにすればよい。前記ペーストはさらにカーボンナノチューブ粒子などの微粒子を含むことが好ましい。   In order to form a photocatalyst film dyed with a photosensitizing dye, for example, a paste containing a photosensitizing dye and photocatalyst particles is applied and dried to support the photocatalyst particles dyed with the dye. Good. The paste preferably further contains fine particles such as carbon nanotube particles.

光触媒粒子は、酸化チタン（ＴｉＯ２）、酸化スズ（ＳｎＯ２）、酸化タングステン（ＷＯ３）、酸化亜鉛（ＺｎＯ）、酸化ニオブ（Ｎｂ２Ｏ５） などの金属酸化物とされ、光増感色素は、例えばビピリジン構造、ターピリジン構造などを含む配位子を有するルテニウム錯体や鉄錯体、ポルフィリン系やフタロシアニン系の金属錯体、さらにはエオシン、ローダミン、メロシアニン、クマリンなどの有機色素などとされる。 The photocatalytic particles are metal oxides such as titanium oxide (TiO 2 ), tin oxide (SnO 2 ), tungsten oxide (WO 3 ), zinc oxide (ZnO), niobium oxide (Nb 2 O 5 ), and are photosensitized. Examples of the dye include ruthenium complexes and iron complexes having a ligand including a bipyridine structure, a terpyridine structure, and the like, porphyrin-based and phthalocyanine-based metal complexes, and organic dyes such as eosin, rhodamine, merocyanine, and coumarin.

電極の周縁部と対極の周縁部との加熱接着は、例えば、光触媒膜およびゲル状固体電解質シートが上側の電極および下側の対極に挟まれた状態で、上型および下型からなる金型によって両側から挟まれて加熱されることで行われることが好ましい。このようにすると、電極の周縁部と対極の周縁部との接着時の熱がゲル状固体電解質シートに伝わって、ゲル状固体電解質シートが溶解することにより、密着性が高められる。   Heat adhesion between the peripheral edge of the electrode and the peripheral edge of the counter electrode is, for example, a mold composed of an upper mold and a lower mold in a state where the photocatalyst film and the gel solid electrolyte sheet are sandwiched between the upper electrode and the lower counter electrode. It is preferable to be performed by being sandwiched from both sides and heated. If it does in this way, the heat | fever at the time of adhesion | attachment with the peripheral part of an electrode and the peripheral part of a counter electrode will be transmitted to a gel-like solid electrolyte sheet, and adhesiveness will be improved by melt | dissolving a gel-like solid electrolyte sheet.

対極の構成としては、金属（アルミニウム、銅、スズなど）またはカーボン製などのメッシュ状電極にゲル状固体電解質を保持させることで対極を構成していることがあり、また、対極用基板の片面上に導電性接着剤層を同基板を覆うように形成し、同接着剤層を介して、別途形成のブラシ状カーボンナノチューブ群を基板に転写することで、対極を構成していることがある。前者は、ゲル状固体電解質シートとは別に、対極の表面にゲル状固体電解質を配置することで、密着性をより向上することができ、後者は、カーボンナノチューブ間に固体電解質が入り込むことで、密着性をより向上することができる。ブラシ状カーボンナノチューブ群を基板に転写する構成では、対極用基板上のブラシ状カーボンナノチューブ群の表面にも固体電解質層を形成し、この固体電解質層の表面に光増感色素で染色された光触媒膜を形成することがより好ましい。   As the configuration of the counter electrode, the counter electrode may be configured by holding a gel solid electrolyte on a mesh electrode made of metal (aluminum, copper, tin, etc.) or carbon, and one side of the counter electrode substrate. A counter electrode may be formed by forming a conductive adhesive layer on the substrate so as to cover the substrate and transferring a group of separately formed brush-like carbon nanotubes to the substrate via the adhesive layer. . The former can further improve the adhesion by placing the gel solid electrolyte on the surface of the counter electrode separately from the gel solid electrolyte sheet, and the latter is because the solid electrolyte enters between the carbon nanotubes. Adhesion can be further improved. In the configuration in which the brush-like carbon nanotube group is transferred to the substrate, a solid electrolyte layer is also formed on the surface of the brush-like carbon nanotube group on the counter electrode substrate, and the photocatalyst dyed with a photosensitizing dye on the surface of the solid electrolyte layer It is more preferable to form a film.

また、電極の構成としては、電極用基板の片面上に透明導電膜を形成し、さらに、この上に固体電解質層を設けることが好ましい。この固体電解質層は、ゲル状固体電解質であってもよく、ヨウ化銅からなる固体電解質であってもよく、後者は、ヨウ化銅（ＣｕＩ）を含むアセトニトリル溶液を滴下し、乾燥によりアセトニトリルを蒸発させることで形成することができる。   Moreover, as a structure of an electrode, it is preferable to form a transparent conductive film on one side of the electrode substrate and further provide a solid electrolyte layer thereon. The solid electrolyte layer may be a gel solid electrolyte or a solid electrolyte made of copper iodide. The latter is a method in which an acetonitrile solution containing copper iodide (CuI) is dropped and dried to dry the acetonitrile. It can be formed by evaporation.

本発明による光電変換素子の製造方法は、透明な電極とこれに対向する対極とを有する光電変換素子を製造する方法であって、電極を作成する工程と、対極用基板の片面上に天然高分子またはその誘導体により固体化されたゲル状固体電解質シートを配置する工程と、電極とゲル状固体電解質シートとの間に光増感色素で染色された光触媒膜を介在させる工程と、電極と対極とを両極間にゲル状固体電解質シートおよび光触媒膜が挟まれるように対向させる工程と、加熱によりゲル状固体電解質シートを溶解する工程と、冷却により溶解した固体電解質を固体化する工程とを含んでいることを特徴とする。   A method for producing a photoelectric conversion element according to the present invention is a method for producing a photoelectric conversion element having a transparent electrode and a counter electrode opposed to the transparent electrode, and a step of creating an electrode and a natural height on one side of the counter electrode substrate. A step of disposing a gel-like solid electrolyte sheet solidified by molecules or derivatives thereof, a step of interposing a photocatalyst film dyed with a photosensitizing dye between the electrode and the gel-like solid electrolyte sheet, and an electrode and a counter electrode Including a step of causing the gelled solid electrolyte sheet and the photocatalyst film to face each other, a step of dissolving the gelled solid electrolyte sheet by heating, and a step of solidifying the solid electrolyte dissolved by cooling It is characterized by being.

固体電解質は、ゲル状シートの形態で用意されて、対極用基板の片面上に配置される。光触媒膜は、ペースト状とされて、電極用透明基板の透明導電膜上または対極用基板のゲル状固体電解質シート上に塗布される。   The solid electrolyte is prepared in the form of a gel-like sheet and disposed on one side of the counter electrode substrate. The photocatalyst film is formed into a paste and is applied onto the transparent conductive film of the electrode transparent substrate or the gel solid electrolyte sheet of the counter electrode substrate.

天然高分子またはその誘導体により固体化されたゲル状固体電解質シートは、加熱されることで溶解し、その後、常温となることで、再び固体化される。加熱時のゲル状固体電解質シートの溶解に伴って、光触媒膜−固体電解質−対極間の密着性が高められる。   The gel-like solid electrolyte sheet solidified with a natural polymer or a derivative thereof is dissolved by heating, and then solidified again at room temperature. As the gelled solid electrolyte sheet dissolves during heating, the adhesion between the photocatalyst film, the solid electrolyte, and the counter electrode is enhanced.

上記の光電変換素子の製造方法において、対極用基板をメッシュ状電極としてこれにゲル状固体電解質を保持させる工程をさらに含んでいることがあり、また、対極用基板の片面上にゲル状固体電解質シートを配置する工程の前に、前記対極用基板の片面上に導電性接着剤層を同基板を覆うように形成する工程と、同接着剤層を介して、別途形成のブラシ状カーボンナノチューブ群を基板に転写する工程と、固体電解質層をブラシ状カーボンナノチューブ群の表面に形成する工程とを含んでいることがある。   The manufacturing method of the photoelectric conversion element may further include a step of holding a gel solid electrolyte as a counter electrode substrate as a mesh electrode, and the gel solid electrolyte on one side of the counter electrode substrate. Before the step of arranging the sheet, a step of forming a conductive adhesive layer on one side of the counter electrode substrate so as to cover the substrate, and a group of brush-like carbon nanotubes separately formed via the adhesive layer And a step of forming a solid electrolyte layer on the surface of the brush-like carbon nanotube group.

対極用基板上のブラシ状カーボンナノチューブ群の表面に固体電解質層を形成し、さらに同層の表面に光増感色素で染色された光触媒膜を形成することで、これら相互間の密着性を高めることができ、これによって発電効率を向上させることができる。また、ブラシ状カーボンナノチューブ群上の固体電解質層の上に光触媒膜が形成されているようにすることで、固体電解質層が光触媒膜の層を超えて透明導電膜側に流れることがなく、短絡の危険性がなくなる。   A solid electrolyte layer is formed on the surface of the brush-like carbon nanotube group on the counter electrode substrate, and a photocatalyst film dyed with a photosensitizing dye is further formed on the surface of the same layer, thereby improving the adhesion between them. This can improve the power generation efficiency. In addition, the photocatalyst film is formed on the solid electrolyte layer on the brush-like carbon nanotube group so that the solid electrolyte layer does not flow beyond the photocatalyst film layer to the transparent conductive film side and is short-circuited. The danger of disappearing.

なお、ブラシ状カーボンナノチューブ群の表面に固体電解質層を形成する前に、ポリアニリン、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）およびポリスチレンスルホネート（ＰＳＳ）の少なくとも１つからなる高分子膜を形成し、同層の上に固体電解質層を形成することが好ましい。   Before forming the solid electrolyte layer on the surface of the brush-like carbon nanotube group, a polymer film composed of at least one of polyaniline, polyethylenedioxythiophene (PEDOT) and polystyrene sulfonate (PSS) is formed, It is preferable to form a solid electrolyte layer thereon.

加熱に際しては、前記光触媒粒子にエネルギービームを照射することが好ましい。エネルギービームとしては、光触媒粒子にエネルギーを与えるものであれば特に制限なく、プラズマ（波長の長いもの）、マイクロ波、可視光（６００ｎｍ以上）や赤外線などが用いられる。   In heating, it is preferable to irradiate the photocatalyst particles with an energy beam. The energy beam is not particularly limited as long as it gives energy to the photocatalyst particles, and plasma (long wavelength), microwave, visible light (600 nm or more), infrared rays, and the like are used.

上記の光電変換素子およびその製造方法において、ゲル状固体電解質シート中に微粒子を含むことが好ましい。微粒子としては、直径１〜５０ｎｍのものが好ましく、セラミック、５ｎｍが例示され、多孔質体とすることもできる。   In said photoelectric conversion element and its manufacturing method, it is preferable that a gel-like solid electrolyte sheet contains microparticles | fine-particles. As the fine particles, those having a diameter of 1 to 50 nm are preferable, and ceramics and 5 nm are exemplified, and a porous body can also be used.

このようにすることで、光電変換効率を維持しつつ、電極・対極間の短絡が抑制でき、また、微粒子を含有させた場合には、入射光（太陽光）を散乱させることにより、さらに光電変換効率を向上することができる。   By doing so, the short circuit between the electrode and the counter electrode can be suppressed while maintaining the photoelectric conversion efficiency. When fine particles are included, the incident light (sunlight) is scattered to further increase the photoelectric conversion efficiency. Conversion efficiency can be improved.

本発明によれば、光増感色素で染色された光触媒膜およびゲル状の固体電解質シートが、電極と対極との間に挟まれた状態で加熱されるので、これら相互間の密着性を高めることができ、これによって発電効率を向上させることができる。   According to the present invention, the photocatalyst film dyed with the photosensitizing dye and the gel-like solid electrolyte sheet are heated while being sandwiched between the electrode and the counter electrode, so that the adhesion between them is increased. This can improve the power generation efficiency.

本発明の実施例を図面に基づいて具体的に説明する。   Embodiments of the present invention will be specifically described with reference to the drawings.

実施例１
図２は、実施例１の光電変換素子を示し、図１は、その製造途中の状態を示している。 Example 1
FIG. 2 shows the photoelectric conversion element of Example 1, and FIG. 1 shows a state in the middle of its manufacture.

図２に示すように、光電変換素子は、負極となる電極(1)と、正極となる対極(2)と、両極(1)(2)間に介在させられた光触媒膜(3)および固体電解質層(4)とからなる。固体電解質層(4)は、図１に示す製造段階では、ゲル状固体電解質シート(12)として用意され、このゲル状固体電解質シート(12)が加熱後冷却されることにより、図２に示すように、光触媒膜(3)および対極(2)に密着した固体電解質層(4)が得られている。   As shown in FIG. 2, the photoelectric conversion element comprises an electrode (1) serving as a negative electrode, a counter electrode (2) serving as a positive electrode, a photocatalytic film (3) interposed between the two electrodes (1) and (2), and a solid It consists of an electrolyte layer (4). The solid electrolyte layer (4) is prepared as a gel-like solid electrolyte sheet (12) in the manufacturing stage shown in FIG. 1, and the gel-like solid electrolyte sheet (12) is cooled after being heated, so that it is shown in FIG. Thus, the solid electrolyte layer (4) in close contact with the photocatalyst film (3) and the counter electrode (2) is obtained.

１．電極の製造
電極(1)は、電極用透明基板(5)の表面に、導電性金属酸化物を含む透明導電膜(6)を形成し、さらに、その上に、固体電解質層(7)を形成した構造である。 1. Production of electrode The electrode (1) is formed by forming a transparent conductive film (6) containing a conductive metal oxide on the surface of a transparent substrate for electrodes (5), and further forming a solid electrolyte layer (7) thereon. It is a formed structure.

電極用透明基板(5)は、熱可塑性樹脂製とされる。固体電解質層(7)は、ヨウ化銅（ＣｕＩ）を含むアセトニトリル溶液を滴下し、乾燥によりアセトニトリルを蒸発させることで形成される。 The electrode transparent substrate (5) is made of a thermoplastic resin. The solid electrolyte layer (7) is formed by dropping an acetonitrile solution containing copper iodide (CuI) and evaporating the acetonitrile by drying.

２．対極の製造
対極(2)は、固体電解質に天然高分子を加えてゲル状とし、このゲル状固体電解質(9)をメッシュ状の銅電極(8)に流し込むことで作成される。固体電解質は、ゲル状に限定されるものではなく、完全固体型の固体電解質であってもよい。また、全てをゲル状にしたものに限定されるものではなく、表面（対極側の面）およびその近傍のみを完全固体型の固体電解質としてもよい。 2. Production of counter electrode The counter electrode (2) is formed by adding a natural polymer to a solid electrolyte to form a gel, and pouring the gel solid electrolyte (9) into a mesh-like copper electrode (8). The solid electrolyte is not limited to a gel, and may be a completely solid type solid electrolyte. Moreover, it is not limited to what made all the gel form, and it is good also considering only the surface (surface of a counter electrode side) and its vicinity as a complete solid type solid electrolyte.

光触媒膜(3)は、光増感色素(11)で染色された光触媒粒子(10)からなる。光触媒膜(3)は、ゲル状固体電解質シート(12)の表面に、光増感色素(11)と光触媒粒子(10)とを含むペーストを塗布した後、乾燥させることにより形成される。ペーストは、光増感色素(11)と光触媒粒子(10)の混合物に例えばアルコールと水を加えて調製することができる。   The photocatalyst film (3) is composed of photocatalyst particles (10) dyed with a photosensitizing dye (11). The photocatalyst film (3) is formed by applying a paste containing the photosensitizing dye (11) and the photocatalyst particles (10) to the surface of the gel-like solid electrolyte sheet (12) and then drying it. The paste can be prepared by adding, for example, alcohol and water to a mixture of the photosensitizing dye (11) and the photocatalyst particles (10).

光増感色素(11)と光触媒粒子(10)とを含むペーストを用いることで、短時間でゲル状固体電解質シート(12)の表面に光増感色素(11)で染色された光触媒粒子(10)を担持させることができる。   By using a paste containing photosensitizing dye (11) and photocatalyst particles (10), photocatalyst particles dyed with photosensitizing dye (11) on the surface of gel-like solid electrolyte sheet (12) in a short time ( 10) can be supported.

光増感色素(11)と光触媒粒子(10)とを含むペーストは、さらにカーボンナノチューブ粒子を含むことが好ましい。この場合、光触媒粒子(10)は平均粒子径が約２０ｎｍであることが好ましく、カーボンナノチューブ粒子は、マルチウオールナノチューブ群（ＭＷＮＴ）の長さ1μｍの粒子(ＭＷＮＴをアルコールに分散し、超音波洗浄器で微粉化し、濾過器で1μｍ以下のＭＷＮＴを取り出したもの)とされる。ＭＷＮＴ以外に、シングルウオールナノチューブ群（ＳＷＮＴ）やダブルウオールナノチューブ群（ＤＷＮＴ）を用いても良い。このようにすると、カーボンナノチューブ粒子により、電子の移動がよりスムーズになり、発電効率の向上につながる。   The paste containing the photosensitizing dye (11) and the photocatalyst particles (10) preferably further contains carbon nanotube particles. In this case, the photocatalyst particle (10) preferably has an average particle diameter of about 20 nm, and the carbon nanotube particle is a multi-wall nanotube group (MWNT) particle having a length of 1 μm (MWNT is dispersed in alcohol and subjected to ultrasonic cleaning. Pulverized with a filter and MWNT of 1 μm or less was taken out with a filter). In addition to MWNT, a single wall nanotube group (SWNT) or a double wall nanotube group (DWNT) may be used. If it does in this way, movement of an electron will become smoother by carbon nanotube particles, and it will lead to improvement in power generation efficiency.

３．ゲル状固体電解質シートの製造
別途、固体電解質に微粒子を混ぜて、ゲル状固体電解質シート(12)を作成する。ゲル状固体電解質シート(12)は、多孔質体（例えば不織布）にゲル状固体電解質を含浸させたものでもよい。 3. Production of gel-like solid electrolyte sheet Separately, a solid electrolyte is mixed with fine particles to prepare a gel-like solid electrolyte sheet (12). The gel-like solid electrolyte sheet (12) may be obtained by impregnating a porous body (for example, a nonwoven fabric) with a gel-like solid electrolyte.

４．素子の組立て
ゲル状固体電解質(9)を含むメッシュ状電極(8)からなる対極(2)の上にゲル状固体電解質シート(12)を配置し、その上に光増感色素(11)を含む光触媒粒子(10)を担持させて光触媒膜(3)を形成する。ついで、電極(1)と対極(2)との間に光触媒膜(3)およびゲル状固体電解質シート(12)が挟まれるように、電極(1)と対極(2)とを重ね合わせて、これらを焼成（加熱）する。焼成に際しては、例えば、ヒーター内蔵の金型(13)(14)が使用される。 4). Assembling the elementA gel-like solid electrolyte sheet (12) is placed on a counter electrode (2) comprising a mesh-like electrode (8) containing a gel-like solid electrolyte (9), and a photosensitizing dye (11) is placed thereon. The photocatalyst film (3) is formed by supporting the photocatalyst particles (10). Next, the electrode (1) and the counter electrode (2) are overlapped so that the photocatalyst film (3) and the gelled solid electrolyte sheet (12) are sandwiched between the electrode (1) and the counter electrode (2), These are fired (heated). For firing, for example, molds (13) and (14) with a built-in heater are used.

すなわち、図２に示すように、平らな下型(13)と下面が開口した筒状の上型(14)とを使用し、電極(1)の周縁部と対極(2)の周縁部とを密着させて５秒〜１分程度加熱する。これにより、熱可塑性樹脂製透明基板(5)の周縁部が対極(2)の周縁部に加熱接着（ヒートシール）され、透明導電膜(6)および固体電解質(7)(9)(12)が電極(1)と対極(2)との間に封入される。ゲル状固体電解質シート(12)は、加熱されることで液化し、光触媒粒子(10)内部に浸透する。その後、冷却することで、ゲル状固体電解質シート(12)は固体化して固体電解質層(4)を形成し、これにより、密着性に優れた光電変換素子が得られる。   That is, as shown in FIG. 2, a flat lower die (13) and a cylindrical upper die (14) with an open bottom surface are used, and the peripheral edge of the electrode (1) and the peripheral edge of the counter electrode (2) Is heated for about 5 seconds to 1 minute. As a result, the peripheral edge of the thermoplastic resin transparent substrate (5) is heat-bonded (heat sealed) to the peripheral edge of the counter electrode (2), and the transparent conductive film (6) and the solid electrolyte (7) (9) (12) Is enclosed between the electrode (1) and the counter electrode (2). The gel-like solid electrolyte sheet (12) is liquefied by being heated and penetrates into the photocatalyst particles (10). Thereafter, by cooling, the gelled solid electrolyte sheet (12) is solidified to form the solid electrolyte layer (4), whereby a photoelectric conversion element having excellent adhesion can be obtained.

なお、図１において、電極(1)および対極(2)は、下型(13)とほぼ同じ大きさ（面積）とされ、電極(1)の透明導電膜(6)は、短絡防止のために、予め、レーザーによって除去されて、これらよりも一回り小さい大きさとされる。これにより、電極(2)の熱可塑性樹脂製透明基板(5)は、透明導電膜(6)を介さずに対極(2)に密着させられる。   In FIG. 1, the electrode (1) and the counter electrode (2) are approximately the same size (area) as the lower die (13), and the transparent conductive film (6) of the electrode (1) is used to prevent a short circuit. In addition, it is removed by a laser in advance, and the size is slightly smaller than these. Thereby, the thermoplastic resin transparent substrate (5) of the electrode (2) is brought into close contact with the counter electrode (2) without passing through the transparent conductive film (6).

この実施例１の構成において、電極(1)の透明基板(5)をＰＥＮ（ポリエチレン・ナフタレート）（厚さ１００μｍ）、透明導電膜(6)をＩＴＯ、対極(2)のゲル状固体電解質(9)およびゲル状固体電解質シート(12)をＤＭＰＩｍＩ、天然高分子をゼラチン、ゲル状固体電解質シート(12)内に混入する微粒子を５ｎｍのセラミック、光触媒粒子(10)を酸化チタン、光増感色素(11)をルテニウム色素、光触媒膜(3)の厚さを０．２ｎｍとし、これらを重ね合わせて３０秒加熱することで、光電変換素子（色素増感太陽電池）を製造し、この１０ｍｍ角の光電変換素子について、ＡＭ１．５、１００ｍＷ／ｃｍ２の標準光源照射により電力変換効率を計測した結果、変換効率は６％であった。 In the configuration of Example 1, the transparent substrate (5) of the electrode (1) is PEN (polyethylene naphthalate) (thickness 100 μm), the transparent conductive film (6) is ITO, and the gelled solid electrolyte (2) ( 9) DMPImI for the gel-like solid electrolyte sheet (12), gelatin for the natural polymer, 5 nm ceramic for the fine particles mixed in the gel-like solid electrolyte sheet (12), titanium oxide for the photocatalyst particles (10), photosensitization The dye (11) is a ruthenium dye and the photocatalyst film (3) is 0.2 nm thick. These are superposed and heated for 30 seconds to produce a photoelectric conversion element (dye-sensitized solar cell). As a result of measuring power conversion efficiency by irradiation of a standard light source of AM 1.5 and 100 mW / cm 2 for the corner photoelectric conversion element, the conversion efficiency was 6%.

実施例２
図３は、実施例２の光電変換素子を示し、図４は、その製造途中の状態を示している。 Example 2
FIG. 3 shows a photoelectric conversion element of Example 2, and FIG. 4 shows a state in the middle of its manufacture.

実施例２の光電変換素子は、実施例１のものと対極の構成が相違しているもので、図３に示すように、この光電変換素子は、負極となる電極(1)と、正極となる対極(20)と、両極(1)(20)間に介在させられた光触媒膜(3)および固体電解質層(4)とからなる。固体電解質層(4)は、図３に示す製造段階では、ゲル状固体電解質シート(12)として用意され、このゲル状固体電解質シート(12)が加熱後冷却されることにより、図４に示すように、光触媒膜(3)および対極(20)のブラシ状カーボンナノチューブ群(24)に密着した固体電解質層(4)が得られている。   The photoelectric conversion element of Example 2 is different from that of Example 1 in the configuration of the counter electrode. As shown in FIG. 3, the photoelectric conversion element includes an electrode (1) serving as a negative electrode, a positive electrode, And a photocatalyst film (3) and a solid electrolyte layer (4) interposed between the two electrodes (1) and (20). The solid electrolyte layer (4) is prepared as a gel-like solid electrolyte sheet (12) in the manufacturing stage shown in FIG. 3, and this gel-like solid electrolyte sheet (12) is cooled after being heated, so that it is shown in FIG. As described above, the solid electrolyte layer (4) adhered to the photocatalyst film (3) and the brush-like carbon nanotube group (24) of the counter electrode (20) is obtained.

１．電極の製造
電極(1)は、実施例１と同じとする
２．対極の製造
対極(20)は、下記の工程で製造する。まず、対極用基板(21)の表面に、導電性金属酸化物を含む透明導電膜(22)を形成し、その上に、導電性接着剤を塗布して導電性接着剤層(23)を形成し、同層(23)の上に、別途、熱化学蒸着、プラズマ化学蒸着などの方法で基材に実質上垂直に形成したブラシ状カーボンナノチューブ群(24)を対極用基板(21)の表面に対して実質状垂直に配向するように転写する。ついで、カーボンナノチューブ群(24)上に、ヨウ化銅からなる固体電解質層(25)を形成する。 1. 1. Production of electrode The electrode (1) is the same as in Example 1. Production of counter electrode The counter electrode (20) is produced by the following process. First, a transparent conductive film (22) containing a conductive metal oxide is formed on the surface of the counter electrode substrate (21), and a conductive adhesive is applied thereon to form a conductive adhesive layer (23). A brush-like carbon nanotube group (24) formed on the same layer (23) and formed substantially perpendicular to the base material by a method such as thermal chemical vapor deposition or plasma chemical vapor deposition is separately formed on the counter electrode substrate (21). Transfer is performed so as to be oriented substantially perpendicular to the surface. Next, a solid electrolyte layer (25) made of copper iodide is formed on the carbon nanotube group (24).

対極用基板(21)および透明導電膜(22)は、電極(1)と同じ構造とされている。対極用基板(21)および透明導電膜(22)は、アルミニウム、銅、スズなどの金属のシートに代えることができる。   The counter electrode substrate (21) and the transparent conductive film (22) have the same structure as the electrode (1). The counter electrode substrate (21) and the transparent conductive film (22) can be replaced with a sheet of metal such as aluminum, copper, or tin.

導電性接着剤層(23)は、カーボン系導電性接着剤からなるものであってよいが、これに限定されない。    The conductive adhesive layer (23) may be made of a carbon-based conductive adhesive, but is not limited thereto.

固体電解質層(25)を形成する前に、ブラシ状カーボンナノチューブ群(24)の表面に導電性高分子膜（図示省略）を形成する。導電性高分子はポリアニリン（ポリエチレンジオキシチオフェン［ＰＥＤＯＴ］、ポリスチレンスルホネート［ＰＳＳ］等であって良い。導電性高分子膜は必須ではないが、同膜を形成することでブラシ状カーボンナノチューブ群(24)と固体電解質層(25)との密着性が向上する。   Before forming the solid electrolyte layer (25), a conductive polymer film (not shown) is formed on the surface of the brush-like carbon nanotube group (24). The conductive polymer may be polyaniline (polyethylenedioxythiophene [PEDOT], polystyrene sulfonate [PSS], etc. The conductive polymer film is not essential, but by forming the film, a group of brush-like carbon nanotubes ( The adhesion between 24) and the solid electrolyte layer (25) is improved.

ブラシ状カーボンナノチューブ群(24)は、対極用基板(21)の表面に対して実質状垂直に配向する以外に、対極用基板(21)の表面に対して傾斜状に設けても良い。この場合、カーボンナノチューブ群の厚さを薄くすることができ、これにより電極厚みを薄くすることができる。結果として、薄膜の光電変換素子（色素増感太陽電池）が実現できる。また、体積当たりのカーボン密度（カーボンナノチューブ群密度）が高まることで、体積当たりカーボン表面積が増加し、体積当たりエネルギー密度と体積当たり出力密度がともに高くなる。   The brush-like carbon nanotube group (24) may be inclined with respect to the surface of the counter electrode substrate (21) in addition to being oriented substantially perpendicular to the surface of the counter electrode substrate (21). In this case, the thickness of the carbon nanotube group can be reduced, and thereby the electrode thickness can be reduced. As a result, a thin film photoelectric conversion element (a dye-sensitized solar cell) can be realized. Further, the carbon density per unit volume (carbon nanotube group density) increases, so that the carbon surface area per unit volume increases, and both the energy density per unit volume and the output density per unit volume increase.

ヨウ化銅からなる固体電解質層(25)は、導電性高分子膜を有する又は有しないブラシ状カーボンナノチューブ群(24)上に、ヨウ化銅（ＣｕＩ）を含むアセトニトリル溶液を滴下した後、乾燥させて、アセトニトリルを蒸発させることにより形成することができる。   The solid electrolyte layer (25) made of copper iodide is prepared by dropping an acetonitrile solution containing copper iodide (CuI) on the brush-like carbon nanotube group (24) with or without a conductive polymer film, followed by drying. And can be formed by evaporating acetonitrile.

３．ゲル状固体電解質シートの製造
ゲル状固体電解質シート(12)は、実施例１と同じとする。 3. Production of gel-like solid electrolyte sheet The gel-like solid electrolyte sheet (12) is the same as in Example 1.

４．素子の組立て
こうして製造した電極(1)と対極(20)を、前者の透明導電膜(6)と後者のブラシ状カーボンナノチューブ群(24)が内側になるように、対向させて、互いに押し付けながら、これらを焼成することで光電変換素子を製造する。 4). While assembling the element, the electrode (1) and the counter electrode (20) thus produced were opposed to each other so that the former transparent conductive film (6) and the latter brush-like carbon nanotube group (24) were inside, and pressed against each other. These are fired to produce a photoelectric conversion element.

焼成は、実施例１と同様にして行うことができる。   Firing can be performed in the same manner as in Example 1.

また、焼成時に、電極(1)側から光触媒膜(3)に向けてエネルギービームを照射することで光触媒粒子(10)間の密着性を向上させることができる。   In addition, the adhesion between the photocatalyst particles (10) can be improved by irradiating an energy beam from the electrode (1) side toward the photocatalyst film (3) during firing.

この実施例２の構成において、電極(1)の透明基板(5)をＰＥＮ（ポリエチレン・ナフタレート）（厚さ１００μｍ）、透明導電膜(6)をＩＴＯ、対極(2)のゲル状固体電解質シート(12)をＤＭＰＩｍＩ、天然高分子をゼラチン、ゲル状固体電解質シート(12)内に混入する微粒子を５ｎｍのセラミック、光触媒粒子(10)を酸化チタン、光増感色素(11)をルテニウム色素、光触媒膜(3)の厚さを０．２ｎｍ、ブラシ状カーボンナノチューブの厚さを５０μｍとし、これらを重ね合わせて３０秒加熱することで、光電変換素子（色素増感太陽電池）を製造し、この１０ｍｍ角の光電変換素子について、ＡＭ１．５、１００ｍＷ／ｃｍ２の標準光源照射により電力変換効率を計測した結果、変換効率は６％であった。 In the configuration of Example 2, the transparent substrate (5) of the electrode (1) is PEN (polyethylene naphthalate) (thickness 100 μm), the transparent conductive film (6) is ITO, and the gel-like solid electrolyte sheet of counter electrode (2) (12) is DMPImI, natural polymer is gelatin, fine particles mixed in gel-like solid electrolyte sheet (12) are 5 nm ceramic, photocatalyst particles (10) are titanium oxide, photosensitizing dye (11) is ruthenium dye, The thickness of the photocatalyst film (3) is 0.2 nm, the thickness of the brush-like carbon nanotube is 50 μm, these are superposed and heated for 30 seconds to produce a photoelectric conversion element (dye-sensitized solar cell), As a result of measuring the power conversion efficiency of this 10 mm square photoelectric conversion element by irradiation with a standard light source of AM 1.5 and 100 mW / cm 2 , the conversion efficiency was 6%.

図１は、実施例１による光電変換素子の製造途中を示す断面図である。FIG. 1 is a cross-sectional view illustrating the process of manufacturing a photoelectric conversion element according to Example 1. 図２は、実施例１による光電変換素子を示す断面図である。FIG. 2 is a cross-sectional view illustrating the photoelectric conversion element according to the first embodiment. 図３は、実施例２による光電変換素子の製造途中を示す断面図である。FIG. 3 is a cross-sectional view illustrating the process of manufacturing a photoelectric conversion element according to Example 2. 図４は、実施例２による光電変換素子を示す断面図である。FIG. 4 is a cross-sectional view illustrating a photoelectric conversion element according to the second embodiment.

符号の説明Explanation of symbols

(1) 電極
(2) 対極
(3) 光触媒膜
(4) 固体電解質
(5) 電極用基板
(6) 透明導電膜
(7) 固体電解質層
(8) メッシュ状電極
(9) 固体電解質層
(10) 光触媒粒子
(11) 光増感色素
(20) 対極
(21) 対極用基板
(22) 透明導電膜
(23) 導電性接着剤層
(24) ブラシ状カーボンナノチューブ群 (1) Electrode
(2) Counter electrode
(3) Photocatalytic film
(4) Solid electrolyte
(5) Electrode substrate
(6) Transparent conductive film
(7) Solid electrolyte layer
(8) Mesh electrode
(9) Solid electrolyte layer
(10) Photocatalyst particles
(11) Photosensitizing dye
(20) Counter electrode
(21) Counter electrode substrate
(22) Transparent conductive film
(23) Conductive adhesive layer
(24) Brush-like carbon nanotube group

Claims (7)

透明な電極とこれに対向する対極とを有する光電変換素子において、前記対極は、対極用基板の片面上に固体電解質層を形成した構造であり、電極の周縁部を除いた部分と対極の周縁部を除いた部分との間に、光増感色素で染色された光触媒膜および天然高分子またはその誘導体により固体化されたゲル状固体電解質シートが挟まれるとともに、電極の周縁部が対極の周縁部に加熱接着されていることを特徴とする、光電変換素子。   In a photoelectric conversion element having a transparent electrode and a counter electrode opposite to the transparent electrode, the counter electrode has a structure in which a solid electrolyte layer is formed on one surface of a counter electrode substrate, and a portion excluding the peripheral portion of the electrode and the peripheral edge of the counter electrode A photocatalytic film dyed with a photosensitizing dye and a gel-like solid electrolyte sheet solidified with a natural polymer or a derivative thereof are sandwiched between the part excluding the part and the peripheral part of the electrode is the peripheral part of the counter electrode A photoelectric conversion element, wherein the photoelectric conversion element is heat-bonded to the part. 前記対極用基板の片面上に導電性接着剤層を同基板を覆うように形成し、同接着剤層を介して、別途形成のブラシ状カーボンナノチューブ群を基板に転写することで、前記対極を構成していることを特徴とする、請求項１記載の光電変換素子。   A conductive adhesive layer is formed on one surface of the counter electrode substrate so as to cover the substrate, and a separately formed brush-like carbon nanotube group is transferred to the substrate via the adhesive layer, whereby the counter electrode is The photoelectric conversion element according to claim 1, wherein the photoelectric conversion element is configured. 透明な電極とこれに対向する対極とを有する光電変換素子を製造する方法であって、電極を作成する工程と、対極用基板の片面上に天然高分子またはその誘導体により固体化されたゲル状固体電解質シートを配置する工程と、電極とゲル状固体電解質シートとの間に光増感色素で染色された光触媒膜を介在させる工程と、電極と対極とを両極間にゲル状固体電解質シートおよび光触媒膜が挟まれるように対向させる工程と、加熱によりゲル状固体電解質シートを溶解する工程と、冷却により溶解した固体電解質を固体化する工程とを含んでいることを特徴とする、光電変換素子の製造方法。   A method for producing a photoelectric conversion element having a transparent electrode and a counter electrode opposite to the transparent electrode, the step of producing the electrode, and a gel-like solidified by a natural polymer or a derivative thereof on one side of the counter electrode substrate A step of disposing a solid electrolyte sheet, a step of interposing a photocatalyst film dyed with a photosensitizing dye between the electrode and the gel-like solid electrolyte sheet, a gel-like solid electrolyte sheet between the electrode and the counter electrode, and A photoelectric conversion element comprising a step of facing the photocatalyst film so as to be sandwiched, a step of dissolving the gel-like solid electrolyte sheet by heating, and a step of solidifying the solid electrolyte dissolved by cooling Manufacturing method. 対極用基板の片面上にゲル状固体電解質シートを配置する工程の前に、前記対極用基板の片面上に導電性接着剤層を同基板を覆うように形成する工程と、同接着剤層を介して、別途形成のブラシ状カーボンナノチューブ群を基板に転写する工程と、固体電解質層をブラシ状カーボンナノチューブ群の表面に形成する工程とを含んでいることを特徴とする、請求項３記載の光電変換素子の製造方法。   Before the step of disposing the gel-like solid electrolyte sheet on one side of the counter electrode substrate, a step of forming a conductive adhesive layer on one side of the counter electrode substrate so as to cover the substrate, and the adhesive layer And a step of transferring a separately formed brush-like carbon nanotube group to a substrate and a step of forming a solid electrolyte layer on the surface of the brush-like carbon nanotube group. A method for producing a photoelectric conversion element. 前記ゲル状固体電解質シート中に微粒子を含むことを特徴とする、請求項３または４に記載の光電変換素子の製造方法。   The method for producing a photoelectric conversion element according to claim 3, wherein the gel-like solid electrolyte sheet contains fine particles. 加熱によりゲル状固体電解質シートを溶解する工程において、前記光触媒粒子にエネルギービームを照射することを特徴とする、請求項３から５のいずれかに記載の光電変換素子の製造方法。   6. The method for producing a photoelectric conversion element according to claim 3, wherein the photocatalyst particles are irradiated with an energy beam in the step of dissolving the gelled solid electrolyte sheet by heating. 電極を作成する工程は、透明基板の片面上に透明導電膜を形成する工程と、透明導電膜上に固体電解質層を形成する工程とを含んでいることを特徴とする、請求項３から６のいずれかに記載の光電変換素子の製造方法。   The step of creating an electrode includes a step of forming a transparent conductive film on one side of a transparent substrate and a step of forming a solid electrolyte layer on the transparent conductive film. The manufacturing method of the photoelectric conversion element in any one of.
JP2008078267A 2008-03-25 2008-03-25 Method for manufacturing photoelectric conversion element Expired - Fee Related JP5339756B2 (en)

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