JP6326815B2 - Solar cell electrode substrate - Google Patents
Solar cell electrode substrate Download PDFInfo
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- JP6326815B2 JP6326815B2 JP2013273026A JP2013273026A JP6326815B2 JP 6326815 B2 JP6326815 B2 JP 6326815B2 JP 2013273026 A JP2013273026 A JP 2013273026A JP 2013273026 A JP2013273026 A JP 2013273026A JP 6326815 B2 JP6326815 B2 JP 6326815B2
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- conductive layer
- solar cell
- layer
- dye
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Images
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Description
本発明は、色素増感型太陽電池用対向電極として好適に用いられる太陽電池用電極基板、前記電極基板からなる対向電極、及び前記対向電極を備えた色素増感型太陽電池に関する。 The present invention relates to an electrode substrate for a solar cell that is suitably used as a counter electrode for a dye-sensitized solar cell, a counter electrode composed of the electrode substrate, and a dye-sensitized solar cell including the counter electrode.
近年、光エネルギーを電力に変換する光電変換素子として、太陽電池が注目されている。中でも、色素増感型太陽電池は、シリコン型太陽電池等に比べて軽量化が期待でき、広い照度範囲で安定して発電できることや、大掛かりな設備を必要とすることなく、比較的安価な材料を用いて製造し得ることなどから、注目されている。 In recent years, solar cells have attracted attention as photoelectric conversion elements that convert light energy into electric power. Above all, dye-sensitized solar cells can be expected to be lighter than silicon solar cells, etc., and can generate power stably over a wide illuminance range, and are relatively inexpensive materials without requiring extensive equipment. It is attracting attention because it can be produced using
色素増感型太陽電池は、通常、光電極、電解質層、対向電極がこの順に並んでなる構造を有する。そして、光電極中の増感色素が光を受けて励起されると、増感色素の電子が取り出される。この電子は、光電極から出て、外部の回路を通って対向電極に移動し、電解質層に移動する。 A dye-sensitized solar cell usually has a structure in which a photoelectrode, an electrolyte layer, and a counter electrode are arranged in this order. And if the sensitizing dye in a photoelectrode receives light and is excited, the electron of a sensitizing dye will be taken out. The electrons exit from the photoelectrode, move to the counter electrode through an external circuit, and move to the electrolyte layer.
かかる色素増感型太陽電池であるが、その電極の導電層は一般に、透明性を確保する観点から、インジウム−スズ酸化物（ＩＴＯ）、フッ素−スズ酸化物（ＦＴＯ）及びインジウム−亜鉛酸化物（ＩＺＯ）などの複合金属酸化物から形成されており、導電層単独では集電能が低いため、従来、電極には外部金属配線を設けることが行われている。 In such a dye-sensitized solar cell, the conductive layer of the electrode is generally indium-tin oxide (ITO), fluorine-tin oxide (FTO), and indium-zinc oxide from the viewpoint of ensuring transparency. Since it is made of a complex metal oxide such as (IZO) and the current collecting ability of the conductive layer alone is low, external metal wiring is conventionally provided on the electrode.
例えば、特許文献１には、２つの色素増感太陽電池セルを同方向に透明絶縁層を介在させて積層し、当該透明絶縁層を貫通し、かつ前記２つの色素増感太陽電池セルを互いに電気的に接続する貫通電極（外部金属配線）を設けてモジュールを構成し、かつ集電能を高めることで、光電変換効率の向上を図る色素増感太陽電池モジュールが開示されている。また、当該文献には、開示される色素増感太陽電池では、前記金属配線が電解質層と接触すると経時的に腐食劣化することから、かかる問題を解決する手段として、複数層の絶縁層により金属配線を絶縁被覆することが開示されている。 For example, in Patent Document 1, two dye-sensitized solar cells are stacked with a transparent insulating layer interposed in the same direction, penetrate through the transparent insulating layer, and the two dye-sensitized solar cells are connected to each other. A dye-sensitized solar cell module is disclosed in which a through-electrode (external metal wiring) that is electrically connected is provided to constitute a module, and the current collecting ability is increased to improve the photoelectric conversion efficiency. Further, in this document, in the disclosed dye-sensitized solar cell, when the metal wiring comes into contact with the electrolyte layer, the corrosion deteriorates with time. Insulating the wiring is disclosed.
本発明は、集電能に優れ、耐食性を有する、色素増感型太陽電池用対向電極として好適に用いられる太陽電池用電極基板、該電極基板からなる色素増感型太陽電池用対向電極、該対向電極を備えてなる色素増感型太陽電池、及び該色素増感型太陽電池を接続してなる太陽電池モジュールを提供することを目的とする。 The present invention has an excellent current collecting ability and corrosion resistance, and is suitably used as a counter electrode for a dye-sensitized solar cell, a counter electrode for a dye-sensitized solar cell comprising the electrode substrate, and the counter electrode It aims at providing the dye-sensitized solar cell provided with an electrode, and the solar cell module formed by connecting the dye-sensitized solar cell.
本発明者らは上記課題を解決すべく鋭意検討を重ねた結果、支持体の一方の面に金属薄膜からなる導電層１を形成し、前記支持体の他方の面に金属薄膜以外の導電膜からなる導電層２を形成し、前記支持体を貫通する貫通配線を設けて前記導電層１と前記導電層２とを互いに電気的に接続し、前記貫通配線及び／又は前記導電層２をカーボンナノチューブを用いて形成した電極基板によれば、前記課題を解決できることを見出し、本発明を完成するに到った。 As a result of intensive studies to solve the above problems, the present inventors formed a conductive layer 1 made of a metal thin film on one surface of the support, and a conductive film other than the metal thin film on the other surface of the support. The conductive layer 2 is formed, and a through wiring penetrating the support is provided to electrically connect the conductive layer 1 and the conductive layer 2 to each other. The through wiring and / or the conductive layer 2 is made of carbon. The present inventors have found that an electrode substrate formed using nanotubes can solve the above-mentioned problems, and have completed the present invention.
すなわち、本発明によれば、
〔１〕支持体と、前記支持体の一方の面に形成された、金属薄膜からなる導電層１と、前記支持体の他方の面に形成された、前記金属薄膜以外の導電膜からなる導電層２と、前記支持体を貫通するように配置され、前記導電層１と前記導電層２とを互いに電気的に接続する貫通配線と、を備えてなり、
（ｉ）前記貫通配線がカーボンナノチューブを含んでなるか、及び／又は
（ｉｉ）前記導電層２がカーボンナノチューブを含んでなる、
太陽電池用電極基板、
〔２〕前記カーボンナノチューブが、平均直径（Ａｖ）と直径の標準偏差（σ）が関係式：０．６０＞３σ／Ａｖ＞０．２０を満たす、前記〔１〕記載の電極基板、
〔３〕前記金属薄膜が銅からなる前記〔１〕又は〔２〕記載の電極基板、
〔４〕前記導電層２の厚さが５０ｎｍ〜１００μｍである前記〔１〕〜〔３〕いずれか記載の電極基板、
〔５〕前記〔１〕〜〔４〕いずれかに記載の電極基板からなる色素増感型太陽電池用対向電極、
〔６〕前記〔５〕に記載の対向電極を備えてなる色素増感型太陽電池、並びに
〔７〕前記〔６〕に記載の色素増感型太陽電池が直列及び／又は並列に接続されてなる太陽電池モジュール、
が、提供される。
That is, according to the present invention,
[1] A support, a conductive layer 1 formed of a metal thin film formed on one surface of the support, and a conductive film formed of a conductive film other than the metal thin film formed on the other surface of the support. A layer 2 and a through-wiring line disposed so as to penetrate the support and electrically connecting the conductive layer 1 and the conductive layer 2 to each other;
(I) the through wiring includes carbon nanotubes, and / or (ii) the conductive layer 2 includes carbon nanotubes,
Solar cell electrode substrate,
[2] The electrode substrate according to the above [1], wherein the carbon nanotube satisfies the relational expression: 0.60> 3σ / Av> 0.20 in terms of an average diameter (Av) and a standard deviation (σ) of the diameter,
[3] The electrode substrate according to [1] or [2], wherein the metal thin film is made of copper,
[4] The electrode substrate according to any one of [1] to [3], wherein the thickness of the conductive layer 2 is 50 nm to 100 μm,
[5] A counter electrode for a dye-sensitized solar cell comprising the electrode substrate according to any one of [1] to [4],
[6] The dye-sensitized solar cell comprising the counter electrode according to [5], and [7] the dye-sensitized solar cell according to [6] connected in series and / or in parallel. Solar cell module,
Is provided.
本発明によれば、集電能に優れ、耐食性を有する、色素増感型太陽電池用対向電極として好適に用いられる太陽電池用電極基板、該電極基板からなる色素増感型太陽電池用対向電極、該対向電極を備えてなる色素増感型太陽電池、及び該色素増感型太陽電池を接続してなる太陽電池モジュールを提供することができる。 According to the present invention, an electrode substrate for a solar cell that is suitably used as a counter electrode for a dye-sensitized solar cell, having excellent current collecting ability and corrosion resistance, a counter electrode for a dye-sensitized solar cell comprising the electrode substrate, It is possible to provide a dye-sensitized solar cell including the counter electrode and a solar cell module formed by connecting the dye-sensitized solar cell.
以下、本発明を、１）太陽電池用電極基板、２）色素増感型太陽電池用対向電極、並びに３）色素増感型太陽電池及び太陽電池モジュール、に項分けして詳細に説明する。 Hereinafter, the present invention will be described in detail by dividing into 1) an electrode substrate for a solar cell, 2) a counter electrode for a dye-sensitized solar cell, and 3) a dye-sensitized solar cell and a solar cell module.
１）太陽電池用電極基板
本発明の太陽電池用電極基板（以下、「電極基板」という場合がある。）は、支持体と、前記支持体の一方の面に形成された、金属薄膜からなる導電層１と、前記支持体の他方の面に形成された、前記金属薄膜以外の導電膜からなる導電層２と、前記支持体を貫通するように配置され、前記導電層１と前記導電層２とを互いに電気的に接続する貫通配線と、を備えてなり、（ｉ）前記貫通配線がカーボンナノチューブを含んでなるか、及び／又は（ｉｉ）前記導電層２がカーボンナノチューブ（以下、「ＣＮＴ」という。）を含んでなる、ものである。
1) Solar Cell Electrode Substrate The solar cell electrode substrate of the present invention (hereinafter sometimes referred to as “electrode substrate”) is composed of a support and a metal thin film formed on one surface of the support. The conductive layer 1, the conductive layer 2 made of a conductive film other than the metal thin film formed on the other surface of the support, and the conductive layer 1 and the conductive layer disposed so as to penetrate the support And (i) the through wiring includes carbon nanotubes, and / or (ii) the conductive layer 2 includes carbon nanotubes (hereinafter referred to as “carbon nanotubes”). CNT ")).
本発明の電極基板において金属薄膜からなる導電層１は集電体として機能する。当該金属薄膜からなる導電層１は、従来の複合金属酸化物などからなる導電層に比べて格段に導電性が大きく、それのみで集電を充分に行うことができる。従って、本発明の電極基板は優れた集電能を有し、集電能を高めるための外部金属配線などを省略することができる。また、かかる導電層１と前記金属薄膜以外の導電膜からなる導電層２とを互いに電気的に接続する貫通配線及び／又は導電層２がＣＮＴを用いて形成されており、かかる貫通配線及び／又は導電層２が、集電能を低下させることなく、導電層１を保護する機能を果たすことから、本発明の電極基板は優れた耐食性を有する。 In the electrode substrate of the present invention, the conductive layer 1 made of a metal thin film functions as a current collector. The conductive layer 1 made of the metal thin film has remarkably higher conductivity than a conductive layer made of a conventional composite metal oxide or the like, and can collect electricity sufficiently by itself. Therefore, the electrode substrate of the present invention has an excellent current collecting ability, and an external metal wiring for enhancing the current collecting ability can be omitted. In addition, a through wiring and / or a conductive layer 2 that electrically connects the conductive layer 1 and the conductive layer 2 made of a conductive film other than the metal thin film are formed using CNTs. Alternatively, since the conductive layer 2 functions to protect the conductive layer 1 without reducing the current collecting ability, the electrode substrate of the present invention has excellent corrosion resistance.
〔支持体〕
支持体としては、特に限定されず、例えば、樹脂基材やガラス基材を用いることができる。本発明の電極基板を、軽量で、屈曲性を有するものとする観点からは、樹脂基材を用いるのが好適である。
前記樹脂基材としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、シンジオタクチックポリスチレン（ＳＰＳ）、ポリフェニレンスルフィド（ＰＰＳ）、ポリカーボネート（ＰＣ）、ポリアリレート（ＰＡｒ）、ポリスルホン（ＰＳＦ）、ポリエステルスルホン（ＰＥＳ）、ポリエーテルイミド（ＰＥＩ）、透明ポリイミド（ＰＩ）、及びシクロオレフィンポリマー（ＣＯＰ）等の合成樹脂からなるものが挙げられる。
支持体の厚さは、所望により適宜決定すればよいが、通常、１０〜１００００μｍである。支持体は透明であってもよく、その場合、支持体の光透過率（測定波長：５００ｎｍ）としては、特に限定されないが、通常、６０％以上、好ましくは７５％以上、より好ましくは８０％以上である。
[Support]
It does not specifically limit as a support body, For example, a resin base material and a glass base material can be used. From the viewpoint of making the electrode substrate of the present invention lightweight and flexible, it is preferable to use a resin base material.
Examples of the resin base material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), and polysulfone (PSF). ), Polyester sulfone (PES), polyetherimide (PEI), transparent polyimide (PI), and cycloolefin polymer (COP).
The thickness of the support may be appropriately determined as desired, but is usually 10 to 10,000 μm. The support may be transparent. In that case, the light transmittance (measurement wavelength: 500 nm) of the support is not particularly limited, but is usually 60% or more, preferably 75% or more, more preferably 80%. That's it.
〔導電層１〕
本発明の電極基板において導電層１は金属薄膜からなる。当該金属薄膜は、電極分野において一般的に用いられる金属材料から形成される。金属材料としては、特に限定されないが、例えば、銅やアルミニウムなどが挙げられる。導電性に優れることから、金属薄膜は銅からなるのが好ましい。
導電層１の厚さは、所望により適宜決定すればよいが、通常、５０ｎｍ〜１００μｍである。
導電層１を構成する導電層１は、金属材料を用い、スパッタリング法やコーティング法等の公知の方法に従って形成することができる。金属薄膜は、通常、用いる支持体の片面全面に形成されていればよいが、所望の集電能が確保されうる限り、適宜、格子状、縞状及び櫛型など、パターン化されていてもよい。そのようなパターン化された金属薄膜は、金属材料を用い、エッチング法や、スクリーン印刷法及びメタルマスク法といった印刷法など、公知の方法に従って形成することができる。
[Conductive layer 1]
In the electrode substrate of the present invention, the conductive layer 1 is made of a metal thin film. The metal thin film is formed from a metal material generally used in the electrode field. Although it does not specifically limit as a metal material, For example, copper, aluminum, etc. are mentioned. In view of excellent conductivity, the metal thin film is preferably made of copper.
The thickness of the conductive layer 1 may be appropriately determined as desired, but is usually 50 nm to 100 μm.
The conductive layer 1 constituting the conductive layer 1 can be formed using a metal material according to a known method such as a sputtering method or a coating method. Usually, the metal thin film only needs to be formed on the entire surface of one side of the support to be used. However, as long as a desired current collecting capability can be ensured, the metal thin film may be appropriately patterned such as a lattice shape, a stripe shape, and a comb shape. . Such a patterned metal thin film can be formed using a metal material according to a known method such as an etching method, a printing method such as a screen printing method and a metal mask method.
〔導電層２〕
導電層２は、導電層１を構成する金属薄膜以外の導電膜からなる。本発明にかかる貫通配線がＣＮＴを含んでなる場合（態様１）、導電層２を構成する導電膜は、電極分野において一般的に用いられる導電材料からなるか、又はＣＮＴを含んでなり、一方、貫通配線がＣＮＴを含んでなるものでない場合（態様２）、該導電膜は、ＣＮＴを含んでなる。
[Conductive layer 2]
The conductive layer 2 is made of a conductive film other than the metal thin film constituting the conductive layer 1. When the through wiring according to the present invention includes CNT (Aspect 1), the conductive film constituting the conductive layer 2 is made of a conductive material generally used in the electrode field, or includes CNT. When the through wiring does not contain CNT (Aspect 2), the conductive film contains CNT.
前記導電材料としては、例えば、酸化スズ、酸化亜鉛等の導電性金属酸化物；ＩＴＯ、ＦＴＯ、ＩＺＯ等の複合金属酸化物；フラーレン等の炭素材料；及びこれらの２種以上の組み合わせ；などが挙げられる。前記態様１の場合、導電層２は、それらの導電材料及び／又はＣＮＴを用いて形成される。本発明の電極基板の集電能を低下させることなく、耐食性を向上させる観点から、導電層２はＣＮＴを含んでなるのが好ましい。一方、前記態様２の場合、導電層２は、ＣＮＴ及び所望により前記導電材料を用いて形成される。ここで、ＣＮＴとしては、公知のいずれのＣＮＴであってもよく、特に限定されない。 Examples of the conductive material include conductive metal oxides such as tin oxide and zinc oxide; composite metal oxides such as ITO, FTO, and IZO; carbon materials such as fullerenes; and combinations of two or more thereof. Can be mentioned. In the case of the aspect 1, the conductive layer 2 is formed using those conductive materials and / or CNTs. From the viewpoint of improving the corrosion resistance without reducing the current collecting ability of the electrode substrate of the present invention, the conductive layer 2 preferably contains CNTs. On the other hand, in the case of the said aspect 2, the conductive layer 2 is formed using CNT and the said conductive material depending on necessity. Here, the CNT may be any known CNT, and is not particularly limited.
本発明の電極基板の集電能を低下させることなく、耐食性を一層向上させる観点から、前記態様１と態様２の場合に共通して、導電層２は後述のＣＮＴ（Ａ）を含んでなるＣＮＴ含有層からなるのがより好ましい。 From the viewpoint of further improving the corrosion resistance without lowering the current collecting ability of the electrode substrate of the present invention, the conductive layer 2 is a CNT comprising CNT (A) described later in common with the first and second embodiments. More preferably, it comprises an inclusion layer.
導電層２は、単層であっても、又は２層以上の複数層であってもよい。後者の場合、各層は、同一の導電材料からなるものであっても、又は相異なる導電材料からなるものであってもよい。
導電層２の厚さは、所望により適宜決定すればよいが、通常、５０ｎｍ〜１００μｍである。
The conductive layer 2 may be a single layer or a plurality of layers of two or more layers. In the latter case, each layer may be made of the same conductive material or may be made of different conductive materials.
The thickness of the conductive layer 2 may be appropriately determined as desired, but is usually 50 nm to 100 μm.
導電層２は、前記導電材料やＣＮＴを用い、前記導電層１について記載される方法に準じて形成することができる。 The conductive layer 2 can be formed according to the method described for the conductive layer 1 using the conductive material or CNT.
さらに、導電層２は、その表面上に、例えば、樹脂、セラミックス及びガラスなどの、公知の絶縁材料を、それぞれ単独で、又は２種以上組み合わせて用いて、例えば、格子状のパターンを描き、適宜、該表面を区分けしてもよい。そのようにすることで、１つの電極基板を複数の電極基板単位に分割することができ、当該電極基板単位には、例えば、個別に太陽電池セルを形成することができる。 Furthermore, the conductive layer 2 is formed on the surface thereof using, for example, a known insulating material such as resin, ceramics, and glass, either alone or in combination of two or more, for example, a lattice-like pattern, The surface may be divided as appropriate. By doing so, one electrode substrate can be divided into a plurality of electrode substrate units, and for example, solar cells can be individually formed in the electrode substrate units.
〔ＣＮＴ含有層〕
本発明にかかるＣＮＴ含有層は、平均直径（Ａｖ）と直径の標準偏差（σ）が関係式：０．６０＞３σ／Ａｖ＞０．２０を満たすＣＮＴ（以下、ＣＮＴ（Ａ）という。）を含んでなる。導電層１を保護する機能をより良好に発揮させる観点から、ＣＮＴ（Ａ）としては、好ましくは０．６０＞３σ／Ａｖ＞０．２５、より好ましくは０．６０＞３σ／Ａｖ＞０．５０を満たすものが、好適である。
[CNT-containing layer]
In the CNT-containing layer according to the present invention, the average diameter (Av) and the standard deviation (σ) of the diameter satisfy the relational expression: 0.60> 3σ / Av> 0.20 (hereinafter referred to as CNT (A)). Comprising. From the viewpoint of better exerting the function of protecting the conductive layer 1, the CNT (A) is preferably 0.60> 3σ / Av> 0.25, more preferably 0.60> 3σ / Av> 0. Those satisfying 50 are preferred.
なお、「３σ」とは、ＣＮＴ（Ａ）の直径の（標本）標準偏差（σ）に３を乗じたものであり、直径分布を示す。そして、「平均直径（Ａｖ）」及び「直径の標準偏差（σ）」は、それぞれ、透過型電子顕微鏡を用いて無作為に選択されたＣＮＴ（Ａ）１００本の直径を測定して求めることができる（後述する平均長さも、同様の方法で長さの測定を行い、その平均値として求められる。）。また、ＣＮＴ（Ａ）の「直径」とは、当該ＣＮＴ（Ａ）の外径を意味する。さらに、本発明にかかるＣＮＴ（Ａ）としては、前述のようにして測定した直径を横軸に、その頻度を縦軸に取ってプロットし、ガウシアンで近似した際に、正規分布を取るものが通常使用される。 “3σ” is obtained by multiplying the (sample) standard deviation (σ) of the diameter of the CNT (A) by 3, and indicates a diameter distribution. The “average diameter (Av)” and “standard deviation of diameter (σ)” are obtained by measuring the diameter of 100 randomly selected CNTs (A) using a transmission electron microscope, respectively. (The average length described later can also be obtained as an average value by measuring the length in the same manner.) The “diameter” of the CNT (A) means the outer diameter of the CNT (A). Further, as the CNT (A) according to the present invention, the diameter measured as described above is plotted on the horizontal axis and the frequency is plotted on the vertical axis, and when it is approximated by Gaussian, it takes a normal distribution. Usually used.
また、本発明では、ＣＮＴ含有層が、導電層１を保護する機能をより一層良好に発揮することから、ＣＮＴ（Ａ）としては、さらに以下の特性を満足するものを用いるのが好適である。 In the present invention, since the CNT-containing layer exhibits the function of protecting the conductive layer 1 more satisfactorily, it is preferable to use a CNT (A) that satisfies the following characteristics. .
ＣＮＴ（Ａ）の平均直径（Ａｖ）は、０．５〜１５ｎｍの範囲とすることが好ましく、より好ましくは１〜１０ｎｍの範囲である。
ＣＮＴ（Ａ）の平均長さは、０．１μｍ〜１ｃｍの範囲とすることが好ましく、より好ましくは０．１μｍ〜１ｍｍの範囲である。
The average diameter (Av) of CNT (A) is preferably in the range of 0.5 to 15 nm, more preferably in the range of 1 to 10 nm.
The average length of CNT (A) is preferably in the range of 0.1 μm to 1 cm, more preferably in the range of 0.1 μm to 1 mm.
ＣＮＴ（Ａ）の比表面積としては、窒素ガス吸着によるＢＥＴ比表面積が、通常、６００ｍ２／ｇ以上、好ましくは７００ｍ２／ｇ以上であり、その上限が、通常、２５００ｍ２／ｇであり、かつ水蒸気吸着によるＢＥＴ比表面積が、通常、０．０１〜５０ｍ２／ｇ、好ましくは０．１〜３０ｍ２／ｇである。また、窒素ガス吸着によるＢＥＴ比表面積に対する水蒸気吸着によるＢＥＴ比表面積の比（水蒸気吸着によるＢＥＴ比表面積／窒素ガス吸着によるＢＥＴ比表面積）が、通常、０．０００１〜０．２、好ましくは０．０００５〜０．１５である。それらの比表面積は、例えば、「ＢＥＬＳＯＲＰ（登録商標）−ｍａｘ」（日本ベル社製）を用いて測定することができる。
さらに、ＣＮＴ（Ａ）の、昇温脱離法における１５０〜９５０℃での、一酸化炭素（ＣＯ）脱離量としては、通常、１００〜１００００μｍｏｌ／ｇであり、かつ二酸化炭素（ＣＯ２）脱離量としては、通常、１〜３０００μｍｏｌ／ｇである。ＣＯとＣＯ２の脱離量は、例えば、日本ベル社製の全自動昇温脱離スペクトル装置「ＴＰＤ−1−ＡＴｗ」により測定することができる。
ＣＮＴ（Ａ）の比表面積及びＣＯとＣＯ２の脱離量が上記範囲内にあると、ＣＮＴ（Ａ）の分散性が高まり好適である。
As the specific surface area of CNT (A), the BET specific surface area by nitrogen gas adsorption is usually 600 m 2 / g or more, preferably 700 m 2 / g or more, and the upper limit is usually 2500 m 2 / g, and BET specific surface area with steam adsorption, usually, 0.01 to 50 m 2 / g, preferably from 0.1~30m 2 / g. The ratio of the BET specific surface area by water vapor adsorption to the BET specific surface area by nitrogen gas adsorption (BET specific surface area by water vapor adsorption / BET specific surface area by nitrogen gas adsorption) is usually 0.0001 to 0.2, preferably 0.00. 0005 to 0.15. Those specific surface areas can be measured using, for example, “BELSORP (registered trademark) -max” (manufactured by Nippon Bell Co., Ltd.).
Furthermore, the amount of carbon monoxide (CO) desorbed at 150 to 950 ° C. in the temperature programmed desorption method of CNT (A) is usually 100 to 10,000 μmol / g, and carbon dioxide (CO 2 ). The desorption amount is usually 1 to 3000 μmol / g. The desorption amount of CO and CO 2 can be measured by, for example, a fully automatic temperature-programmed desorption spectrometer “TPD-1-ATw” manufactured by Bell Japan.
When the specific surface area of CNT (A) and the desorption amount of CO and CO 2 are within the above ranges, the dispersibility of CNT (A) is increased, which is preferable.
ＣＮＴ（Ａ）の質量密度は、０．００２〜０．２ｇ／ｃｍ３の範囲とすることが好ましい。なお、ＣＮＴ（Ａ）の質量密度は、後述のＣＮＴ（Ａ）の製造方法により直接的に得られるＣＮＴ（Ａ）の配向集合体として測定した値である。 The mass density of CNT (A) is preferably in the range of 0.002 to 0.2 g / cm 3 . In addition, the mass density of CNT (A) is a value measured as an aligned aggregate of CNT (A) obtained directly by a method for producing CNT (A) described later.
ＣＮＴ（Ａ）は、単層のものであっても、多層のものであってもよいが、単層から５層のものが好ましく、単層のものがより好ましい。 The CNT (A) may be a single layer or a multilayer, but a single layer to five layers are preferable, and a single layer is more preferable.
加えて、ＣＮＴ（Ａ）は、複数の微小孔を有することが好ましい。ＣＮＴ（Ａ）は、中でも、孔径が２ｎｍよりも小さいマイクロ孔を有するのが好ましく、その存在量は、下記の方法で求めたマイクロ孔容積で、好ましくは０．４ｍＬ／ｇ以上、より好ましくは０．４３ｍＬ／ｇ以上、更に好ましくは０．４５ｍＬ／ｇ以上であり、上限としては、通常、０．６５ｍＬ／ｇ程度である。なお、マイクロ孔容積は、例えば、ＣＮＴ（Ａ）の調製方法及び調製条件を適宜変更することで調整することができる。
ここで、「マイクロ孔容積（Ｖｐ）」は、ＣＮＴ（Ａ）の液体窒素温度（７７Ｋ）での窒素吸着等温線を測定し、相対圧Ｐ／Ｐ０＝０．１９における窒素吸着量をＶとして、式（Ｉ）：Ｖｐ＝（Ｖ／２２４１４）×（Ｍ／ρ）より、算出することができる。なお、Ｐは吸着平衡時の測定圧力、Ｐ０は測定時の液体窒素の飽和蒸気圧であり、 式（Ｉ）中、Ｍは吸着質（窒素）の分子量２８．０１０、ρは吸着質（窒素）の７７Ｋにおける密度０．８０８ｇ／ｃｍ３である。マイクロ孔容積は、例えば、「ＢＥＬＳＯＲＰ（登録商標）−ｍｉｎｉ」（日本ベル（株）製）を使用して容易に求めることができる。
In addition, the CNT (A) preferably has a plurality of micropores. Among them, CNT (A) preferably has micropores having a pore size smaller than 2 nm, and the abundance thereof is a micropore volume determined by the following method, preferably 0.4 mL / g or more, more preferably It is 0.43 mL / g or more, more preferably 0.45 mL / g or more, and the upper limit is usually about 0.65 mL / g. In addition, micropore volume can be adjusted by changing suitably the preparation method and preparation conditions of CNT (A), for example.
Here, “micropore volume (Vp)” is a nitrogen adsorption isotherm at the liquid nitrogen temperature (77K) of CNT (A), and the amount of nitrogen adsorption at relative pressure P / P0 = 0.19 is V. , Formula (I): Vp = (V / 22414) × (M / ρ). P is the measurement pressure at the time of adsorption equilibrium, P0 is the saturated vapor pressure of liquid nitrogen at the time of measurement, and in formula (I), M is the molecular weight of adsorbate (nitrogen) 28.010, and ρ is the adsorbate (nitrogen). ) At 77K with a density of 0.808 g / cm 3 . The micropore volume can be easily determined using, for example, “BELSORP (registered trademark) -mini” (manufactured by Nippon Bell Co., Ltd.).
以上の特性を有するＣＮＴ（Ａ）は、例えば、表面にＣＮＴ製造用触媒層を有する基材（以下、「ＣＮＴ製造用基材」ということがある。）上に、原料化合物及びキャリアガスを供給して、化学的気相成長法（ＣＶＤ法）によりＣＮＴを合成する際に、系内に微量の酸化剤を存在させることで、ＣＮＴ製造用触媒層の触媒活性を飛躍的に向上させるという方法（スーパーグロース法；ＷＯ２００６／０１１６５５号パンフレット参照）において、基材表面への触媒層の形成をウェットプロセスにより行い、アセチレンを主成分とする原料ガス（例えば、アセチレンを５０体積％以上含むガス）を用いることにより、効率的に製造することができる。 The CNT (A) having the above characteristics supplies, for example, a raw material compound and a carrier gas onto a substrate having a CNT production catalyst layer on its surface (hereinafter sometimes referred to as “CNT production substrate”). Then, when synthesizing CNTs by chemical vapor deposition method (CVD method), a method of dramatically improving the catalytic activity of the catalyst layer for producing CNTs by making a small amount of oxidizing agent present in the system. (Super growth method; refer to pamphlet of WO 2006/011655). A catalyst layer is formed on the surface of a substrate by a wet process, and a raw material gas mainly containing acetylene (for example, a gas containing 50% by volume or more of acetylene) is used. By using it, it can manufacture efficiently.
また、ＣＮＴ（Ａ）は、表面にカルボキシル基等の官能基が導入されたものであってもよい。官能基の導入は、過酸化水素や硝酸等を用いる公知の酸化処理法により行うことができる。さらに、ＣＮＴ（Ａ）は金属ナノ粒子を担持させたものであってもよい。 Further, the CNT (A) may be one having a functional group such as a carboxyl group introduced on the surface. The functional group can be introduced by a known oxidation treatment method using hydrogen peroxide, nitric acid or the like. Furthermore, CNT (A) may carry metal nanoparticles.
ＣＮＴ含有層は、例えば、溶媒として水やアルコール等を用い、ＣＮＴ（Ａ）、及び所望により分散剤、結着剤及び導電助剤等のその他の成分を溶媒中で混合し、ＣＮＴ（Ａ）を分散させることで、ＣＮＴ（Ａ）分散液を調製し、この分散液を支持体上に塗布し、得られた塗膜を乾燥することで形成することができる。混合処理や分散処理は、例えば、ジェットミルや超音波分散機などを用いる公知の方法に従って行うことができる。また、金属薄膜層への塗布は、例えば、ディッピング法、ロールコート法、グラビアコート法、スクリーン印刷法などの公知の方法に従って行うことができる。得られた塗膜の乾燥は、例えば、熱風乾燥法、熱ロール乾燥法、赤外線照射法などの公知の方法により行うことができる。また、塗膜を乾燥後、水などに塗膜を浸し、分散剤を除去し、再度乾燥させてＣＮＴ含有層を得てもよい。 The CNT-containing layer uses, for example, water or alcohol as a solvent, and mixes CNT (A) and other components such as a dispersant, a binder, and a conductive aid in a solvent, if desired. Can be formed by preparing a CNT (A) dispersion, applying the dispersion onto a support, and drying the resulting coating film. The mixing process and the dispersion process can be performed according to a known method using, for example, a jet mill or an ultrasonic disperser. Moreover, application | coating to a metal thin film layer can be performed in accordance with well-known methods, such as a dipping method, a roll coat method, a gravure coat method, a screen printing method, for example. The obtained coating film can be dried by a known method such as a hot air drying method, a hot roll drying method, or an infrared irradiation method. Moreover, after drying a coating film, a coating film may be immersed in water etc., a dispersing agent may be removed, and it may be dried again, and a CNT containing layer may be obtained.
前記分散剤としては、例えば、界面活性剤や高分子材料などが挙げられる。界面活性剤としては、分散能が高いことからイオン性界面活性剤が好ましい。分散剤の具体例としては、ポリスチレンスルホン酸、コンドロイチン硫酸、ヒアルロン酸、カルボキシメチルセルロース及びそれらの誘導体などが挙げられる。中でも、カルボキシメチルセルロース及びその誘導体が好ましい。分散剤は、それぞれ単独で、又は２種以上を組み合わせて用いることができる。
前記結着剤や導電助剤についても、公知のものを、適宜用いることができる。
Examples of the dispersant include a surfactant and a polymer material. As the surfactant, an ionic surfactant is preferable because of high dispersibility. Specific examples of the dispersant include polystyrene sulfonic acid, chondroitin sulfate, hyaluronic acid, carboxymethyl cellulose, and derivatives thereof. Of these, carboxymethylcellulose and its derivatives are preferred. A dispersing agent can be used individually or in combination of 2 or more types, respectively.
A well-known thing can also be used suitably also about the said binder and a conductive support agent.
ＣＮＴ含有層は、支持体上の全面に形成されていてもよいが、導電層１を保護する機能を果たしうる限り、適宜、格子状、縞状及び櫛型など、パターン化されていてもよい。パターン化は、スクリーン印刷法及びメタルマスク法といった印刷法など、公知の方法により行うことができる。 The CNT-containing layer may be formed on the entire surface of the support, but may be appropriately patterned such as a lattice shape, a stripe shape, and a comb shape as long as the function of protecting the conductive layer 1 can be achieved. . The patterning can be performed by a known method such as a printing method such as a screen printing method and a metal mask method.
〔貫通配線〕
貫通配線は、前記支持体を貫通するように配置されており、前記支持体を介在させて積層された、前記導電層１と前記導電層２とを互いに電気的に接続する。支持体が導電層１と導電層２とを支持しうる限り、支持体における貫通配線の数は特に限定されない。貫通配線の断面形状としては、特に限定されないが、通常、円形が好ましい。
[Through wiring]
The through wiring is disposed so as to penetrate the support, and electrically connects the conductive layer 1 and the conductive layer 2 stacked with the support interposed therebetween. As long as the support can support the conductive layer 1 and the conductive layer 2, the number of through wirings in the support is not particularly limited. The cross-sectional shape of the through wiring is not particularly limited, but a circular shape is usually preferable.
貫通配線は、例えば、導電層１及び／又は導電層２が形成されていてもよい支持体に、炭酸ガス（ＣＯ２）レーザー、紫外線レーザー及びエキシマレーザー等のレーザー光を照射するか、又はドリルを用いる公知の方法に従って孔を開け、当該孔部を導電材料により充填することで形成することができる。孔径としては、通常、１０〜２００μｍ程度が好ましい。 For example, the penetrating wiring irradiates a support on which the conductive layer 1 and / or the conductive layer 2 may be formed with a laser beam such as a carbon dioxide gas (CO 2 ) laser, an ultraviolet laser, and an excimer laser, or a drill. A hole can be formed according to a known method using, and the hole is filled with a conductive material. As a hole diameter, about 10-200 micrometers is preferable normally.
前記態様１の場合、貫通配線はＣＮＴを含んでなる。本発明の電極基板の集電能を低下させることなく、耐食性を一層向上させる観点から、かかるＣＮＴとしては前記ＣＮＴ（Ａ）が好ましい。この場合、孔部の充填は、例えば、導電材料として前記ＣＮＴ（Ａ）の分散液を用い、孔部に当該分散液を注入し、適宜、加熱乾燥させて溶媒を除去することにより行うことができる。
一方、前記態様２の場合、貫通配線はＣＮＴを含んでなるものではないため、孔部の充填は、ＣＮＴ以外の導電材料を用いる公知の方法に従って行うことができる。例えば、銀や銅を含む公知の導電性ペーストを孔部に注入し、適宜、加熱硬化したり、無電解めっきと電界めっきとにより銅を孔部に充填することにより、孔部を充填することができる。
In the case of the first aspect, the through wiring includes CNT. From the viewpoint of further improving the corrosion resistance without reducing the current collecting ability of the electrode substrate of the present invention, the CNT (A) is preferred as the CNT. In this case, for example, the filling of the holes can be performed by using the dispersion liquid of the CNT (A) as a conductive material, injecting the dispersion liquid into the holes, and appropriately drying by heating to remove the solvent. it can.
On the other hand, in the case of the above-described aspect 2, since the through wiring does not contain CNT, the filling of the hole can be performed according to a known method using a conductive material other than CNT. For example, filling a hole by injecting a known conductive paste containing silver or copper into the hole, and appropriately heating and curing, or filling the hole with copper by electroless plating and electroplating Can do.
本発明の電極基板は、支持体に対し、上記に従って、導電層１、導電層２及び貫通配線を順次形成することにより、製造することができる。 The electrode substrate of the present invention can be produced by sequentially forming the conductive layer 1, the conductive layer 2, and the through wiring on the support in accordance with the above.
本発明の電極基板は、公知の太陽電池において電極材料として好適に用いることができる。太陽電池としては、特に限定されるものではなく、例えば、単結晶シリコン型太陽電池、多結晶シリコン型太陽電池、微結晶シリコン型太陽電池、多結合型シリコン系太陽電池等の結晶シリコン系太陽電池；アモルファスシリコン型太陽電池；ＧａＡｓ系太陽電池、ＣＩＳ系太陽電池、ＣｄＴｅ系太陽電池などの化合物系太陽電池；色素増感型太陽電池、有機薄膜型太陽電池などの有機系太陽電池；などが挙げられる。中でも、本発明の電極基板は、色素増感型太陽電池（ＤＳＣ）の対向電極に好適に用いられる。 The electrode substrate of the present invention can be suitably used as an electrode material in known solar cells. The solar cell is not particularly limited. For example, a crystalline silicon solar cell such as a single crystal silicon solar cell, a polycrystalline silicon solar cell, a microcrystalline silicon solar cell, or a multi-bonded silicon solar cell. Amorphous silicon solar cells; compound solar cells such as GaAs solar cells, CIS solar cells and CdTe solar cells; organic solar cells such as dye-sensitized solar cells and organic thin film solar cells; It is done. Especially, the electrode substrate of this invention is used suitably for the counter electrode of a dye-sensitized solar cell (DSC).
２）色素増感型太陽電池用対向電極
本発明の色素増感型太陽電池用対向電極（以下、対向電極という。）は、本発明の電極基板からなる。本発明の電極基板は、導電層２として、例えば、前記ＣＮＴ含有層を有する場合、当該ＣＮＴ含有層は酸化還元触媒としても機能しうるため、本発明の電極基板はそのまま、対向電極として用いることできる。
本発明の電極基板において導電層１は、優れた導電性を有しており、当該層のみで充分な集電を行うことができる。従って、本発明の対向電極では、従来、集電能を高めるために用いられる外部金属配線などを省略することができる。なお、本発明の対向電極には、所望により外部金属配線が設けられていてもよい。
また、一般に、色素増感型太陽電池の対向電極における導電層は電解質層の溶液などと接触し、時間の経過とともに腐食劣化するが、本発明の対向電極は、導電層１と導電層２とを互いに電気的に接続する貫通配線及び／又は導電層２がＣＮＴを用いて形成されており、かかる貫通配線及び／又は導電層２が、集電能を低下させることなく、導電層１を保護する機能を果たすことから、金属薄膜からなる導電層１と電解質層との接触が防止されて腐食劣化が抑えられるため、優れた耐食性を有する。
本発明の対向電極は、その製造に、従来、触媒として用いられる高価な白金を必要とせず、所定の分散液を用いて、例えば、ロールツーロール方式により、簡便かつ低コストに製造することができる。
2) Counter electrode for dye-sensitized solar cell The counter electrode for dye-sensitized solar cell of the present invention (hereinafter referred to as counter electrode) is composed of the electrode substrate of the present invention. When the electrode substrate of the present invention has the CNT-containing layer as the conductive layer 2, for example, the CNT-containing layer can also function as a redox catalyst, so the electrode substrate of the present invention is used as it is as a counter electrode. it can.
In the electrode substrate of the present invention, the conductive layer 1 has excellent conductivity, and sufficient current collection can be performed only by the layer. Therefore, in the counter electrode of the present invention, it is possible to omit an external metal wiring or the like conventionally used for increasing the current collecting ability. The counter electrode of the present invention may be provided with an external metal wiring if desired.
In general, the conductive layer in the counter electrode of the dye-sensitized solar cell comes into contact with the solution of the electrolyte layer and the like, and corrodes with time. However, the counter electrode of the present invention includes the conductive layer 1 and the conductive layer 2. The through-wiring and / or the conductive layer 2 that are electrically connected to each other are formed using CNTs, and the through-wiring and / or the conductive layer 2 protects the conductive layer 1 without reducing the current collecting ability. Since it fulfills its function, contact between the conductive layer 1 made of a metal thin film and the electrolyte layer is prevented, and corrosion deterioration is suppressed, so that it has excellent corrosion resistance.
The counter electrode of the present invention does not require expensive platinum conventionally used as a catalyst for its production, and can be produced simply and at low cost, for example, by a roll-to-roll method using a predetermined dispersion. it can.
３）色素増感型太陽電池及び太陽電池モジュール
本発明の色素増感型太陽電池は、光電極、電解質層、及び対向電極をこの順に有し、この対向電極として、本発明の対向電極を用いるものである。
本発明の対向電極は、導電層１として、導電性に非常に優れた金属薄膜層を有しており、外部金属配線などを用いずとも、充分な集電能を有する。また、当該導電層１は、ＣＮＴを含んでなる貫通配線及び／又は導電層２により電解質層との接触が防止されており、耐食性を有する。それゆえ、本発明の対向電極を備えた本発明の色素増感型太陽電池はセルの大面積化に適しており、例えば、少なくとも１辺の長さが３ｍ以上、好適には、少なくとも１辺の長さが５ｃｍ以上のサイズを有する大面積セルを製造可能である。なお、通常、当該１辺の長さの上限としては１００ｃｍ程度である。
3) Dye-sensitized solar cell and solar cell module The dye-sensitized solar cell of the present invention has a photoelectrode, an electrolyte layer, and a counter electrode in this order, and the counter electrode of the present invention is used as the counter electrode. Is.
The counter electrode of the present invention has a metal thin film layer with excellent conductivity as the conductive layer 1, and has a sufficient current collecting ability without using an external metal wiring or the like. Further, the conductive layer 1 is prevented from contact with the electrolyte layer by the through wiring and / or the conductive layer 2 containing CNT, and has corrosion resistance. Therefore, the dye-sensitized solar cell of the present invention provided with the counter electrode of the present invention is suitable for increasing the cell area. For example, the length of at least one side is 3 m or more, and preferably at least one side. A large-area cell having a size of 5 cm or more can be manufactured. Usually, the upper limit of the length of one side is about 100 cm.
本発明の色素増感型太陽電池の一例を図１に示す。
図１に示す色素増感型太陽電池は、光電極（透明電極）１０、電解質層２０、対向電極３０がこの順に並んでなる構造を有する。また、矢印は電子の動きを示す。
An example of the dye-sensitized solar cell of the present invention is shown in FIG.
The dye-sensitized solar cell shown in FIG. 1 has a structure in which a photoelectrode (transparent electrode) 10, an
光電極１０は、光電極基板１０ａと、その上に形成された多孔質半導体微粒子層１０ｂと、この多孔質半導体微粒子層の表面に増感色素が吸着されて形成された増感色素層１０ｃとからなる。
The
光電極基板１０ａは、多孔質半導体微粒子層１０ｂ等を担持する役割と、集電体としての役割を担うものである。
光電極基板１０ａとしては、公知の透明樹脂やガラスのシートの上に、ＩＴＯ、ＦＴＯ及びＩＺＯ等の複合金属酸化物からなる導電膜を積層してなるものが挙げられる。
The
Examples of the
多孔質半導体微粒子層１０ｂは、半導体微粒子を含有する多孔質状の層である。多孔質状の層であることで、増感色素の吸着量が増え、変換効率が高い色素増感型太陽電池が得られやすくなる。
半導体微粒子としては、酸化チタン、酸化亜鉛、酸化スズ等の金属酸化物の粒子が挙げられる。
半導体微粒子の粒子径（一次粒子の平均粒子径）は、好ましくは２〜８０ｎｍ、より好ましくは２〜６０ｎｍである。粒子径が小さいことで、抵抗を低下させることができる。
多孔質半導体微粒子層の厚みは、特に限定されないが、通常、０．１〜５０μｍ、好ましくは５〜３０μｍである。
多孔質半導体微粒子層は、プレス法、水熱分解法、泳動電着法、バインダーフリーコーティング法等の公知の方法により形成することができる。
The porous semiconductor
Examples of the semiconductor fine particles include metal oxide particles such as titanium oxide, zinc oxide, and tin oxide.
The particle diameter of semiconductor fine particles (average particle diameter of primary particles) is preferably 2 to 80 nm, more preferably 2 to 60 nm. Resistance can be reduced because the particle size is small.
Although the thickness of a porous semiconductor fine particle layer is not specifically limited, Usually, 0.1-50 micrometers, Preferably it is 5-30 micrometers.
The porous semiconductor fine particle layer can be formed by a known method such as a press method, a hydrothermal decomposition method, an electrophoretic electrodeposition method, or a binder-free coating method.
増感色素層１０ｃは、光によって励起されて多孔質半導体微粒子層１０ｂに電子を渡し得る化合物（増感色素）が、多孔質半導体微粒子層１０ｂの表面に吸着されてなる層である。
増感色素としては、シアニン色素、メロシアニン色素、オキソノール色素、キサンテン色素、スクワリリウム色素、ポリメチン色素、クマリン色素、リボフラビン色素、ペリレン色素等の有機色素；鉄、銅、ルテニウム等の金属のフタロシアニン錯体やポルフィリン錯体等の金属錯体色素；等が挙げられる。
増感色素層１０ｃは、例えば、増感色素の溶液中に多孔質半導体微粒子層１０ｂを浸漬する方法や、増感色素の溶液を多孔質半導体微粒子層１０ｂ上に塗布する方法等の公知の方法により形成することができる。
The sensitizing
Sensitizing dyes include organic dyes such as cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarin dyes, riboflavin dyes, perylene dyes; phthalocyanine complexes of metals such as iron, copper, ruthenium, and porphyrins. Metal complex dyes such as complexes; and the like.
The sensitizing
光電極は、図１に示すものに限定されず、光を受けることで、外部の回路４０に電子を放出し得る電極であればよく、色素増感型太陽電池の光電極として公知のものを用いることができる。
The photoelectrode is not limited to the one shown in FIG. 1, and any electrode that can emit electrons to the
電解質層２０は、光電極１０と対向電極３０とを分離するとともに、電荷移動を効率よく行わせるための層である。
電解質層２０は、通常、支持電解質、酸化還元対（酸化還元反応において可逆的に酸化体及び還元体の形で相互に変換しうる一対の化学種）、溶媒等を含有する。
The
The
支持電解質としては、リチウムイオン、イミダゾリウムイオン、４級アンモニウムイオン等の陽イオンを含む塩が挙げられる。 Examples of the supporting electrolyte include salts containing cations such as lithium ions, imidazolium ions, and quaternary ammonium ions.
酸化還元対としては、酸化された増感色素を還元し得るものであれば、公知のものを用いることができる。酸化還元対としては、塩素化合物−塩素、ヨウ素化合物−ヨウ素、臭素化合物−臭素、タリウムイオン（ＩＩＩ）−タリウムイオン（Ｉ）、ルテニウムイオン（ＩＩＩ）−ルテニウムイオン（ＩＩ）、銅イオン（ＩＩ）−銅イオン（Ｉ）、鉄イオン（ＩＩＩ）−鉄イオン（ＩＩ）、コバルトイオン（ＩＩＩ）−コバルトイオン（ＩＩ）、バナジウムイオン（ＩＩＩ）−バナジウムイオン（ＩＩ）、マンガン酸イオン−過マンガン酸イオン、フェリシアン化物−フェロシアン化物、キノン−ヒドロキノン、フマル酸−コハク酸等が挙げられる。 As the redox pair, any known one can be used as long as it can reduce the oxidized sensitizing dye. As redox pairs, chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, thallium ion (III) -thallium ion (I), ruthenium ion (III) -ruthenium ion (II), copper ion (II) -Copper ion (I), Iron ion (III)-Iron ion (II), Cobalt ion (III)-Cobalt ion (II), Vanadium ion (III)-Vanadium ion (II), Manganate ion-Permanganate And ions, ferricyanide-ferrocyanide, quinone-hydroquinone, fumaric acid-succinic acid, and the like.
溶媒としては、太陽電池の電解質層の形成用溶媒として公知のものを用いることができる。溶媒としては、アセトニトリル、メトキシアセトニトリル、メトキシプロピオニトリル、Ｎ，Ｎ−ジメチルホルムアミド、エチルメチルイミダゾリウムビストリフルオロメチルスルホニルイミド、炭酸プロピレン等が挙げられる。 As a solvent, a well-known thing can be used as a solvent for forming the electrolyte layer of a solar cell. Examples of the solvent include acetonitrile, methoxyacetonitrile, methoxypropionitrile, N, N-dimethylformamide, ethylmethylimidazolium bistrifluoromethylsulfonylimide, propylene carbonate, and the like.
電解質層２０は、その構成成分を含有する溶液（電解液）を光電極１０上に塗布したり、光電極１０と対向電極３０を有するセルを作製し、その隙間に電解液を注入することで形成することができる。
The
対向電極３０は、本発明の対向電極であり、支持体３０ｃを介在させて積層された、導電層１３０ａと導電層２ ３０ｂとを互いに電気的に接続する貫通配線３０ｄとからなる。導電層２３０ｂは、前記ＣＮＴ（Ａ）を構成材料とし、この例では、金属成分を含まない。
The
図１に示す色素増感型太陽電池においては、次のようなリサイクルが繰り返されることで、光エネルギーが電気エネルギーに変換される。すなわち、（ｉ）増感色素１０ｃが光を受けて励起されると、増感色素１０ｃの電子が取り出される。（ｉｉ）この電子は、光電極１０から出て、外部の回路４０を通って対向電極３０に移動し、さらにその導電層２３０ｂ（触媒層）を介して、電解質層２０に移動する。（ｉｉｉ）電解質層２０に含まれる酸化還元対（還元剤）により、酸化状態の増感色素が還元され、増感色素１０ｃが再生され、再び光を吸収できる状態に戻る。
In the dye-sensitized solar cell shown in FIG. 1, light energy is converted into electric energy by repeating the following recycling. That is, (i) when the sensitizing
本発明の色素増感型太陽電池は、図１に示すものに限定されず、光電極、電解質層及び対向電極の他に、保護層、反射防止層、ガスバリア層等の機能層を有していてもよい。
また、本発明の色素増感型太陽電池は、前記の通りの本発明の対向電極を備えたものであり、通常、その電解質層は液状であるが、これに限定されず、支持体上に、透明導電層、半導体層、固体電解質層及び対向電極を順に重ねてなる、電解質を固体化した、モノリシック型の色素増感太陽電池であってもよい。固体電解質としては、例えば、ヨウ化銅やチオシアン化銅といった一価銅化合物などのｐ型半導体が挙げられる。
本発明の色素増感型太陽電池は、太陽を光源とするものに限定されず、例えば屋内照明を光源とするものであってもよい。
The dye-sensitized solar cell of the present invention is not limited to that shown in FIG. 1, and has functional layers such as a protective layer, an antireflection layer, and a gas barrier layer in addition to the photoelectrode, the electrolyte layer, and the counter electrode. May be.
Further, the dye-sensitized solar cell of the present invention is provided with the counter electrode of the present invention as described above, and the electrolyte layer is usually in a liquid state, but is not limited thereto, and is on the support. Further, it may be a monolithic dye-sensitized solar cell in which a transparent conductive layer, a semiconductor layer, a solid electrolyte layer, and a counter electrode are sequentially stacked and the electrolyte is solidified. Examples of the solid electrolyte include p-type semiconductors such as monovalent copper compounds such as copper iodide and copper thiocyanide.
The dye-sensitized solar cell of the present invention is not limited to one using the sun as a light source, and may be one using indoor lighting as a light source, for example.
本発明の色素増感型太陽電池は、対向電極として本発明の対向電極を備えるものである。このため、耐久性に優れ、光電変換効率が高く、さらに量産性に優れるものである。
上記特性が特に活かされることから、本発明の色素増感型太陽電池は、携帯型太陽電池や屋内用太陽電池として好ましく用いられる。
The dye-sensitized solar cell of the present invention includes the counter electrode of the present invention as a counter electrode. For this reason, it is excellent in durability, has high photoelectric conversion efficiency, and is excellent in mass productivity.
Since the above characteristics are particularly utilized, the dye-sensitized solar cell of the present invention is preferably used as a portable solar cell or an indoor solar cell.
〔太陽電池モジュール〕
本発明の太陽電池モジュールは、本発明の色素増感型太陽電池が直列及び／又は並列に接続されてなるものである。
本発明の太陽電池モジュールは、例えば、本発明の色素増感型太陽電池を平面状または曲面状に配列し、各電池間に非導電性の隔壁を設けるとともに、各電池の光電極や対向電極を導電性の部材を用いて電気的に接続することで得ることができる。
かかる太陽電池モジュールの構造としては、高電圧化を図る観点からは、セル構造体単位を直列に多数並べる直列接続型が好適である。かかる構造としては、公知のＷ型やＺ型が挙げられる。また、前記モノシリック型の太陽電池を直列に接続してなるモジュールであってもよい。
用いる色素増感型太陽電池の数は特に限定されず、目的の電圧に応じて適宜決定することができる。
[Solar cell module]
The solar cell module of the present invention is obtained by connecting the dye-sensitized solar cells of the present invention in series and / or in parallel.
The solar cell module of the present invention includes, for example, the dye-sensitized solar cells of the present invention arranged in a planar shape or a curved surface, and provided with non-conductive partition walls between the cells, as well as the photoelectrode and counter electrode of each cell. Can be obtained by electrical connection using a conductive member.
As a structure of such a solar cell module, a series connection type in which a large number of cell structure units are arranged in series is preferable from the viewpoint of increasing the voltage. Examples of such a structure include a known W type and Z type. Moreover, the module formed by connecting the monolithic solar cells in series may be used.
The number of dye-sensitized solar cells to be used is not particularly limited and can be appropriately determined according to the target voltage.
〔製造例１〕光電極の製造
インジウム−スズ酸化物（ＩＴＯ）をスパッタ処理したポリエチレンナフタレートフィルム（ＩＴＯ−ＰＥＮフィルム、フィルム厚み２００μｍ、ＩＴＯ厚み２００ｎｍ、シート抵抗１５Ω／□）のＩＴＯ面上に、バインダーフリーの酸化チタンペースト（ＰＥＣＣ−Ｃ０１−０６、ペクセル・テクノロジーズ社製）を、ベーカー式アプリケーターを用いて、塗布厚み１５０μｍとなるように塗布した。得られた塗膜を常温で１０分間乾燥させた後、１５０℃の恒温層中でさらに５分間加熱乾燥して、ＩＴＯ−ＰＥＮフィルムと多孔質半導体微粒子層とからなる積層体を得た。
この積層体を５ｃｍ四方の大きさに切り取り、さらに積層体の２ｍｍ内側より、多孔質半導体微粒子層を形成した。これを増感色素溶液〔増感色素：ルテニウム錯体（Ｎ７１９、ソラロニクス社製）、溶媒：アセトニトリル、ｔｅｒｔ−ブタノール、濃度：０．４ｍＭ〕に、４０℃で２時間浸漬させることで、増感色素を多孔質半導体微粒子層に吸着させた。浸漬処理の後、積層体をアセトニトリルで洗浄し、乾燥させることで光電極を得た。
[Production Example 1] Production of photoelectrode On the ITO surface of a polyethylene naphthalate film (ITO-PEN film, film thickness 200 μm, ITO thickness 200 nm, sheet resistance 15 Ω / □) sputtered with indium-tin oxide (ITO) Then, a binder-free titanium oxide paste (PECC-C01-06, manufactured by Pexel Technologies) was applied using a Baker type applicator so as to have a coating thickness of 150 μm. The obtained coating film was dried at room temperature for 10 minutes, and then further heated and dried in a constant temperature layer at 150 ° C. for 5 minutes to obtain a laminate composed of an ITO-PEN film and a porous semiconductor fine particle layer.
This laminate was cut to a size of 5 cm square, and a porous semiconductor fine particle layer was formed from 2 mm inside the laminate. The sensitizing dye is immersed in a sensitizing dye solution [sensitizing dye: ruthenium complex (N719, manufactured by Solaronics), solvent: acetonitrile, tert-butanol, concentration: 0.4 mM] at 40 ° C. for 2 hours. Was adsorbed on the porous semiconductor fine particle layer. After the immersion treatment, the laminate was washed with acetonitrile and dried to obtain a photoelectrode.
〔製造例２〕電解液の調製
ヨウ素０．０５ｍｏｌ／Ｌ、ヨウ化リチウム０．１ｍｏｌ／Ｌ、ｔ−ブチルピリジン０．５ｍｏｌ／Ｌ、および１，２−ジメチル−３−プロピルイミダゾリウムヨージド０．６ｍｏｌ／Ｌとなるように、これらをメトキシアセトニトリルに溶解して、電解液を得た。
[Production Example 2] Preparation of electrolyte solution Iodine 0.05 mol / L, lithium iodide 0.1 mol / L, t-butylpyridine 0.5 mol / L, and 1,2-dimethyl-3-propylimidazolium iodide 0 These were dissolved in methoxyacetonitrile so as to be 6 mol / L to obtain an electrolytic solution.
〔実施例１〕
容量５０ｍＬのガラス容器に、後述のＣＮＴ（１）を０．００５ｇと、分散剤としてのカルボキシメチルセルロースナトリウム塩（ＣＭＣ）を０．００５ｇと、を量りとり、純水１０ｇを加えた後、硝酸を用いてｐＨを４に調整した。これをバス型超音波洗浄機（ＢＲＡＮＳＯＮ社製、５５１０Ｊ−ＭＴ（４２ｋＨｚ、１８０Ｗ）を用いて、２時間分散処理を行い、水分散液を得た。
なお、前記ＣＮＴ（１）は、ＷＯ２００６／０１１６５５号パンフレットの記載に従い、基材表面への触媒層の形成をウェットプロセスにより行い、アセチレンを主成分とする原料ガスを用いて、スーパーグロース法により調製した。当該ＣＮＴは、主に単層ＣＮＴから構成され、窒素ガス吸着によるＢＥＴ比表面積が８０４ｍ２／ｇ、水蒸気吸着によるＢＥＴ比表面積が２．４ｍ２／ｇ、それらの比表面積の比が０．００３、ＣＯ脱離量が７９７μｍｏｌ／ｇ、ＣＯ２脱離量が２９２μｍｏｌ／ｇ、マイクロ孔容積が０．４４ｍＬ／ｇであった。また、平均直径（Ａｖ）が３．３ｎｍ、直径分布（３σ）が１．９ｎｍ、（３σ／Ａｖ）が０．５８であり、平均長さが５００μｍであった。
[Example 1]
In a glass container having a capacity of 50 mL, 0.005 g of CNT (1) described later and 0.005 g of carboxymethylcellulose sodium salt (CMC) as a dispersant were weighed, and after adding 10 g of pure water, nitric acid was added. Was used to adjust the pH to 4. This was subjected to a dispersion treatment for 2 hours using a bath type ultrasonic cleaner (manufactured by BRANSON, 5510J-MT (42 kHz, 180 W) to obtain an aqueous dispersion.
The CNT (1) is prepared by a super-growth method using a raw material gas mainly composed of acetylene by forming a catalyst layer on the surface of the substrate by a wet process according to the description in the pamphlet of WO 2006/011655. did. The CNT is mainly composed of single-walled CNT, has a BET specific surface area of 804 m 2 / g by nitrogen gas adsorption, a BET specific surface area of 2.4 m 2 / g by water vapor adsorption, and a ratio of these specific surface areas is 0.003. The CO desorption amount was 797 μmol / g, the CO 2 desorption amount was 292 μmol / g, and the micropore volume was 0.44 mL / g. The average diameter (Av) was 3.3 nm, the diameter distribution (3σ) was 1.9 nm, (3σ / Av) was 0.58, and the average length was 500 μm.
（ａ）対向電極
無電解銅めっき処理したシクロオレフィン樹脂製基材（基材厚さ２００μｍ、銅箔厚さ２００ｎｍ、サイズ５ｃｍ四方）にドリルで孔（孔径５０μｍ）を格子状に１００個あけ、上記ＣＮＴ（１）の水分散液を当該孔に注入し、８０℃で５分間乾燥させて水を除去する操作を繰り返すことにより、貫通配線を形成した。次いで、前記基材の、銅箔が形成された面とは反対の面上に、前記水分散液を、バーコーター（テスター産業社製、ＳＡ−２０３、Ｎｏ．１０）を用いて、塗布厚さ２２．９μｍとなるように塗布した。得られた塗膜を上記と同様の条件で乾燥させた後、該塗膜が形成された面を水に１０分間浸し分散剤を除去して再度同様に乾燥させることで対向電極を得た。
(A) Counter electrode 100 holes (hole diameter 50 μm) were drilled in a lattice shape by drilling a cycloolefin resin base material (base material thickness 200 μm, copper foil thickness 200 nm, size 5 cm square) treated with electroless copper plating, By penetrating the water dispersion of the CNT (1) into the hole and drying it at 80 ° C. for 5 minutes to remove water, through wiring was formed. Next, on the surface of the substrate opposite to the surface on which the copper foil is formed, the aqueous dispersion is applied using a bar coater (SA-203, No. 10 manufactured by Tester Sangyo Co., Ltd.). It was applied so as to have a thickness of 22.9 μm. The obtained coating film was dried under the same conditions as described above, and then the surface on which the coating film was formed was immersed in water for 10 minutes to remove the dispersant and dried again in the same manner to obtain a counter electrode.
（ｂ）色素増感型太陽電池
サーリンフィルム（厚さ２５μｍ、デュポン社製）を５ｃｍ四方に切り取り、スペーサーフィルムを作製した。前記対向電極と製造例１で得た光電極基板とを、このスペーサーフィルムをはさんで導電面が内側になるように対向させて貼り合せ、１１０℃に加熱したホットプレートの上で１分間熱圧着させた。
放冷後、対向電極に穴をあけ、この穴から製造例２で得た電解液を注液した。電解液を注液後、サーリンフィルム（厚み２５μｍ、デュポン社製）を用いて、電解液の注入に用いた穴を封じることで色素増感型太陽電池を得た。
(B) Dye-sensitized solar cell A Surlyn film (thickness 25 μm, manufactured by DuPont) was cut into 5 cm squares to produce a spacer film. The counter electrode and the photoelectrode substrate obtained in Production Example 1 were bonded together with the spacer film sandwiched between them so that the conductive surface was on the inside, and heated for 1 minute on a hot plate heated to 110 ° C. Crimped.
After allowing to cool, a hole was made in the counter electrode, and the electrolytic solution obtained in Production Example 2 was injected from this hole. After injecting the electrolytic solution, a dye-sensitized solar cell was obtained by sealing the hole used for injecting the electrolytic solution using a Surlyn film (thickness 25 μm, manufactured by DuPont).
１０・・・光電極(透明電極)
１０ａ・・・光電極基板
１０ｂ・・・多孔質半導体微粒子層
１０ｃ・・・増感色素層
１０ｄ・・・支持体
１０ｅ・・・導電膜
２０・・・電解質層
３０・・・対向電極
３０ａ・・・導電層１
３０ｂ・・・導電層２
３０ｃ・・・支持体
３０ｄ・・・貫通配線
４０・・・外部の回路
10 ... Photo electrode (transparent electrode)
10a ...
30b ... conductive layer 2
30c ...
Claims (7)
（ｉ）前記貫通配線がカーボンナノチューブを含んでなるか、及び／又は
（ｉｉ）前記導電層２がカーボンナノチューブを含んでなり、
前記導電層１がパターン化された金属薄膜からなる、
太陽電池用電極基板。 A support, a conductive layer 1 formed of a metal thin film formed on one surface of the support, and a conductive layer 2 formed of a conductive film other than the metal thin film formed on the other surface of the support; A through-wiring line disposed so as to penetrate the support and electrically connecting the conductive layer 1 and the conductive layer 2 to each other,
(I) the or through wiring comprises a carbon nanotube, and / or (ii) the conductive layer 2 is Ri name contains carbon nanotubes,
The conductive layer 1 is made of a patterned metal thin film,
Solar cell electrode substrate.
A solar cell module in which the dye-sensitized solar cells according to claim 6 are connected in series and / or in parallel.
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