JP2001035551A - Pigment-sensitized type solar cell - Google Patents
Pigment-sensitized type solar cellInfo
- Publication number
- JP2001035551A JP2001035551A JP11206299A JP20629999A JP2001035551A JP 2001035551 A JP2001035551 A JP 2001035551A JP 11206299 A JP11206299 A JP 11206299A JP 20629999 A JP20629999 A JP 20629999A JP 2001035551 A JP2001035551 A JP 2001035551A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- solar cell
- fine particles
- sensitized solar
- platinum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は色素増感型太陽電池
に関し、特に白金、白金合金、パラジウム、または、パ
ラジウム合金の金属微粒子のプラズモン増強効果を利用
した色素増感型太陽電池に関する。The present invention relates to a dye-sensitized solar cell, and more particularly to a dye-sensitized solar cell utilizing the plasmon enhancing effect of fine particles of platinum, platinum alloy, palladium, or palladium alloy.
【０００２】[0002]
【従来の技術】可視光領域の利用が可能で理論変換効率
が高く、人体に無害とされる酸化チタンを用いる新しい
太陽電池として、色素増感型太陽電池が知られている
（特開平１−２２０３８０号公報、特開平５−５０４０
２３号公報等）。2. Description of the Related Art A dye-sensitized solar cell is known as a new solar cell using titanium oxide which can be used in the visible light region, has a high theoretical conversion efficiency, and is harmless to the human body. 220380, JP-A-5-5040
No. 23).
【０００３】図４はこの色素増感型太陽電池の構成を示
す概念図である。例えば板ガラスなどの２枚の透明基板
１の各内側に、それぞれ透明導電膜２を形成して電極と
する。透明導電膜２には、例えば、フッ素ドープ酸化
錫、酸化インジウム、ＩＴＯ、ＡＴＯなどが用いられ
る。FIG. 4 is a conceptual diagram showing the structure of this dye-sensitized solar cell. For example, a transparent conductive film 2 is formed inside each of two transparent substrates 1 such as a sheet glass to form electrodes. For the transparent conductive film 2, for example, fluorine-doped tin oxide, indium oxide, ITO, ATO, or the like is used.
【０００４】一方の基板表面に触媒となる白金若しくは
炭素をコーティングして（図示せず）カソード電極とす
る。他方の基板には、例えば酸化チタンなどの金属酸化
物膜４を形成して、その表面に色素６を吸着、担持して
アノード電極とする。この金属酸化物膜４は、表面積を
大きくするために、例えば焼結した多孔質５で形成され
る。これら電極間には、電解液や固体伝導体からなる酸
化還元電解質３を挟み込むことで、酸化還元電解質中の
酸化還元対が、両電極間の電子の移動に寄与する。A surface of one substrate is coated with platinum or carbon as a catalyst (not shown) to form a cathode electrode. On the other substrate, for example, a metal oxide film 4 such as titanium oxide is formed, and the dye 6 is adsorbed and carried on the surface to form an anode electrode. This metal oxide film 4 is formed of, for example, sintered porous material 5 in order to increase the surface area. By interposing an oxidation-reduction electrolyte 3 made of an electrolytic solution or a solid conductor between these electrodes, the oxidation-reduction pair in the oxidation-reduction electrolyte contributes to the transfer of electrons between the two electrodes.
【０００５】酸化チタンなどは短波長の光しか吸収しな
いので、太陽光を効率よく電気エネルギーに変換するた
めの増感材として色素が用いられる。この色素は光吸収
剤として働き、太陽光を吸収して電子を金属酸化物膜に
注入して発電が行われる。例えば色素のルテニウム錯体
は、太陽光の可視領域の光を吸収し、ルテニウム金属・
配位子軌道遷移により励起された電子が金属酸化物の伝
導帯に移り、光電流となる。このようにして、光を吸収
すると両電極間に電圧が発生する太陽電池が構成され
る。[0005] Since titanium oxide or the like absorbs only short-wavelength light, a dye is used as a sensitizer for efficiently converting sunlight into electric energy. The dye functions as a light absorber, absorbs sunlight, injects electrons into the metal oxide film, and generates power. For example, ruthenium complexes of dyes absorb light in the visible region of sunlight,
The electrons excited by the ligand orbital transition move to the conduction band of the metal oxide and become a photocurrent. In this way, a solar cell is generated in which a voltage is generated between both electrodes when light is absorbed.
【０００６】この型の太陽電池はこのように色素を増感
剤として用いることから、「色素増感型太陽電池」とも
呼ばれる。[0006] Since this type of solar cell uses a dye as a sensitizer, it is also called a "dye-sensitized solar cell".
【０００７】既に量産されているシリコン太陽電池で
は、シリコンのｐｎ接合によってバンドの勾配が形成さ
れ、光照射によって生成した電子と正孔とが内部電界に
よって分離され、起電力が発生する。これに対して、酸
化チタンなどの金属酸化物膜４を利用した太陽電池で
は、太陽光で励起された色素６の電子のみが酸化チタン
微粒子に注入され、電子と正孔の再結合による損失がほ
とんどない。そして、電子注入により酸化された色素６
は、酸化還元電解質３中に存在するドナーによって速や
かに還元され、初期状態へ戻る。従って、シリコン太陽
電池では光エネルギーの吸収と電子の伝達が同じシリコ
ン半導体の中で行われているのと異なり、酸化チタンを
用いた太陽電池では、光エネルギーの吸収と電子の伝達
が別々のところで行われている。これは植物がクロロフ
ィルで光エネルギーを吸収し、細胞膜中のメディエータ
ーで電子を伝達しているのとよく似た構造である。In a silicon solar cell that has already been mass-produced, a band gradient is formed by a pn junction of silicon, and electrons and holes generated by light irradiation are separated by an internal electric field, thereby generating an electromotive force. On the other hand, in a solar cell using a metal oxide film 4 such as titanium oxide, only electrons of the dye 6 excited by sunlight are injected into the titanium oxide fine particles, and loss due to recombination of electrons and holes is reduced. rare. The dye 6 oxidized by the electron injection
Is quickly reduced by the donor present in the redox electrolyte 3 and returns to the initial state. Therefore, unlike silicon solar cells, where absorption of light energy and transmission of electrons are performed in the same silicon semiconductor, absorption of light energy and transmission of electrons are different in a solar cell using titanium oxide. Is being done. This is similar to the way plants absorb light energy with chlorophyll and transmit electrons with mediators in cell membranes.
【０００８】グレッツェルらは、ナノスケールの酸化チ
タン微粒子を焼結した多孔質の酸化チタン膜を用いるこ
とにより表面積を投影面積の約１０００倍とし、色素
に、酸化チタンなどの薄膜と相性が良く、太陽光を効率
よく吸収する、ルテニウム錯体（ＲｕＬ2（ＮＣＳ）2，
Ｌ＝４，４’−ジカルボキシ−２，２’ビピリジン）
（以下、「Ｒｕ色素」という）を用い、酸化還元電解質
に、アセトニトリル（９０ｖｏｌ％）と、３メチル２オ
キサゾリジノン（１０ｖｏｌ％）の混合溶媒にヨウ素と
ヨウ化リチウムを加えた電解液を用いてＩ-／Ｉ3 -を酸
化還元対としたときに、ＡＭ１．５（エアマス１．５：
地球の中緯度における太陽スペクトルの太陽光）に対し
て１０％の変換効率が得られることを報告している（M.
K.Nazeeruddin et al., J. Am. Chem. Soc. 1993, 115,
6382）。[0008] Grettzel et al. Use a porous titanium oxide film obtained by sintering nanoscale titanium oxide fine particles to make the surface area approximately 1000 times the projected area, and the dye is compatible with a thin film such as titanium oxide. Ruthenium complex (RuL 2 (NCS) 2 , which efficiently absorbs sunlight
L = 4,4'-dicarboxy-2,2'bipyridine)
(Hereinafter referred to as "Ru dye"), and using an electrolyte obtained by adding iodine and lithium iodide to a mixed solvent of acetonitrile (90 vol%) and 3-methyldioxazolidinone (10 vol%) as a redox electrolyte. - / I 3 - when redox pairs, AM 1.5 (air mass 1.5:
It has been reported that a conversion efficiency of 10% can be obtained for the Earth's mid-latitude solar spectrum (sunlight in the solar spectrum) (M.
K. Nazeeruddin et al., J. Am. Chem. Soc. 1993, 115,
6382).
【０００９】[0009]
【発明が解決しようとする課題】この色素増感型太陽電
池は構成元素が安価で安全性が高く、実用化が期待され
ている。しかし、既に広く用いられているシリコン太陽
電池の光電変換効率は２０％を超えるものもある。その
ため、色素増感型太陽電池は更なる光電変換効率の向上
が望まれている。The dye-sensitized solar cell is inexpensive, has high safety, and is expected to be put to practical use. However, some silicon solar cells already widely used have a photoelectric conversion efficiency exceeding 20%. Therefore, it is desired that the dye-sensitized solar cell be further improved in photoelectric conversion efficiency.
【００１０】そこで本発明は、色素増感型太陽電池の光
電変換効率を従来より一層向上させることを目的とす
る。Accordingly, an object of the present invention is to further improve the photoelectric conversion efficiency of a dye-sensitized solar cell as compared with the conventional one.
【００１１】[0011]
【課題を解決するための手段】色素増感型太陽電池にお
いて、金、銀、または銅の金属微粒子を用いれば、表面
プラズモンによる増強効果が得られることが知られてい
る（特開平９−２５９９４３号公報）。しかし、ハロゲ
ン系の酸化還元電解質が、これら金属微粒子と反応して
溶解してしまう。例え金であっても、微粒子、薄膜の状
態では室温で容易に溶解されでしまう。そこで本発明者
は、白金、白金合金、パラジウム、パラジウム合金に注
目し、研究を進めた。It is known that in a dye-sensitized solar cell, the use of gold, silver, or copper metal fine particles can enhance the effect of surface plasmon (Japanese Patent Application Laid-Open No. 9-259943). No.). However, the halogen-based redox electrolyte reacts and dissolves with these metal fine particles. Even if it is gold, it is easily dissolved at room temperature in the state of fine particles and thin film. Therefore, the present inventor paid attention to platinum, a platinum alloy, palladium, and a palladium alloy, and proceeded with research.
【００１２】図２は、ＰｔＡｇ系合金微粒子によるＲｕ
色素の吸光度の増強効果を示す。図２中、横軸の波長
（単位：ｎｍ）に対して縦軸は吸光度（無次元数）を示
し、「△」は、ガラス基板にＲｕ色素のみを担持した場
合、「○」は、ガラス基板にＰｔＡｇ系合金微粒子溶液
を、塗布、乾燥してＰｔＡｇ系合金微粒子膜を形成し、
Ｒｕ色素を担持した場合である。Ｒｕ色素のみの吸光度
に比べ、ＰｔＡｇ系微粒子膜上のＲｕ色素の吸光度が、
可視光から近赤外領域にかけて増強されていることが分
かる。FIG. 2 shows Ru by PtAg-based alloy fine particles.
5 shows the effect of enhancing the absorbance of the dye. In FIG. 2, the vertical axis indicates absorbance (dimensionless number) with respect to the wavelength (unit: nm) on the horizontal axis, “△” indicates that the glass substrate carries only the Ru dye, and “「 ”indicates glass. A PtAg-based alloy fine particle solution is applied to the substrate and dried to form a PtAg-based alloy fine particle film,
This is the case where a Ru dye is supported. Compared to the absorbance of the Ru dye alone, the absorbance of the Ru dye on the PtAg-based fine particle membrane is:
It can be seen that the intensity is enhanced from the visible light to the near infrared region.
【００１３】図３は、図２のＰｔＡｇ系合金微粒子をＰ
ｔ微粒子に変えた以外は図２と同様の図である。ここに
おいてもＰｔＡｇ系合金微粒子同様の吸光度の増強がみ
られる。同様のことが、白金、白金合金の他、パラジウ
ム、パラジウム合金でも確認された。FIG. 3 shows the PtAg-based alloy fine particles of FIG.
FIG. 4 is a view similar to FIG. 2 except that t fine particles are used. Also in this case, an increase in absorbance similar to that of the PtAg-based alloy fine particles is observed. The same was confirmed for palladium and palladium alloys in addition to platinum and platinum alloys.
【００１４】これら金属微粒子は、太陽光の照射により
表面プラズモン吸収による光エネルギーの吸収が起こ
り、色素との共鳴や色素への電荷移動により、可視光か
ら近赤外領域において色素の吸光度の増強効果がある。
この色素の光吸収の増強効果により光電流の増加が引き
起こされ、光電変換効率を向上させることができる。These metal fine particles absorb light energy due to surface plasmon absorption when irradiated with sunlight, and the effect of enhancing the absorbance of the dye from visible light to the near infrared region by resonance with the dye and charge transfer to the dye. There is.
An increase in photocurrent is caused by the effect of enhancing the light absorption of the dye, and the photoelectric conversion efficiency can be improved.
【００１５】更に、これらは微粒子状態でもハロゲン系
の酸化還元電解質によって溶解されないことが確認され
た。Further, it was confirmed that they were not dissolved by the halogen-based redox electrolyte even in a fine particle state.
【００１６】本発明者は、これらの事実より、本発明を
完成するに至った。すなわち、上記課題を解決するため
の本発明の色素増感型太陽電池は、一方の透明基板の内
側に透明導電膜を形成し、表面に白金若しくは炭素をコ
ーティングしたカソード電極と、他方の透明基板の内側
に透明導電膜及び金属酸化物膜を順次形成し、この金属
酸化物膜の表面に色素を担持したアノード電極とを、酸
化還元電解質を介して対向させ、光の吸収によりこれら
電極間に電圧が発生するようにした色素増感型太陽電池
であって、前記色素の近傍に金属微粒子を配したことを
特徴とする。The present inventors have completed the present invention based on these facts. In other words, the dye-sensitized solar cell of the present invention for solving the above-mentioned problem has a transparent conductive film formed inside one transparent substrate, a cathode electrode coated with platinum or carbon on the surface, and the other transparent substrate. A transparent conductive film and a metal oxide film are sequentially formed on the inside of the metal oxide film. An anode electrode supporting a dye is opposed to the surface of the metal oxide film via a redox electrolyte, and light is absorbed between these electrodes. A dye-sensitized solar cell in which a voltage is generated, wherein metal fine particles are arranged near the dye.
【００１７】この金属微粒子には、白金（Ｐｔ）、白金
合金、パラジウム（Ｐｄ）、または、パラジウム合金の
微粒子が適している。As the fine metal particles, fine particles of platinum (Pt), a platinum alloy, palladium (Pd), or a palladium alloy are suitable.
【００１８】前記金属酸化物は、酸化チタン（Ｔｉ
Ｏ2）、酸化亜鉛（ＺｎＯ）、酸化ニオブ（Ｎｂ
2Ｏ5）、酸化錫（ＳｎＯ2）、または、チタン酸ストロ
ンチウム（ＳｒＴｉＯ3）を用いることができる。The metal oxide is titanium oxide (Ti)
O 2 ), zinc oxide (ZnO), niobium oxide (Nb)
2 O 5 ), tin oxide (SnO 2 ), or strontium titanate (SrTiO 3 ) can be used.
【００１９】前記色素には、ルテニウム錯体、または、
キサンテン系色素を用いることができる。The dye may be a ruthenium complex or
Xanthene dyes can be used.
【００２０】前記酸化還元電解質には、ヨウ素、臭素、
または、塩素のハロゲンを含む電解液または固体伝導体
を用いることができる。The redox electrolyte includes iodine, bromine,
Alternatively, an electrolytic solution containing a halogen of chlorine or a solid conductor can be used.
【００２１】[0021]
【発明の実施の形態】本発明の色素増感型太陽電池の構
成を図１を用いて説明する。図１は図４における色素６
及び金属微粒子７を含む金属酸化物膜４をより詳細に示
した概念図である。色素増感型太陽電池は透明導電膜
（例えば、フッ素ドープ酸化錫）のついたガラス基板１
の透明導電膜２に白金をコーティングした（図示せず）
カソード電極と、透明導電膜（例えばフッ素ドープ酸化
錫）２のついたガラス基板１上に多孔質の金属酸化物膜
４を形成し、金属酸化物５の表面に色素６および金属微
粒子７を担持した光電極であるアノード電極と、酸化還
元電解質３とから構成されている。DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of a dye-sensitized solar cell of the present invention will be described with reference to FIG. FIG. 1 shows the dye 6 in FIG.
FIG. 3 is a conceptual diagram showing a metal oxide film 4 including metal fine particles 7 in more detail. The dye-sensitized solar cell is a glass substrate 1 having a transparent conductive film (for example, fluorine-doped tin oxide).
Platinum coated transparent conductive film 2 (not shown)
A porous metal oxide film 4 is formed on a glass substrate 1 provided with a cathode electrode and a transparent conductive film (for example, fluorine-doped tin oxide) 2, and a dye 6 and metal fine particles 7 are carried on the surface of the metal oxide 5. And a redox electrolyte 3.
【００２２】酸化還元電解質３はヨウ素系酸化還元電解
質でありアセトニトリル（９０ｖｏｌ％）と３メチル２
オキサゾリジノン（１０ｖｏｌ％）の混合溶媒にヨウ素
とヨウ化リチウムを加えたものであり、ヨウ素酸化還元
対（Ｉ3 -／Ｉ-）として働き、カソード電極とアノード
電極間の電子移動に寄与している。The oxidation-reduction electrolyte 3 is an iodine-based oxidation-reduction electrolyte, which is composed of acetonitrile (90 vol%) and 3-methyl 2
It is a mixture of oxazolidinone (10 vol%) with iodine and lithium iodide added thereto, and serves as an iodine redox couple (I 3 − / I − ), contributing to electron transfer between a cathode electrode and an anode electrode. .
【００２３】多孔質の金属酸化物膜４は、例えば酸化チ
タンで形成することができる。色素６は例えばルテニウ
ム錯体からなる色素を用いると、太陽光の可視領域の光
を吸収してルテニウム金属・配位子軌道遷移により励起
された電子が酸化チタンの伝導帯に移り光電流となる。The porous metal oxide film 4 can be formed of, for example, titanium oxide. When the dye 6 is a dye composed of, for example, a ruthenium complex, the light excited in the visible region of sunlight is absorbed, and the electrons excited by the transition of the ruthenium metal / ligand orbit move to the conduction band of the titanium oxide to become a photocurrent.
【００２４】金属微粒子７は、例えば白金微粒子、白金
がモル比で５０％以上の白金合金微粒子、パラジウム微
粒子、パラジウムがモル比で５０％以上のパラジウム合
金微粒子を用いると、ヨウ素系酸化還元電解質に溶解消
失せず色素近傍に配することができる。これら微粒子は
色素に化学結合や吸着により直接配してもよく、ＴｉＯ
2に化学結合や吸着した結果としてＴｉＯ2に担持された
色素近傍に配してもよい。As the metal fine particles 7, for example, platinum fine particles, platinum alloy fine particles having a platinum molar ratio of 50% or more, palladium fine particles, or palladium alloy fine particles having a palladium molar ratio of 50% or more can be used as an iodine-based oxidation-reduction electrolyte. It can be placed near the dye without dissolving and disappearing. These fine particles may be directly disposed on the dye by chemical bonding or adsorption.
2 may be arranged in the vicinity of a dye supported on TiO 2 as a result of chemical bonding or adsorption to 2 .
【００２５】色素近傍に配した金属微粒子の粒径は１〜
１００ｎｍが好ましく、１〜１０ｎｍがより好ましい。
配置方法としてはこれら微粒子の分散液に色素を担持し
たＴｉＯ2膜を浸漬する方法がある。微粒子分散液は、
例えば貴金属溶解溶液に還元剤、高分子分散剤を添加し
て作製することができる。また、真空容器内で気化させ
た貴金属の再凝固微粒子を溶媒中に捕獲して作製するこ
ともできる。The particle size of the metal fine particles disposed near the dye is 1 to
100 nm is preferable, and 1 to 10 nm is more preferable.
As an arrangement method, there is a method of immersing a TiO 2 film carrying a dye in a dispersion of these fine particles. The fine particle dispersion is
For example, it can be prepared by adding a reducing agent and a polymer dispersant to a noble metal solution. Further, it can also be produced by capturing the recoagulated fine particles of a noble metal vaporized in a vacuum vessel in a solvent.
【００２６】また、市販の貴金属の溶解溶液に色素を担
持したＴｉＯ2膜を浸漬後、水素還元や光還元により貴
金属微粒子を析出させてもよい。例えば、白金ではＨ2
ＰｔＣｌ6・６Ｈ2Ｏや、〔Ｐｔ（ＮＨ3）4〕（ＮＯ3）2
水溶液に浸漬後、還元してＰｔを色素近傍に析出させて
もよい。Alternatively, after immersing the TiO 2 film carrying the dye in a commercially available solution of a noble metal, fine particles of the noble metal may be precipitated by hydrogen reduction or photoreduction. For example, for platinum, H 2
PtCl 6 · 6H 2 O and, [Pt (NH 3) 4] (NO 3) 2
After immersion in the aqueous solution, Pt may be reduced to precipitate near the dye.
【００２７】これら白金、白金合金、パラジウム、パラ
ジウム合金の各金属微粒子は、太陽光の照射により表面
プラズモン吸収による光エネルギーの吸収が起こり、色
素との共鳴や色素への電荷移動により可視光から近赤外
領域において色素の吸光度の増強効果がある。この色素
の光吸収の増強効果により光電流の増加が引き起こされ
光電変換効率を向上させることができる。Each of these fine particles of platinum, platinum alloy, palladium, and palladium alloy absorbs light energy due to surface plasmon absorption due to irradiation of sunlight, and resonates with the dye and transfers electric charges to the dye to make the near-visible light more visible. There is an effect of enhancing the absorbance of the dye in the infrared region. This effect of enhancing the light absorption of the dye causes an increase in photocurrent, which can improve photoelectric conversion efficiency.
【００２８】[0028]
【実施例】本発明を以下の実施例により説明する。しか
し、本発明はこれに限定されるものではない。The present invention will be described with reference to the following examples. However, the present invention is not limited to this.
【００２９】実施例１ ・・・ 以下の条件で、本発明
の色素増感型太陽電池を構成し、その特性を評価した。
透明導電膜を形成した透明基板には市販のフッ素ドープ
ＳｎＯ2ガラス（日本板硝子製、導電層膜厚４５０ｎ
ｍ）を用いた。金属酸化物膜には、多孔質酸化チタンと
して平均粒径１５ｎｍのＴｉＯ2ペースト（Solaronix社
製）を用いた。Example 1 A dye-sensitized solar cell of the present invention was constructed under the following conditions, and its characteristics were evaluated.
A commercially available fluorine-doped SnO 2 glass (Nippon Sheet Glass, conductive layer thickness 450 n
m) was used. For the metal oxide film, a TiO 2 paste (manufactured by Solaronix) having an average particle size of 15 nm was used as porous titanium oxide.
【００３０】フッ素ドープＳｎＯ2ガラス上にＴｉＯ2ペ
ーストを塗布し、自然乾燥後、５００℃で３０分間電気
炉で焼成を行った。一回の塗布で約２μｍ厚のＴｉＯ2
多孔質膜が形成された。ＴｉＯ2多孔質膜をＲｕ色素溶
液に浸漬し、８０℃で２時間還流を行い、ＴｉＯ2多孔
質表面にＲｕ色素を担持した。Ｒｕ色素溶液はエタノー
ルに３×１０-4ｍｏｌ／Ｌ（Ｌ：リットル）のＲｕ色素
（Solaronix社製Ruthenium535）を溶解させることによ
り作製した。A TiO 2 paste was applied on a fluorine-doped SnO 2 glass, dried naturally, and fired in an electric furnace at 500 ° C. for 30 minutes. TiO 2 about 2 μm thick by one application
A porous film was formed. The TiO 2 porous film was immersed in a Ru dye solution and refluxed at 80 ° C. for 2 hours to carry the Ru dye on the TiO 2 porous surface. The Ru dye solution was prepared by dissolving 3 × 10 −4 mol / L (L: liter) of Ru dye (Ruthenium 535 manufactured by Solaronix) in ethanol.
【００３１】Ｒｕ色素を担持したＴｉＯ2多孔質膜をＰ
ｔＡｇ系微粒子が単分散した溶液に浸漬し、エタノール
で洗浄後自然乾燥させることによりＲｕ色素表面にＰｔ
Ａｇ系微粒子を吸着させた。単分散ＰｔＡｇ系微粒子溶
液は白金と銀のモル比を４：１にし、酸化還元電解質に
溶解するのを防いだ。以上のようにして光電極であるア
ノード電極を形成した。The TiO 2 porous membrane supporting the Ru dye is made of P
By immersing in a solution in which tAg-based fine particles are monodispersed, washing with ethanol, and naturally drying, Pt is added to the Ru dye surface.
Ag-based fine particles were adsorbed. The monodisperse PtAg-based fine particle solution had a molar ratio of platinum to silver of 4: 1 to prevent dissolution in the redox electrolyte. As described above, an anode electrode serving as a photoelectrode was formed.
【００３２】一方、カソード電極はフッ素ドープＳｎＯ
2ガラス表面にスパッタリング法で白金をコーティング
して形成した。カソード電極とアノード電極とを対向さ
せて電池構造を形成し、隙間に酸化還元電解質を注入し
た。酸化還元電解質はヨウ素系電解液であり、アセトニ
トリル（９０ｖｏｌ％）と３メチル２オキサゾリジノン
（１０ｖｏｌ％）の混合溶媒にヨウ素とヨウ化リチウム
を加えたものである。On the other hand, the cathode electrode is made of fluorine-doped SnO.
(2) Platinum was coated on the glass surface by a sputtering method to form a film. A battery structure was formed with the cathode electrode and the anode electrode facing each other, and a redox electrolyte was injected into the gap. The oxidation-reduction electrolyte is an iodine-based electrolyte, which is obtained by adding iodine and lithium iodide to a mixed solvent of acetonitrile (90 vol%) and 3-methyl-2-oxazolidinone (10 vol%).
【００３３】参照用に同一プロセスでＰｔＡｇ系微粒子
を吸着させない従来型の太陽電池も形成した。それら
の、太陽電池に対してＡＭ１．５のソーラーシミュレー
タで１０００Ｗ／ｍ2の疑似太陽光を照射して電流電圧
特性を測定した。その結果、従来型太陽電池の変換効率
が３％であったのに対し、ＰｔＡｇ系微粒子を色素近傍
に配した太陽電池では変換効率が６％と、２倍に向上し
た。For reference, a conventional solar cell which does not adsorb PtAg-based fine particles by the same process was also formed. The solar cells were irradiated with 1000 W / m 2 of pseudo sunlight using a solar simulator of AM 1.5 to measure current-voltage characteristics. As a result, the conversion efficiency of the conventional solar cell was 3%, whereas the conversion efficiency of the solar cell in which the PtAg-based fine particles were arranged in the vicinity of the dye was 6%, which was twice as high.
【００３４】実施例２ ・・・ ＰｔＡｇ系微粒子をＰ
ｔ微粒子とした他は、実施例１と同様にして本発明の色
素増感型太陽電池を構成し、その特性を評価した。Example 2 PtAg based fine particles
Except for using t fine particles, a dye-sensitized solar cell of the present invention was constructed in the same manner as in Example 1, and its characteristics were evaluated.
【００３５】また、参照用に同一プロセスでＰｔ微粒子
を吸着させない従来型の太陽電池も形成した。Further, a conventional solar cell which does not adsorb Pt fine particles by the same process was formed for reference.
【００３６】これら作成した太陽電池に対して、実施例
１と同様に特性を測定した。その結果、従来型太陽電池
の変換効率が３％であったのに対し、Ｐｔ微粒子を色素
近傍に配した太陽電池では変換効率が５％と、約１．７
倍に向上した。The characteristics of these solar cells were measured in the same manner as in Example 1. As a result, the conversion efficiency of the conventional solar cell was 3%, while the conversion efficiency of the solar cell in which Pt fine particles were arranged in the vicinity of the dye was 5%, which is about 1.7.
Improved by a factor of two.
【００３７】実施例３ ・・・ ＰｔＡｇ系微粒子をＰ
ｄ微粒子とした他は、実施例１と同様にして本発明の色
素増感型太陽電池を構成し、その特性を評価した。Example 3 PtAg-based fine particles were converted to P
A dye-sensitized solar cell of the present invention was constructed in the same manner as in Example 1 except that the fine particles were d, and the characteristics were evaluated.
【００３８】また、参照用に同一プロセスでＰｄ微粒子
を吸着させない従来型の太陽電池も形成した。Further, a conventional solar cell in which Pd fine particles were not adsorbed by the same process was formed for reference.
【００３９】これら作成した太陽電池に対して、実施例
１と同様に特性を測定した。その結果、従来型太陽電池
の変換効率が３％であったのに対し、Ｐｄ微粒子を色素
近傍に配した太陽電池では変換効率が４．５％と、１．
５倍に向上した。The characteristics of these solar cells were measured in the same manner as in Example 1. As a result, the conversion efficiency of the conventional solar cell was 3%, while the conversion efficiency of the solar cell in which Pd fine particles were arranged in the vicinity of the dye was 4.5%.
5 times improvement.
【００４０】実施例４ ・・・ ＰｔＡｇ系微粒子をＰ
ｄＡｇ系微粒子とした他は、実施例１と同様にして本発
明の色素増感型太陽電池を構成し、その特性を評価し
た。Example 4 PtAg based fine particles
A dye-sensitized solar cell of the present invention was constructed in the same manner as in Example 1 except that dAg-based fine particles were used, and its characteristics were evaluated.
【００４１】また、参照用に同一プロセスでＰｄＡｇ系
微粒子を吸着させない従来型の太陽電池も形成した。Further, for reference, a conventional solar cell not adsorbing PdAg-based fine particles was formed in the same process.
【００４２】これら作成した太陽電池に対して、実施例
１と同様に特性を測定した。その結果、従来型太陽電池
の変換効率が３％であるのに対し、ＰｄＡｇ系微粒子を
色素近傍に配した太陽電池では、変換効率が４．８％
と、１．６倍に向上した。The characteristics of these solar cells were measured in the same manner as in Example 1. As a result, while the conversion efficiency of the conventional solar cell is 3%, the conversion efficiency of the solar cell in which PdAg-based fine particles are arranged near the dye is 4.8%.
1.6 times higher.
【００４３】[0043]
【発明の効果】本発明の色素増感型太陽電池により、白
金、白金合金、パラジウム、または、パラジウム合金を
金属酸化物表面に担持された色素近傍に配することによ
り、色素の吸光度が増強される。さらに、ヨウ素系酸化
還元電解質を用いることにより大きな光電流が容易に取
り出せるため、光電変換効率を向上させることができ
る。According to the dye-sensitized solar cell of the present invention, by disposing platinum, a platinum alloy, palladium, or a palladium alloy near a dye supported on a metal oxide surface, the absorbance of the dye is enhanced. You. Furthermore, by using an iodine-based redox electrolyte, a large photocurrent can be easily taken out, so that the photoelectric conversion efficiency can be improved.
【図１】本発明にかかる色素増感型太陽電池の構成を示
す概念図である。FIG. 1 is a conceptual diagram showing a configuration of a dye-sensitized solar cell according to the present invention.
【図２】金属微粒子として白金−銀を使った場合の吸光
度の増強を示す、吸光度−波長曲線である。FIG. 2 is an absorbance-wavelength curve showing enhancement of absorbance when platinum-silver is used as metal fine particles.
【図３】金属微粒子として白金を使った場合の吸光度の
増強を示す、吸光度−波長曲線である。FIG. 3 is an absorbance-wavelength curve showing enhancement of absorbance when platinum is used as metal fine particles.
【図４】従来の色素増感型太陽電池の構成を示す概念図
である。FIG. 4 is a conceptual diagram showing a configuration of a conventional dye-sensitized solar cell.
【符号の説明】 １ 透明基板 ２ 透明導電膜 ３ 酸化還元電解質 ４ 金属酸化物膜 ５ 金属酸化物微粒子 ６ 色素 ７ 金属微粒子[Description of Signs] 1 transparent substrate 2 transparent conductive film 3 redox electrolyte 4 metal oxide film 5 metal oxide fine particles 6 dye 7 metal fine particles
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１１年８月３０日（１９９９．８．３
０）[Submission date] August 30, 1999 (1999.8.3)
0)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００４[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００４】一方の基板表面に触媒となる白金若しくは
炭素をコーティングして（図示せず）カソード電極とす
る。他方の基板には、例えば酸化チタンなどの金属酸化
物膜４を形成して、その表面に色素（図示せず）を吸
着、担持してアノード電極とする。この金属酸化物膜４
は、表面積を大きくするために、例えば焼結した多孔質
（図示せず）で形成される。これら電極間には、電解液
や固体伝導体からなる酸化還元電解質３を挟み込むこと
で、酸化還元電解質中の酸化還元対が、両電極間の電子
の移動に寄与する。A surface of one substrate is coated with platinum or carbon as a catalyst (not shown) to form a cathode electrode. A metal oxide film 4 of, for example, titanium oxide is formed on the other substrate, and a dye (not shown) is adsorbed and carried on the surface to form an anode electrode. This metal oxide film 4
To increase the surface area, e.g. sintered porous
(Not shown) . By interposing an oxidation-reduction electrolyte 3 made of an electrolytic solution or a solid conductor between these electrodes, the oxidation-reduction pair in the oxidation-reduction electrolyte contributes to the transfer of electrons between the two electrodes.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００７】既に量産されているシリコン太陽電池で
は、シリコンのｐｎ接合によってバンドの勾配が形成さ
れ、光照射によって生成した電子と正孔とが内部電界に
よって分離され、起電力が発生する。これに対して、酸
化チタンなどの金属酸化物膜４を利用した太陽電池で
は、太陽光で励起された色素（図示せず）の電子のみが
酸化チタン微粒子に注入され、電子と正孔の再結合によ
る損失がほとんどない。そして、電子注入により酸化さ
れた色素（図示せず）は、酸化還元電解質３中に存在す
るドナーによって速やかに還元され、初期状態へ戻る。
従って、シリコン太陽電池では光エネルギーの吸収と電
子の伝達が同じシリコン半導体の中で行われているのと
異なり、酸化チタンを用いた太陽電池では、光エネルギ
ーの吸収と電子の伝達が別々のところで行われている。
これは植物がクロロフィルで光エネルギーを吸収し、細
胞膜中のメディエーターで電子を伝達しているのとよく
似た構造である。In a silicon solar cell that has already been mass-produced, a band gradient is formed by a pn junction of silicon, and electrons and holes generated by light irradiation are separated by an internal electric field, thereby generating an electromotive force. On the other hand, in a solar cell using a metal oxide film 4 such as titanium oxide, only electrons of a dye (not shown) excited by sunlight are injected into the titanium oxide fine particles, and electrons and holes are regenerated. There is almost no coupling loss. The dye (not shown) oxidized by the electron injection is rapidly reduced by the donor present in the redox electrolyte 3 and returns to the initial state.
Therefore, unlike silicon solar cells, where absorption of light energy and transmission of electrons are performed in the same silicon semiconductor, absorption of light energy and transmission of electrons are different in a solar cell using titanium oxide. Is being done.
This is similar to the way plants absorb light energy with chlorophyll and transmit electrons with mediators in cell membranes.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１１】[0011]
【課題を解決するための手段】色素増感型太陽電池にお
いて、金、銀、または銅の金属微粒子を用いれば、表面
プラズモンによる増強効果が得られることが知られてい
る（特開平９−２５９９４３号公報）。しかし、ハロゲ
ン系の酸化還元電解質が、これら金属微粒子と反応して
溶解してしまう。例え金であっても、微粒子、薄膜の状
態では室温で容易に溶解されてしまう。そこで本発明者
は、白金、白金合金、パラジウム、パラジウム合金に注
目し、研究を進めた。It is known that in a dye-sensitized solar cell, the use of gold, silver, or copper metal fine particles can enhance the effect of surface plasmon (Japanese Patent Application Laid-Open No. 9-259943). No.). However, the halogen-based redox electrolyte reacts and dissolves with these metal fine particles. Even at gold particles, thus it is readily dissolved at room temperature in the form of a thin film. Therefore, the present inventor paid attention to platinum, a platinum alloy, palladium, and a palladium alloy, and proceeded with research.
Claims (6)
成し、表面に白金若しくは炭素をコーティングしたカソ
ード電極と、他方の透明基板の内側に透明導電膜及び金
属酸化物膜を順次形成し、この金属酸化物膜の表面に色
素を担持したアノード電極とを、酸化還元電解質を介し
て対向させ、光の吸収によりこれら電極間に電圧が発生
するようにした色素増感型太陽電池であって、前記色素
の近傍に金属微粒子を配したことを特徴とする色素増感
型太陽電池。1. A transparent conductive film is formed inside one transparent substrate, a cathode electrode coated with platinum or carbon on the surface, and a transparent conductive film and a metal oxide film are sequentially formed inside the other transparent substrate. A dye-sensitized solar cell in which a dye-supported anode electrode is opposed to the surface of the metal oxide film via a redox electrolyte, and a voltage is generated between the electrodes by light absorption. A dye-sensitized solar cell, wherein metal fine particles are arranged in the vicinity of the dye.
合金、パラジウム（Ｐｄ）、または、パラジウム合金の
微粒子である請求項１記載の色素増感型太陽電池。2. The dye-sensitized solar cell according to claim 1, wherein the metal fine particles are fine particles of platinum (Pt), a platinum alloy, palladium (Pd), or a palladium alloy.
Ｏ2）、酸化亜鉛（ＺｎＯ）、酸化ニオブ（Ｎｂ
2Ｏ5）、酸化錫（ＳｎＯ2）、または、チタン酸ストロ
ンチウム（ＳｒＴｉＯ3）で形成される請求項１または
請求項２記載の色素増感型太陽電池。3. The method according to claim 1, wherein the metal oxide film is made of titanium oxide (Ti).
O 2 ), zinc oxide (ZnO), niobium oxide (Nb)
3. The dye-sensitized solar cell according to claim 1, wherein the dye-sensitized solar cell is formed of 2 O 5 ), tin oxide (SnO 2 ), or strontium titanate (SrTiO 3 ). 4.
キサンテン系色素である請求項１記載〜請求項３いずれ
かに記載の色素増感型太陽電池。4. The method according to claim 1, wherein the dye is a ruthenium complex or
The dye-sensitized solar cell according to any one of claims 1 to 3, which is a xanthene-based dye.
または、塩素のハロゲンを含む電解液である請求項１〜
請求項４いずれかに記載の色素増感型太陽電池。5. The method according to claim 5, wherein the redox electrolyte is iodine, bromine,
Or an electrolytic solution containing halogen of chlorine.
The dye-sensitized solar cell according to claim 4.
または、塩素のハロゲンを含む固体伝導体である請求項
１〜請求項４いずれかに記載の色素増感型太陽電池。6. The method according to claim 1, wherein the redox electrolyte is iodine, bromine,
5. The dye-sensitized solar cell according to claim 1, which is a solid conductor containing halogen of chlorine. 6.
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|---|---|---|---|
| JP20629999A JP4514251B2 (en) | 1999-07-21 | 1999-07-21 | Dye-sensitized solar cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20629999A JP4514251B2 (en) | 1999-07-21 | 1999-07-21 | Dye-sensitized solar cell |
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| Publication Number | Publication Date |
|---|---|
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|---|---|---|---|
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Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100416502B1 (en) * | 2001-10-18 | 2004-01-31 | 한국전자통신연구원 | Dye-sensitized solar cells including titanium silicalite-2 |
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