200824170 (1) 九、發明說明 【發明所屬之技術領域】 本發明關於一種具有白金膜之電極的製造方法、特別 是具有有用於作爲色素增感太陽能電池對極之白金膜之電 極的製造方法。 【先前技術】 Φ 於1991年，由瑞士洛桑工科大學之格拉茲爾（MichaelBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrode having a platinum film, and more particularly to a method for producing an electrode for use as a platinum film of a dye-sensitized solar cell. [Prior Art] Φ In 1991, by Grazl, Lausanne University of Technology, Switzerland (Michael
Gitzel)，所發表的新型態色素增感太陽能電池，相較於 以往之矽氧烷型太陽能電池，由於所使用材料價格便宜， 製造步驟比較單純，可大幅削減製造成本，其實用化有所 期待。 此方式之色素增感太陽能電池中，需要對於電解液中 存在的氧化還原對（例如，、Γ等）於電極表面由氧化體 快速成爲還原體的反應（例如，l3^2e_ = 3r的反應）具有觸 # 媒機能的對極。該對極可使用將觸媒能高的白金載持於附 有導電膜[例如ITO(銦·錫氧化物）、SiiO等]的導電性基 板上者。白金載持的方法，一般可使用濺鍍法（參照專利 文獻1 )、蒸鎞法（參照專利文獻2)。然而’該等方法考慮 ’ 於量產化、大面積化時，由需要具備大型真空室的裝置， 生產性亦低、設備費亦高，無法削減製造成本。再者’亦 有報導根據該等方法所製作之對極，白金溶解於碘電解質 ，而無耐久性。 其他的方法而言，專利文獻3中揭示以電鍍於導電層 -4- 200824170 (2) 表面載持白金粒子的方法。然而，此方法由於白金粒子係 以粒子載持，考慮有密著強度低且耐久性亦有問題。再者 ，此方法係使用硝酸脂強酸作爲電解液，於強酸性下的電 鍍，使用於酸性弱的導電膜（例如ITO、SnO等）之基板或 金屬基板，有導電膜的溶解、基板的溶解等問題。 ^ 再者，於金屬材料上進行電鍍、無電場鍍敷時，不得 不經由酸處理等除去金屬材料表面的氧化膜，前處理步驟 φ 亦爲複雜，產生有害物，於環境上亦有問題。 [專利文獻1]日本特開2000-173680號公報 [專利文獻2]日本特開2000-3 63 30號公報 [專利文獻3]日本特開2003_ 3 689 7號公報 【發明內容】 發明欲解決的問題 本發明爲解決上述以往技術中存在的問題，以提供具 • 有更優異白金膜之電極製造方法，特別是有用於作爲色素 增感太陽能電池的對極之具有白金膜的電極的製造方法爲 課題。 本發明者們，爲解決上述課題致力硏究的結果發現， 使用Ρ Η 2以上的白金水溶液作爲電解液而進行電鍍，於 導電膜上形成密著強度充分且均依的白金膜狀，而完成本 發明。 亦即’本發明之具有白金膜之電極的製造方法，爲依 序進行下述步驟： -5- 200824170 (3) (a) 陰極、陽極、電解液及電源的準備步驟，其係使 層合有導電膜的基板作爲陰極，使pH 2以上的白金水溶 液作爲電解液的準備步驟； (b) 將該陰極連接於該電源的負極（-極），該陽極連接 於該電源之正極（+極）之同時，藉由將兩電極浸漬於該電 ‘ 解液且於兩電極間施加電壓進行電鍍，於該陰極之該導電 膜上形成白金膜的步驟；以及 # (c)將形成有該白金膜之陰極取出的步驟。 再者，本發明係以根據該方法所製造之電極使用作爲 色素增改太陽能電池的對極爲特徵。 根據本發明，於白金水溶液中經由電鍍法的電極製作 ，可使用銦·錫氧化物（ITO)等，酸性弱的材料，可以短 時間選擇性地於導電膜上形成白金膜。電鍍法相較於以往 之灘鍍法等，爲價格低的製造方法，可對於色素增感太陽 能電池的製造成本有所貢獻。再者，所形成之白金膜亦較 ® 濺鍍法所形成者，更爲耐久力優異，可對於耐久性的色素 增改太陽能電池的製造有所貢獻。 【實施方式】 (1)步驟U) 本步驟爲本發明製造方法上所必要之陰極、陽極、電 解液及電源的準備步驟。 (i)電解液 200824170 (4) 本發明方法中所使用之電解液，係使用pH 2以上之 白金水溶液。 使用於本發明之白金水溶液中所使用之白金化合物’ 雖然只要適合於電鍍者之任意者皆可，但以四氯白金（Π) 酸鉀[K2PtCl4]、二氯四胺白金（II)[Pt(NH3)4Cl2 · H20]、 * 二硝基二胺白金（II)[Pt(N02)2(NH3)2]、六氯白金（IV)酸6 水合物[H2PtCl6 · 6H20]、六胺白金（IV)甲磺酸鹽 Φ [Pt(NH3)6(CH3S03)4]等水溶性之二價或四價之白金化合物特 爲適合。 各白金化合物的濃度，以白金的重量而言，可使用 0.1至10g/L的濃度爲適合，較佳可於1.5至2.5g/L的濃度 範圍使用。 再者，必要時，亦可添加肼等作爲還原劑、羥基胺鹽 等作爲安定劑的添加物。 本溶液之pH爲2以上係重要者。本溶液之pH爲未達 Φ 2之強酸時，至形成白金膜爲止持續電鍍，所製得之白金 膜立即剝離，無法期待良好的電池性能（參照專利文獻1第 0 031段）。考慮基材的性質、白金的析出速度等，雖可調 整最適pH，但由基板上導電膜保護的觀點，pH的範圍較 ^ 佳爲4至13，再較佳爲7至1 1(7除外）。pH調整劑可適宜地 使用硝酸、氨水、氫氧化鉀等。 (Π)陰極 本發明所使用之陰極爲層合有導電膜的基板。 200824170 (5) 基板可使用玻璃基板、塑膠基板、金屬基板等，不特 定選擇基板材質。如後述方式，特別是根據本發明之方法 ’使用金屬基板時，不需要表面氧化膜的去除等，可簡單 地進行電鍍。使用作爲金屬基板之金屬材料，由對碘之耐 腐飩性觀點而言，較佳爲鈦、不鏽鋼等。 • 由低電阻率的觀點而言，導電層較佳爲可含有添加物 之氧化錫、銦·錫氧化物（ITO)膜（氧化銦中較佳含有5至 φ 15重量％之氧化錫），亦可爲氧化錫中摻雜（dope)有氟或銻 者。該等導電層可經由濺鍍法、蒸鍍法、旋塗法等已知方 法，層合於上述基板。經由濺鍍法、蒸鍍法等，表面的導 電膜（第一導電層）爲平滑地層合時，且分散於有機溶劑等 IT0奈米粒子（粒徑爲5至10〇nm，較佳爲10至50nm)等粒子 ，塗佈於上述第一導電層上形成第二導電層，使表面基大 ，提升觸媒性能而佳。 # (iii)其他 其他之陽極、電源等，可使用電鍍中通常所使用者。 陽極可適宜使用例如碳電極、白金電極等。 * (2)步驟（b) 本步驟爲進行電鍍的步驟。 電鍍浴溫度可適宜地使用室溫至8 0 °C，較佳可使用室 溫至6 0 °C。 、 由析出速度調控的觀點而言，電流密度一般調控爲 -8 - 200824170 (6) 0.1至10A/dm2的電流密度進行爲佳，較佳調控爲2.5至 6A/dm2進行。 電鍍時間雖受到溫度、電流密度等的影響，但由觸媒 性能及成本的觀點而言，可使用0.1至5分鐘，較佳爲0.25 至1.0分鐘。 根據本電鍍步驟，可於陰極導電膜上選擇性地形成白 金膜。經由白金於導電膜上形成膜，具有密著性、緻密性 Φ 之機械強度良好，白金膜反射光而於發電時賦予反射光， 效率提升等有利點。 (3)步驟（c) 本步驟係將於上述（a)、（b)所製造之形成有白金膜之 陰極取出的步驟。 取出的陰極，水洗、乾燥後，可適宜使用作爲色素增 感太陽能電池的對極。 # 以下列舉實施例更詳細說明本發明。 [實施例] 第1圖顯示電鍍的模式圖。 容器1內的白金水溶液2中，浸漬於單側層合有導電層 7之基板6及相對電極3。 白金水溶液，除了實施例4以外，使用藉由氨水（含量 25重量°/〇，使六胺白金（IV)甲磺酸鹽水溶液調整爲PH 10.8者。該白金水溶液中，六胺白金（IV)甲磺酸鹽濃度爲 200824170 (7) 6.9§/1^(白金爲2§/1〇，該白金水溶液的液溫爲19°〇。 使用碳電極作爲相對電極。 電鍍係將直流電源5的負極（-極）連接於層合有導電 層7之基板6，直流電極5的正極（+極）連接於相對電極3， 於此狀態，以兩電極間的電流成爲Ο.ΙΑ/dm2至ΙΟΑ/dm2的 • 方式，施加電壓，於層合於基板6之導電層7的表面，選擇 性地形成白金膜8，可如第2圖所示之對極4。 Φ 更詳而言之，如下述方式之實施例1至3及比較例1及2 中，分別製作對極4。如實施例1，電鍍係於pH 2以上， 較佳爲7以上的白金水溶液中進行，如ITO之酸性弱的導 電層，可不損傷ITO而進行白金鍍敷。 再者，如實施例3，鈦金屬等，表面具有氧化皮膜之 金屬材料，於一般電鍍中，不除去氧化皮膜無法進行鍍敷 ，經由於表面層合導電層，不進行氧化皮膜除去之複雜的 前處理而可簡單地進行電鍍。電鍍係於層合有導電層之面 # ，選擇性地鍍敷，由於無導電層的面則不鍍敷，對於對極 的製作非常有利。 (實施例1) ' 單面層合有導電層7之基板6，使用於玻璃基板上蒸鍍 有銦.錫氧化物（IΤΌ，氧化銦中含有大約1 〇重量％的氧化 錫）者（膜厚20 0nm)。電鍍前之蒸鍍有IT0的導電膜表面的 電子顯微鏡照相示於第4圖。 電鍍的電流密度爲5A/dm2，時間爲0.5分鐘。電鍍之 -10- 200824170 (8) 後，水洗形成有白金膜的基板，於11 0 °c乾燥（白金膜厚度 5nm)。電鍍後之蒸鍍有ITO的導電膜表面的電子顯微鏡 照相示於第5圖。電鍍前後的表面無差異，亦無法辨認有 白金粒子，咸信白金爲膜狀均一地析出。 ^ (實施例2) 與實施例1相同，準備蒸鍍有作爲導電膜ITO之玻璃 # 基板，於該基板上，再旋塗ITO粒子濃度1〇質量％的有機 溶劑溶液（有機溶劑：異丙醇），於1 1 〇 °C乾燥5分鐘，將其 作爲陰極進行電鍍（旋塗膜厚400nm)。 電鍍的電流密度爲5A/dm2，時間爲0.5分鐘。電鍍之 後，水洗形成有白金膜的基板，於ll〇°C乾燥（白金膜厚度 5 nm) 〇 (比較例1) • 與實施例1相同，使用玻璃基板上蒸鍍有ITO作爲導 電層者做爲基板，該導電層表面藉由濺鍍裝置（日立製作 所製造，E- 1 0 3 0型離子濺鍍機），載持20nm厚的白金。 (實施例3) 使用鈦金屬板上旋塗平均粒徑12nm之IT0粒子濃度 1 0質量％的有機溶劑溶液（有機溶劑：異丙醇），於1 1 〇°c乾 燥5分鐘者。（膜厚400nm)。 電鍍的電流密度爲5A/dm2 ’時間爲〇.5分鐘。電鍍之 -11 - 200824170 (9) 後，水洗形成有白金膜的基板，於110°c乾燥（白金膜厚度 (比較例2 ) 與實施例2同樣，基板係使用鈦金屬板，經由濺鍍裝 置於該表面載持20nm厚的白金。 • (實施例4) 使用藉由氨水（含有12.5重量％)，使六胺白金（IV)甲 磺酸鹽水溶液調整爲pH 2.1者，作爲白金水溶液。此時， 六胺白金（IV)甲磺酸鹽濃度爲6.9g/L(白金爲2g/L)，該白 金水溶液的液溫爲1 9 °C。 基板係使用與實施例1相同之於玻璃基板上蒸鍍有作 爲導電膜ITO者，電鍍的電流密度爲5A/dm2，時間爲0.5 分鐘。 φ 電鍍之後，水洗，於1 10°C乾燥（白金膜厚度4nm)。 (性能評估） 使用實施例1、2、3、4及比較例1、2中所製造之各個 ’ 電極作爲對極，分別製作第3圖之色素增感性太陽能電池 〇 對於該等，使用I-V測試，求出變換效率η[%]、開 放電壓 Voc[V]、短路電流 Jsc[mA/cm2]、曲線因子FF， 評估上述實施例及比較例之各電極組裝作爲對極之色素增 -12- 200824170 (10) 感性太陽能電池的性能。其結果示於表1。 由表1所不結果可知’經由電鍍方法’顯示與經由濺 鍍方法同樣良好的電池性能。再者，根據實施例2，再於 表面追加的附著ITO粒子，表面積增加，變換效率可更爲 良好。 再者’於實施例4中’電解液的ρ Η爲酸性（2.1 )的結 果，與實施例1相比，白金厚度稍微變薄。因此，觸媒性 能與實施例1相比爲稍稍降低。 [表1] 變換效率 開放電壓 短路電流 曲線因子 電池面積 η『％1 Vocm Jsc[mA/cm2] FF [cm2] 實施例1 4.65 0.77 9.89 0.61 0.254 實施例2 5.42 0.72 10.77 0.70 0.224 比較例1 5.53 0.72 10.87 0.70 0.210 實施例3 5.61 0.74 10.73 0.71 0.205 比較例2 5.74 0.74 11.26 0.69 0.264 實施例4 3.60 0.69 10.10 0.51 0.269Gitzel), a new type of sensitized sensitized solar cell, has a cheaper manufacturing process and a significantly lower manufacturing cost than the conventional siloxane-type solar cell. look forward to. In the dye-sensitized solar cell of this type, it is necessary to react a redox pair (for example, ruthenium, etc.) present in the electrolyte on the surface of the electrode to rapidly become a reducing body by an oxidant (for example, a reaction of l3^2e_ = 3r) It has the opposite pole of the #Media function. The counter electrode can be used by supporting platinum having a high catalytic energy on a conductive substrate having a conductive film [e.g., ITO (indium tin oxide), SiiO, etc.]. As a method of carrying the platinum, a sputtering method (see Patent Document 1) and a steaming method (see Patent Document 2) can be generally used. However, when these methods are considered to be mass-produced and large-area, devices requiring a large vacuum chamber have low productivity and high equipment costs, and the manufacturing cost cannot be reduced. Furthermore, it has been reported that the platinum produced by these methods is dissolved in an iodine electrolyte without durability. In other methods, Patent Document 3 discloses a method of plating platinum particles on a surface of a conductive layer -4- 200824170 (2). However, in this method, since the platinum particles are supported by particles, it is considered that the adhesion strength is low and the durability is also problematic. Furthermore, this method uses a strong acid of nitrate as an electrolyte, and is plated under strong acidity, and is used for a substrate or a metal substrate of a weakly acidic conductive film (for example, ITO, SnO, etc.), which dissolves the conductive film and dissolves the substrate. And other issues. ^ In addition, when electroplating or electroless plating is performed on a metal material, the oxide film on the surface of the metal material must be removed by acid treatment, and the pretreatment step φ is also complicated, causing harmful substances and environmental problems. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-163680 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2000-3 63 No. In order to solve the above problems in the prior art, the present invention provides a method for producing an electrode having a more excellent platinum film, and in particular, a method for producing an electrode having a platinum film as a counter electrode of a dye-sensitized solar cell is Question. As a result of the inventors of the present invention, it has been found that a platinum aqueous solution of Ρ 2 or more is used as an electrolytic solution for electroplating, and a platinum film having a sufficient adhesion strength and uniformity is formed on the conductive film. this invention. That is, the manufacturing method of the electrode having the platinum film of the present invention is carried out in the following steps: -5- 200824170 (3) (a) Preparation steps of the cathode, the anode, the electrolyte, and the power source, which are laminated a substrate having a conductive film as a cathode, and a platinum aqueous solution having a pH of 2 or higher as a preparation step of the electrolytic solution; (b) connecting the cathode to a negative electrode (-pole) of the power source, the anode being connected to a positive electrode of the power source (+ pole) At the same time, a step of forming a platinum film on the conductive film of the cathode by immersing the two electrodes in the electric solution and applying a voltage between the electrodes, and #(c) forming the platinum The step of taking out the cathode of the membrane. Further, the present invention is characterized by the use of an electrode manufactured by the method as a dye-enhanced solar cell. According to the present invention, it is possible to form a platinum film on the conductive film in a short time by using an electrode made of an electroplating method in an aqueous solution of platinum, such as indium tin oxide (ITO) or the like, which is weak in acidity. The electroplating method is a low-cost manufacturing method compared to the conventional beach plating method, and contributes to the manufacturing cost of the dye-sensitized solar cell. Furthermore, the formed platinum film is more durable than those formed by the ® sputtering method, and contributes to the manufacture of a durable dye-modified solar cell. [Embodiment] (1) Step U) This step is a preparation step of a cathode, an anode, an electrolyte, and a power source which are necessary for the production method of the present invention. (i) Electrolyte 200824170 (4) The electrolytic solution used in the method of the present invention is a platinum aqueous solution having a pH of 2 or more. The platinum compound used in the aqueous platinum solution of the present invention is as long as it is suitable for any of the electroplating, but potassium tetrachloroplatinum (K2PtCl4), dichlorotetramine platinum (II) [Pt (NH3)4Cl2 · H20], * Dinitrodiamine platinum (II) [Pt(N02)2(NH3)2], hexachloroplatinum (IV) acid 6 hydrate [H2PtCl6 · 6H20], hexamine white gold ( IV) A water-soluble divalent or tetravalent platinum compound such as methanesulfonate Φ [Pt(NH3)6(CH3S03)4] is particularly suitable. The concentration of each platinum compound may be suitably from 0.1 to 10 g/L in terms of the weight of platinum, and preferably from 1.5 to 2.5 g/L. Further, if necessary, an additive such as a reducing agent or a hydroxylamine salt may be added as a stabilizer. It is important that the pH of the solution is 2 or more. When the pH of the solution is not more than Φ 2 , the plating is continued until the formation of the platinum film, and the obtained platinum film is immediately peeled off, and good battery performance cannot be expected (refer to paragraph 0 031 of Patent Document 1). Considering the properties of the substrate, the deposition rate of platinum, etc., although the optimum pH can be adjusted, the pH range is preferably from 4 to 13, more preferably from 7 to 1 1 (except 7) from the viewpoint of protection of the conductive film on the substrate. ). As the pH adjuster, nitric acid, ammonia water, potassium hydroxide or the like can be suitably used. (Π) Cathode The cathode used in the present invention is a substrate in which a conductive film is laminated. 200824170 (5) A glass substrate, a plastic substrate, a metal substrate, etc. can be used as the substrate, and the substrate material is not selected. As will be described later, in particular, when the metal substrate is used in accordance with the method of the present invention, it is not necessary to remove the surface oxide film, and the plating can be easily performed. The metal material used as the metal substrate is preferably titanium, stainless steel or the like from the viewpoint of corrosion resistance to iodine. • From the viewpoint of low resistivity, the conductive layer is preferably a tin oxide or indium tin oxide (ITO) film which may contain an additive (5 to 15% by weight of tin oxide is preferably contained in indium oxide). It can also be doped with tin or antimony in the tin oxide. These conductive layers may be laminated on the substrate by a known method such as a sputtering method, a vapor deposition method, or a spin coating method. When the conductive film (first conductive layer) on the surface is smoothly laminated by a sputtering method, a vapor deposition method, or the like, it is dispersed in an IT0 nanoparticle such as an organic solvent (particle diameter is 5 to 10 nm, preferably 10). The particles are coated on the first conductive layer to form a second conductive layer to a large surface area, thereby improving the performance of the catalyst. # (iii) Others Other anodes, power supplies, etc., can be used by ordinary users in electroplating. As the anode, for example, a carbon electrode, a platinum electrode or the like can be suitably used. * (2) Step (b) This step is the step of plating. The temperature of the plating bath can be suitably from room temperature to 80 ° C, preferably from room temperature to 60 ° C. From the viewpoint of the regulation of the deposition rate, the current density is generally controlled to be -8 - 200824170 (6). The current density of 0.1 to 10 A/dm 2 is preferably performed, preferably 2.5 to 6 A/dm 2 . Although the plating time is affected by temperature, current density, etc., it can be used for 0.1 to 5 minutes, preferably 0.25 to 1.0 minutes from the viewpoint of catalyst performance and cost. According to this plating step, a platinum film can be selectively formed on the cathode conductive film. The film is formed on the conductive film via platinum, and has good adhesion and compactness. Φ has good mechanical strength, and the platinum film reflects light to provide reflected light during power generation, and the efficiency is improved. (3) Step (c) This step is a step of taking out the cathode formed with the platinum film produced in the above (a) and (b). After the taken-out cathode is washed with water and dried, it can be suitably used as a counter electrode of a dye-sensitized solar cell. # The following examples illustrate the invention in more detail. [Embodiment] Fig. 1 is a view showing a pattern of electroplating. The platinum aqueous solution 2 in the container 1 is immersed in the substrate 6 and the counter electrode 3 on which the conductive layer 7 is laminated on one side. In the platinum aqueous solution, in addition to Example 4, an aqueous solution of hexamine white gold (IV) methanesulfonate was adjusted to pH 10.8 by aqueous ammonia (content: 25 wt./min.), in the aqueous platinum solution, hexamine platinum (IV). The methanesulfonate concentration is 200824170 (7) 6.9§/1^ (platinum is 2§/1〇, the liquid temperature of the platinum aqueous solution is 19°〇. The carbon electrode is used as the opposite electrode. The electroplating system is the negative electrode of the DC power supply 5 (-pole) is connected to the substrate 6 on which the conductive layer 7 is laminated, and the positive electrode (+ pole) of the DC electrode 5 is connected to the opposite electrode 3. In this state, the current between the electrodes becomes Ο.ΙΑ/dm2 to ΙΟΑ/ In the mode of dm2, a voltage is applied to the surface of the conductive layer 7 laminated on the substrate 6, and the platinum film 8 is selectively formed, as shown in Fig. 2, which is the counter electrode 4. Fig. 2 More specifically, as follows In the first to third embodiments and the comparative examples 1 and 2, the counter electrode 4 was produced. In the first embodiment, the electroplating was carried out in an aqueous platinum solution having a pH of 2 or higher, preferably 7 or more, such as weak acidity of ITO. The conductive layer can be plated with platinum without damaging the ITO. Further, as in Example 3, titanium metal, etc., the surface A metal material having an oxide film can be plated without removing the oxide film during general plating, and can be easily plated by laminating the conductive layer on the surface without complicated pretreatment of the oxide film removal. The surface # of the conductive layer is selectively plated, and the surface without the conductive layer is not plated, which is very advantageous for the fabrication of the counter electrode. (Embodiment 1) 'The substrate 6 on which the conductive layer 7 is laminated on one side It is used for vapor deposition of indium tin oxide (IΤΌ, indium oxide containing about 1% by weight of tin oxide) on a glass substrate (film thickness: 20 nm). The surface of the conductive film of the IT0 is deposited by electroplating. The electron micrograph is shown in Fig. 4. The current density of the electroplating is 5 A/dm2 for 0.5 min. After electroplating-10-200824170 (8), the substrate formed with the platinum film is washed with water and dried at 110 °c (platinum) The film thickness was 5 nm. The electron micrograph of the surface of the conductive film on which ITO was deposited after electroplating was shown in Fig. 5. There was no difference in the surface before and after electroplating, and platinum particles were not recognized, and the salty platinum was uniformly precipitated in a film form. ^ (Embodiment 2) In the same manner as in the first embodiment, a glass substrate as a conductive film ITO was deposited, and an organic solvent solution (organic solvent: isopropanol) having an ITO particle concentration of 1% by mass was spin-coated on the substrate, at 1 1 〇. After drying at ° C for 5 minutes, it was electroplated as a cathode (spin coating film thickness: 400 nm). The current density of plating was 5 A/dm 2 for 0.5 minute. After plating, the substrate formed with platinum film was washed with water at ll ° ° C. Drying (platinum film thickness: 5 nm) 〇 (Comparative Example 1): In the same manner as in Example 1, a substrate on which a ITO was deposited as a conductive layer on a glass substrate was used as a substrate, and the surface of the conductive layer was produced by a sputtering apparatus (manufactured by Hitachi, Ltd.). , E- 1 0 3 0 type ion sputtering machine), carrying 20nm thick platinum. (Example 3) A titanium oxide plate was spin-coated with an organic solvent solution (organic solvent: isopropanol) having an average particle diameter of 12 nm and an organic solvent solution (organic solvent: isopropanol) at 10 ° C for 5 minutes. (film thickness 400 nm). The current density of the plating was 5 A/dm 2 'time was 〇5 minutes. Plating -11 - 200824170 (9), the substrate on which the platinum film was formed was washed with water, and dried at 110 ° C (platinum film thickness (Comparative Example 2). Similarly to Example 2, the substrate was made of a titanium metal plate, and passed through a sputtering apparatus. 20 nm thick platinum was carried on the surface. (Example 4) An aqueous solution of hexamine white gold (IV) methanesulfonate was adjusted to pH 2.1 by using ammonia water (containing 12.5% by weight) as a platinum aqueous solution. The hexamine white gold (IV) methanesulfonate concentration was 6.9 g/L (white gold was 2 g/L), and the liquid temperature of the platinum aqueous solution was 19 ° C. The substrate was the same as in Example 1 on a glass substrate. The conductive film ITO was vapor-deposited, and the current density of the plating was 5 A/dm 2 for 0.5 minute. After φ plating, it was washed with water and dried at 10 ° C (platinum film thickness: 4 nm). (Performance evaluation) Example of use In each of the 'electrodes produced in 1, 2, 3, and 4 and Comparative Examples 1 and 2, a dye-sensitized solar cell of Fig. 3 was produced as a counter electrode, and the conversion efficiency η was obtained by using an IV test. %], open voltage Voc [V], short circuit current Jsc [mA/cm2], curve factor FF, The performance of each of the electrodes of the above examples and comparative examples was evaluated as the performance of the inductive solar cell of the opposite electrode. The results are shown in Table 1. From the results of Table 1, it is known that 'via the plating method' The battery performance was as good as that of the sputtering method. Further, according to Example 2, the surface area was further increased by the adhesion of the ITO particles, and the conversion efficiency was further improved. Further, in Example 4, the electrolyte solution was used. As a result of ρ Η being acidic (2.1), the thickness of platinum was slightly thinner than in Example 1. Therefore, the catalyst performance was slightly lower than that of Example 1. [Table 1] Conversion efficiency open voltage short-circuit current curve factor Battery area η "%1 Vocm Jsc [mA/cm2] FF [cm2] Example 1 4.65 0.77 9.89 0.61 0.254 Example 2 5.42 0.72 10.77 0.70 0.224 Comparative Example 1 5.53 0.72 10.87 0.70 0.210 Example 3 5.61 0.74 10.73 0.71 0.205 Comparison Example 2 5.74 0.74 11.26 0.69 0.264 Example 4 3.60 0.69 10.10 0.51 0.269
(發明品耐久性的評估） 爲了調查電池的耐久性，以碘與碘化鋰分別爲0.03 Μ 、0.3 Μ的濃度的方式，溶解於3 -甲氧基丙腈製作電解液 ，於該電解液中浸漬上述實施例2之電極，於80 °C保持48 小時。之後，將其取出，使用該電極作爲對極，製作如第 3圖所示之色素增感性太陽能電池，於上述同樣方式評估 性能。其結果示於表2。 -13- 200824170 (11) (比較品耐久性評估） 爲了比較本發明電極的耐久性，與上述發明品製作同 樣的電解液，於該電解液中浸漬上述比較例1之電極’於 8 0°C保持48小時。之後，將其取出，使用該電極作爲對極 •，製作如第3圖所示之色素增感性太陽能電池，於上述同 樣方式評估性能。其結果不於表2。 [表2] 變換效率 開放電壓 短路電流 曲線因子 電池面積 η『％1 Voc[Vl Jsc[mA/cm2l FF [cm2] 發明品耐久性評估 4,89 0.75 9.60 0.68 0.249 比較品耐久性評估 0.40 0.72 2.34 0.24 0.228 由表2所示結果可知，經由電鍍方法與經由濺鍍方法 相比較，可確認耐久性優異。 [產業上可利用性] 根據本發明的方法所製造之電提，於其導電膜表面， 白金形成均一的膜’同時密著強度充分，有用於作爲色素 增感太陽能電池的對極。 再者，根據本發明，由於僅於必要部分形成導電層， 可僅於必要部分形成白金膜’可削減成本。此外，以金屬 板等使用本發明的方法時，不需要表面氧化皮膜的去除等 處理，可於表面形成導電膜而簡單地電鍍。 -14- 200824170 (12) 【圖式簡單說明】 第1圖爲顯示電鍍型態之模式剖面圖。 第2圖爲顯示使用本發明之電極作爲色素增感太陽能 電池的對極時的基本構成之模式剖面圖。 第3圖爲第2圖中所顯示之使用作爲色素增感太陽能電 池的對極的電極之模式剖面圖。 第4圖爲實施例1中電鍍前ITO玻璃導電膜表面之電 子顯微鏡照相圖（8萬倍）。 第5圖爲實施例1中電鍍後ITO玻璃導電膜表面之電 子顯微鏡照相圖（10萬倍）。 【主要元件符號說明】 1 :容器 2 :白金水溶液 3 :碳電極 4 :對極 5 :直流電源 6 :基板 7 :導電層 8 :白金膜 9 :半導體電極 1 〇 :透明導電層 1 1 ·透明基板 -15- 200824170 (13) 12 :光電極 13 :電解液(Evaluation of Durability of Invention) In order to investigate the durability of the battery, an electrolyte solution was prepared by dissolving the electrolyte in the form of a concentration of 0.03 、 and 0.3 碘 of iodine and lithium iodide, respectively. The electrode of the above Example 2 was immersed and kept at 80 ° C for 48 hours. Thereafter, the film was taken out, and the electrode was used as a counter electrode to prepare a dye-sensitized solar cell as shown in Fig. 3, and the performance was evaluated in the same manner as above. The results are shown in Table 2. -13-200824170 (11) (Comparative product durability evaluation) In order to compare the durability of the electrode of the present invention, the same electrolytic solution as that of the above invention was produced, and the electrode of the above Comparative Example 1 was immersed in the electrolytic solution at 80°. C is kept for 48 hours. Thereafter, the electrode was taken out and the electrode was used as a counter electrode. A dye-sensitized solar cell as shown in Fig. 3 was produced, and the performance was evaluated in the same manner as described above. The result is not in Table 2. [Table 2] Conversion efficiency Open voltage Short-circuit current curve factor Battery area η "%1 Voc [Vl Jsc [mA/cm2l FF [cm2] Durability evaluation of invention product 4,89 0.75 9.60 0.68 0.249 Comparative product durability evaluation 0.40 0.72 2.34 0.24 0.228 As a result of the results shown in Table 2, it was confirmed that the durability was excellent by the plating method as compared with the sputtering method. [Industrial Applicability] According to the electrowinning method produced by the method of the present invention, platinum forms a uniform film on the surface of the conductive film, and the adhesion strength is sufficient, and it is used as a counter electrode for a dye-sensitized solar cell. Further, according to the present invention, since the conductive layer is formed only in the necessary portion, the platinum film can be formed only in the necessary portion, and the cost can be reduced. Further, when the method of the present invention is used as a metal plate or the like, treatment such as removal of the surface oxide film is not required, and a conductive film can be formed on the surface to be easily plated. -14- 200824170 (12) [Simple description of the drawing] Fig. 1 is a schematic cross-sectional view showing the plating pattern. Fig. 2 is a schematic cross-sectional view showing a basic configuration in which an electrode of the present invention is used as a counter electrode of a dye-sensitized solar cell. Fig. 3 is a schematic cross-sectional view showing the electrode used as the counter electrode of the dye-sensitized solar cell shown in Fig. 2. Fig. 4 is a photomicrograph (80,000 times) of the surface of the ITO glass conductive film before electroplating in Example 1. Fig. 5 is a photomicrograph (100,000 times) of the surface of the electroconductive film of ITO glass after electroplating in Example 1. [Main component symbol description] 1 : Container 2 : Platinum aqueous solution 3 : Carbon electrode 4 : Counter electrode 5 : DC power supply 6 : Substrate 7 : Conductive layer 8 : Platinum film 9 : Semiconductor electrode 1 〇 : Transparent conductive layer 1 1 · Transparent Substrate-15- 200824170 (13) 12: Photoelectrode 13: Electrolyte
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