201025626 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種太陽能電池，特別是一種俗稱第三代有機太陽能電 池的染料敏化太陽能電池(Dye-Sensitized Solar Cell，DSSC)。 【先前技術】 按，能源短缺問題已經無法繼續漠視，是以，有越來越多替代性能源 的技術被發表’其中，又以關於電力系統的替代方案最多，而太陽能電池 即是其中一種* 目前太陽能電池領域已經由俗稱第一代矽晶片製成之太陽能電池、第 二代砷化鎵(GaAs)製成之太陽能電池，進化到目前第三代之染料敏化製成 之太陽能電池(DSSC)。前二者，具有發展較早，效率高，應用廣泛的優勢， 但卻也因為原料取得不易而價格昂貴，第二代太陽能電池之製作成本雖然 較第一代太陽能電池更為便宜，但所使用的坤卻是一種毒性強之重金屬， 對於環境會造成嚴重之污染；而第三代的敏化染料太陽能電池其主要結構 是由導電玻璃作成的透明基材、載有染料敏化之多孔性半導體材料、電解 質以及對電極所構成’其原料取得容易，且具備有可大面積製作、可透光 性、製程簡便、成本低廉以及可挽曲等多項優點，因此被期許有朝一曰可 以替代第一代以及第二代太陽能電池。 然而，染料敏化太陽能電池為一種化學電池，其電解質的存在是必須 的，而目前經使用的電解質可以區分為液態、膠態以及固態三種，三者之 中，又以液態電解質的光電轉換效率最高，為最好氧化還原材料的選擇， 所以大部分的敏化染料太陽能電池能仍是以液態電解質為主，而液態電解 201025626 質中所使㈣械溶❹具有高揮雜，又，敏絲料太陽麟池具有的 可繞性也造成電解液封裝困難度提高，相對來說，有機溶劑容易因為封裝 不良或老化而揮發，電池即會因電解質失衡或電解質外漏造成使用效率 大幅降低，甚至失效；參閱第i s，為習知敏化染料太陽能電池結構其 係具有二載有導電薄膜51之透明基材52，於二透明基材52之間設置一載 '有光敏染料53之半導體層54以及一相對電極56,於半導體層54以及相對 •電極54間設置一電解質58，外部並利用封膝60封閉半導體層54、相對電 ❹極56以及電解㈣’藉此，避免電解質58與負極接觸，但，電池用以注 入電解質58之灌注孔52卜係以蓋玻片62與熱溶勝64封孔，其接著性較 不理想，經過高溫曝曬或高渔環境長期影響，熱溶膠64將產生老化現象造 成漏液。其次，染職化電池之透明基板電阻率相當的高，因此電池内電 流傳導距離必須小於1公分町，才可以避免因内電阻的損失造成電池效 率降低，偏要使敏化染料太陽能電池的發電量達到高功率與高瓦特數時， 必須將許多小面積的電池單元進行適當串、並聯設計；故，大面積化的敏 〇 化染料電池必須對多數電池單元先製作内部電流收集線來提高其轉換效 率，再將内部電流收集線引出集結成對外導線，才能獲取所需電力，目前 國内外所發表的電池模組結構，大致可以區分為，如第二(a)圖之0型、第 一(b)圖之z型、第二(C)圖之W型、第二(d)圖之S型，以及第3圖所示， 中華民國專利1241721號所發表之式樣，當中除了 g型不需切斷導電膜以 外，但其效率不彰，其餘四者都必須經雷射雕割法或刀輪畫線法切斷導電 膜，使電池模組陣列呈2〜η排後，再使用導電材料以複雜交錯之印刷方法 201025626 反覆地轉印’才能製作所需的電池模組，嚴然使得製作過程過於繁複β 有鑑於此，本發明提出一種染料敏化電池，以有效改善前述之該些問 題。 【發明内容】 本發明之主要目的係在提供一種敏化染料太陽能電池，其有效降低電 解質内有機溶劑揮發可能性，且可強化電池結構避免電解質外滲，因而更 • 有利於電池的長期使用。 0 本發明之次要目的係在提供一種敏化染料太陽能電池，其大面積生產 時，無須經過切割，係在製作完成後，直接於電池單元外部進行串、並聯 之連結線路，減少大面積製程的繁瑣步驟，縮短電池模組製作時程。 本發明之又一目的係在提供一種敏化染料太陽能電池，其提高光線於 電池模組内重複反射的效果，使得光電轉換效率更高。 為逹上述目的，本發明揭露之染料敏化太陽能電池，包括有一第一透 月基板、一第一透明基板、一半導體層、一相對電極屠、一框膠以及一封 〇 塞；此第一透明基板及第二透明基板係採相對設置，各透明基板内面載有 ^ 一導電薄膜，且第二透明基板具有一灌注孔，此半導體層設置於第一透明 基板之導電薄膜上，其載有光敏染料，而此相對電極層又設於第二透明基 板之導電薄膜上，並面對半導體層，而電解質係位在半導體層以及相對電 極層之間，係藉由框膠的包覆來避免電解質外滲；栓塞則是透過黏著劑封 閉第二透明基板的灌注孔，使得電解質無外渗之虞。 底下藉由具艘實施例配合所附的圖式詳加說明，便於審查委員更容易 7 201025626 瞭解辨別本創作之目的、技術内容、特點及其所達成之功效β 【實施方式】 本發明揭卜種敏化染料太陽能電池’除了改善封裝方式來解決習知 敏化染料太陽能電池電解質容易外滲之缺失外，並可以簡單的方式製作大 面積電池模組。 參閱第4圖，係為本發明太陽能電池之結構示意圖。如圖所示，本發 ‘ 明係包含有-第---第二透明基板12、14 ' -半導體層16、一相對電極 φ 層18、一電解質20、一框膠22、一检塞24以及一光學反射層26。其中透 明基板12、14係具有導電性·，且第一透明基板12載有一第一導電膜 (TCO)121 ’第二透明基板14上載有一第二導電薄膜(TC〇)141，此二透明基 板12、14並以導電薄膜(TC0)121、141相對之方式作對應設置，另外，第 二透明基板14並具有一灌注孔M2。半導體層16為奈米晶體層，且設置在 第一透明基板12之第一導電薄膜(TC0)121上，其層體中並已浸注有光敏 染料161。相對電極層18設置在第二透明基板14之第二導電薄膜(TC〇)141 ❹上’且面對該半導艘層16。而電解質20透過第二透明基板14之灌注孔142 填入半導體層16以及相對電極層ι8間之空隙，並經由高分子聚合物黏著 劑作成之框膠22封隔於第一透明基板12以及第二透明基板14間，且此框 膠22並包覆半導體層16、相對電極層18以及電解質2〇。 重點在於，此栓塞24係以玻璃或金屬材質製成，包括一柱部241以及 一連結該柱部241之蓋部242，將栓塞24與RTV膠、UV膠或AB膠等熱 塑性高分子黏著劑28結合，如此一來，栓塞24之柱部241會密合於第二 201025626 透明基板14之灌注孔142中，且其蓋部242緊貼合第二透明基板14外表 面。而光學反射層26更是以具有反射性質之稜鏡片、反射鏡片或擴散片等 材質製成’其貼置於第二透明基板14外表面，可以增加電池内光線反射效 果，提高光線利用率。 藉此，本發明之染料敏化太陽能電池以不易腐蝕老化之材質作為封印 、 第二透明基板之灌注孔材料，強化電池結構，有效避免電解質外滲的可能 ' 性’且能降低電解質内有機溶劑的揮發，更有利於電池的長期使用。再者’ _ 透過光學反射層可以加強光線於電池模組内的光線利用率，增加光電轉換 能量，而提昇本電池效率。 當然’對本發明而言，上述各元件材質係為熟知本領域之技術者可以 輕易均等置換。舉例來說，此透明基板可以是硬式或是軟式，其中硬式基 板可為導電玻璃，而軟式基板可以是PI、PE、PET、PVE、PP ' PS、PC、 PMMA其中一者或上述材質混合製成。而導電薄膜(TCO)則可以使用氧化 銦錫(ITO)或氟摻雜的氧化錫(FT〇)或鋁摻雜的氧化鋅(AZO)來製作。另外， Q 半導體層除了二氧化鈦(Ti〇2)以外，也可以是氧化辞(ZNO)。同理，光敏染 料之選擇可以是釕金屬錯合物染劑或有機化合物染劑或天然植物染劑等染 劑°相對電極層則可採用鉑元素或者碳元素等。電解質以液態電解液為佳， 如碘、碘化鉀、碘化鋰、離子液體、乙醇(Ethoal)、乙晴(AcN)或甲氧基丙晴 (MPN)等，當然也可以是膠態電解液或者固態電解液》最後，框膠之選用， 如玻璃膠材、高分子黏著膠材(如UV膠、AB膠、RTV膠)等。故，舉凡材 質之置換都應視為本發明均等實施，也不能以之限定本發明之專利範圍。 201025626 另外，實際製作本發明之敏化染料太陽能電池時，更可以配入需求 之功率以及瓦特數，透過適當地串並聯接線，增加電池模艇輸=:以及 輪出縣，參閲第5圈至第6圖所示，將上述說明之電池結構視為單一電 池單元1〇，依需求將複數電池單元10並列，使得相鄰電池單元關之第 -透明基板I2以及第二透明基板M树接，再以金屬導線初，如鋼、銀、 '錫或鐵等金屬線’或者是銀膠等導電膝體，於電池單元10外部進行串並聯 增加輪iH龍’亦或者，進行並聯增加輸丨驗(圖中未示）。 ® 如此一來，本發明之敏化染料太陽能電池在大面積製作時無須經過切 割’當製作完成後，直接於電池單元外部進行串、並聯結線，可以減少大 面積製程的繁瑣步驟，縮短電池模組製作時程。 以上所述係藉由實施例說明本發明之特點，其目的在使熟習該技術者 能暸解本發明之Θ谷並據以實施’而非限定本發明之專利範圍，故，凡其 他未脫離本發明所揭示之精神所完成之等效修飾或修改 ，仍應包含在以下 所述之申請專利範圍中。 ® 【圖式簡單說明】 第1圖係為習用敏化染料太陽能電池之結構示意圖。 第2(a)圖為習知<3型敏化染料電池之結構示意圖。 第2(b)圖為習知Z型敏化染料電池之結構示意圖。 第2(c)圖為習知冒型敏化染料電池之結構示意圖。 第2(d)圖為習知8型敏化染料電池之結構示意囷。 第3圖係為習知另一種敏化染料電池之結構示意圖。 201025626 第4圖係為本發明敏化染料太陽能電池結構之側視圖。 第5圖係為第4圖之正視圖。 第6圖係為第4圖之俯視圖。 【主要元件符號說明】 10電池 12第一透明基板 121第一導電薄膜 14第二透明基板 141第二導電薄膜 142 灌注孔 16半導體層 161光敏染料 18相對電極層 20電解質 22框膠 24栓塞 241 柱部 242 蓋部 26光學反射層 28黏著劑 ❿ 30導線 習用圖號說明： 51 導電薄膜 52 透明基材 521 灌注孔 53 光敏染料 54 半導體層 56 相對電極 58 電解質 60 封膠 62 玻片 64熱溶膠201025626 IX. Description of the Invention: [Technical Field] The present invention relates to a solar cell, and more particularly to a Dye-Sensitized Solar Cell (DSSC) commonly known as a third-generation organic solar cell. [Prior Art] According to the problem of energy shortage, it is no longer possible to ignore it. Therefore, more and more alternative energy technologies have been published. Among them, the most alternative to power systems, and solar cells are one of them* At present, solar cells in the field of solar cells have been made from solar cells commonly known as first-generation germanium wafers, solar cells made of second-generation gallium arsenide (GaAs), and have evolved into the third generation of dye-sensitized solar cells (DSSC). ). The former two have the advantages of early development, high efficiency and wide application, but they are also difficult to produce and expensive. The production cost of the second generation solar cell is cheaper than that of the first generation solar cell, but it is used. Kun is a toxic heavy metal that causes serious pollution to the environment. The third generation of sensitized dye solar cells are mainly made of transparent glass made of conductive glass and dye-sensitized porous semiconductor. The material, the electrolyte and the counter electrode are easy to manufacture, and have many advantages such as large-area production, light transmissibility, simple process, low cost, and flexibility. Therefore, it is expected to replace the first one. Generation and second generation solar cells. However, the dye-sensitized solar cell is a chemical battery, and the presence of an electrolyte is necessary, and the currently used electrolyte can be classified into three types: liquid, colloidal, and solid, and among them, the photoelectric conversion efficiency of the liquid electrolyte. The highest, is the choice of the best redox materials, so most of the sensitizing dye solar cells can still be based on liquid electrolytes, while the liquid electrolysis 201025626 is made of (4) mechanically dissolved cesium with high volatility, and, sensitive The susceptibility of the solar lining pool also increases the difficulty of encapsulation of the electrolyte. Relatively speaking, the organic solvent is easily volatilized due to poor packaging or aging, and the battery is greatly reduced in efficiency due to electrolyte imbalance or electrolyte leakage. The invention is a conventional sensitized dye solar cell structure having a transparent substrate 52 carrying a conductive film 51, and a semiconductor layer 54 carrying the photosensitive dye 53 and a spacer between the two transparent substrates 52. The opposite electrode 56 is provided with an electrolyte 58 between the semiconductor layer 54 and the opposite electrode 54 and is externally closed by the sealing knee 60 The conductor layer 54, the opposite electric drain 56, and the electrolysis (4) ' thereby avoiding the contact of the electrolyte 58 with the negative electrode, but the perfusion hole 52 for injecting the electrolyte 58 by the battery is sealed with the cover glass 62 and the thermal seal 64. The adhesion is less than ideal. After long-term exposure to high temperature exposure or high fishing environment, the hot melt 64 will cause aging to cause leakage. Secondly, the transparent substrate resistivity of the dyed battery is quite high, so the current conduction distance in the battery must be less than 1 cm, so that the battery efficiency can be avoided due to the loss of internal resistance, and the sensitized dye solar cell is required to generate electricity. When the amount reaches high power and high wattage, many small-area battery cells must be properly serially and parallelly designed. Therefore, large-area sensitive dye cells must first make internal current collection lines for most battery cells to improve their capacity. Conversion efficiency, and then the internal current collection line is brought out to form an external conductor to obtain the required power. At present, the battery module structure published at home and abroad can be roughly divided into, for example, the second (a) figure, type 0, first (b) The z-type of the figure, the W-type of the second (C) diagram, the S-type of the second (d) diagram, and the pattern published by the Republic of China Patent No. 1241721, except for the g-type. It is necessary to cut off the conductive film, but its efficiency is not good. The other four must cut the conductive film by laser scribing or knife wheel line drawing, so that the battery module array is 2~η rows, then use conductive material The method of printing of complex cross 201025626 repeatedly transferred 'to make the desired battery module, however such strict manufacturing process too complicated β view, to provide a dye-sensitized cell of the present invention, effective to improve the problem of the plurality. SUMMARY OF THE INVENTION The main object of the present invention is to provide a sensitized dye solar cell which can effectively reduce the possibility of volatilization of an organic solvent in an electrolyte, and can strengthen the battery structure to prevent electrolyte extravasation, thereby further facilitating long-term use of the battery. 0 The secondary object of the present invention is to provide a sensitized dye solar cell, which does not need to be cut when it is produced in a large area, and is connected to the outside of the battery unit directly after the completion of the production, thereby reducing the large-area process. The cumbersome steps to shorten the battery module production time. Still another object of the present invention is to provide a sensitized dye solar cell which enhances the effect of repeated reflection of light in a battery module, resulting in higher photoelectric conversion efficiency. For the above purposes, the dye-sensitized solar cell disclosed by the present invention comprises a first moon-permeable substrate, a first transparent substrate, a semiconductor layer, a counter electrode, a frame glue, and a plug; The transparent substrate and the second transparent substrate are disposed opposite to each other, and the inner surface of each transparent substrate carries a conductive film, and the second transparent substrate has a filling hole. The semiconductor layer is disposed on the conductive film of the first transparent substrate and carries a photosensitive dye, wherein the opposite electrode layer is disposed on the conductive film of the second transparent substrate and faces the semiconductor layer, and the electrolyte is located between the semiconductor layer and the opposite electrode layer, and is covered by the sealant of the sealant to avoid Electrolyte extravasation; embolization is to close the perfusion hole of the second transparent substrate through the adhesive, so that the electrolyte has no extravasation. It is easier to review the committee by the detailed description of the embodiment with the attached drawings. 7 201025626 Understand the purpose, technical content, characteristics and the effect achieved by the present invention. [Embodiment] The present invention is disclosed. A sensitized dye solar cell 'in addition to improving the packaging method to solve the problem of easy leakage of the electrolyte of the conventional sensitized dye solar cell, and making a large-area battery module in a simple manner. Referring to Fig. 4, it is a schematic structural view of a solar cell of the present invention. As shown in the figure, the present invention includes a first---second transparent substrate 12, 14' - a semiconductor layer 16, an opposite electrode φ layer 18, an electrolyte 20, a sealant 22, and a check plug 24. And an optically reflective layer 26. The transparent substrate 12 and 14 are electrically conductive, and the first transparent substrate 12 carries a first conductive film (TCO) 121 ′. The second transparent substrate 14 carries a second conductive film (TC 〇) 141. The two transparent substrates 12 and 14 are disposed correspondingly in a manner opposite to the conductive films (TC0) 121 and 141. Further, the second transparent substrate 14 has a filling hole M2. The semiconductor layer 16 is a nanocrystal layer and is disposed on the first conductive film (TC0) 121 of the first transparent substrate 12, and the layered body is impregnated with the photosensitive dye 161. The opposite electrode layer 18 is disposed on the second conductive film (TC〇) 141 of the second transparent substrate 14 and faces the semi-conductor layer 16. The electrolyte 20 is filled into the gap between the semiconductor layer 16 and the opposite electrode layer ι8 through the filling hole 142 of the second transparent substrate 14, and is sealed on the first transparent substrate 12 by the sealant 22 made of the polymer adhesive. Between the two transparent substrates 14, the sealant 22 covers the semiconductor layer 16, the opposite electrode layer 18, and the electrolyte 2'. The main point is that the plug 24 is made of glass or metal, and includes a column portion 241 and a cover portion 242 connecting the column portion 241, and the plug 24 and a thermoplastic polymer adhesive such as RTV glue, UV glue or AB glue. 28, in combination, the post portion 241 of the plug 24 is in close contact with the filling hole 142 of the second 201025626 transparent substrate 14, and the cover portion 242 is in close contact with the outer surface of the second transparent substrate 14. The optical reflective layer 26 is made of a reflective material, a reflective lens or a diffusion sheet, which is placed on the outer surface of the second transparent substrate 14, which can increase the light reflection effect in the battery and improve the light utilization efficiency. Thereby, the dye-sensitized solar cell of the invention is used as a sealing material and a perfusion hole material of the second transparent substrate by using a material which is not susceptible to corrosion and aging, thereby strengthening the battery structure, effectively avoiding the possibility of electrolyte extravasation and reducing the organic solvent in the electrolyte. The volatilization is more conducive to the long-term use of the battery. Furthermore, _ _ through the optical reflective layer can enhance the light utilization efficiency of the light in the battery module, increase the photoelectric conversion energy, and improve the efficiency of the battery. Of course, for the purposes of the present invention, the materials of the above-mentioned components can be easily and equally replaced by those skilled in the art. For example, the transparent substrate may be hard or soft, wherein the hard substrate may be conductive glass, and the flexible substrate may be one of PI, PE, PET, PVE, PP 'PS, PC, PMMA or the above materials. to make. The conductive film (TCO) can be formed using indium tin oxide (ITO) or fluorine-doped tin oxide (FT〇) or aluminum-doped zinc oxide (AZO). Further, the Q semiconductor layer may be an oxidized word (ZNO) in addition to titanium dioxide (Ti〇2). Similarly, the photosensitive dye may be selected from a ruthenium metal complex dye or an organic compound dye or a natural plant dye. The opposite electrode layer may be a platinum element or a carbon element. The electrolyte is preferably a liquid electrolyte such as iodine, potassium iodide, lithium iodide, ionic liquid, ethanol (Ethoal), acetonitrile (AcN) or methoxypropyl (MPN), etc., of course, it may be a colloidal electrolyte or Solid electrolyte" Finally, the choice of frame glue, such as glass glue, polymer adhesive (such as UV glue, AB glue, RTV glue). Therefore, the replacement of all materials should be considered as equalization of the present invention, and the scope of the invention should not be limited. 201025626 In addition, when actually manufacturing the sensitized dye solar cell of the present invention, it is possible to allocate the required power and wattage, and increase the battery mold boat transmission by appropriately connecting the series and parallel wiring =: and the round out county, see the fifth circle As shown in FIG. 6 , the battery structure described above is regarded as a single battery unit 1 , and the plurality of battery cells 10 are juxtaposed as required, so that the first transparent substrate I2 and the second transparent substrate M connected to the adjacent battery cells are connected. Then, at the beginning of the metal wire, such as steel, silver, 'tin wire such as tin or iron' or conductive rubber body such as silver glue, serially and parallelly increase the wheel iH dragon' on the outside of the battery unit 10, or to increase the parallel connection. Test (not shown). In this way, the sensitized dye solar cell of the invention does not need to be cut during large-area production. When the production is completed, the string and parallel connection are directly performed outside the battery unit, which can reduce the cumbersome steps of the large-area process and shorten the battery mode. Group production schedule. The above description is based on the embodiments of the present invention, and the purpose of the invention is to enable those skilled in the art to understand the present invention and to implement the invention without limiting the scope of the invention. Equivalent modifications or modifications made by the spirit of the invention should still be included in the scope of the claims described below. ® [Simple description of the diagram] Figure 1 is a schematic diagram of the structure of a conventional sensitized dye solar cell. Fig. 2(a) is a schematic view showing the structure of a conventional <3 type sensitized dye battery. Figure 2(b) is a schematic view showing the structure of a conventional Z-type sensitized dye battery. Figure 2(c) is a schematic view showing the structure of a conventional sensitized dye battery. Figure 2(d) is a schematic diagram of the structure of a conventional Type 8 sensitized dye battery. Figure 3 is a schematic view showing the structure of another sensitized dye battery. 201025626 Figure 4 is a side view of the structure of the sensitized dye solar cell of the present invention. Figure 5 is a front view of Figure 4. Figure 6 is a plan view of Figure 4. [Main component symbol description] 10 battery 12 first transparent substrate 121 first conductive film 14 second transparent substrate 141 second conductive film 142 filling hole 16 semiconductor layer 161 photosensitive dye 18 opposite electrode layer 20 electrolyte 22 frame glue 24 plug 241 column Portion 242 Cover portion 26 Optically reflective layer 28 Adhesive ❿ 30 Wire Usage Description: 51 Conductive film 52 Transparent substrate 521 Filling hole 53 Photosensitive dye 54 Semiconductor layer 56 Counter electrode 58 Electrolyte 60 Sealing 62 Slide 64 Thermal sol