TWI383511B - Electrochemical fabricating method thereof flexible dye-sensitized solar cell - Google Patents

Description

Electrochemical manufacturing method of flexible dye-sensitized solar cell

The present invention relates to a dye-sensitized solar cell and a method of manufacturing the same, and more particularly to a dye-sensitized solar cell having light weight and flexibility characteristics and an electrochemical manufacturing method thereof.

According to the US Department of Energy, the current global oil stock is about 40 years, the natural gas stock is about 60 years, and the coal stock is about 200 years. The global energy demand will reach twice the current level in 2050, and will reach the current three in 2100. In recent years, due to the soaring oil prices, the fourth energy crisis is about to come. The search for new energy has also become an industry that countries are currently developing. In recent years, due to the development of nanotechnology and advanced materials, it has helped to improve the conversion efficiency of solar cells. Therefore, single/polycrystalline solar cells, amorphous germanium solar cells, Improvements in technologies such as thin-film solar cells and wet solar cells are receiving attention from advanced countries.

At present, the main alternative energy sources are: fuel cell, methanol, biomass, bioenergy, solar energy, tidal energy and wind energy, etc., and this wave of green technology trends, and the most popular solar energy market is the most popular, due to the improvement of environmental awareness. The warning of the energy crisis has stimulated the vigorous development of the solar cell industry. Therefore, both academics and industry have invested considerable manpower and capital to develop solar cell-related technologies, and the government has regarded the solar cell industry as the next generation. One of the key development projects. Energy policy has long had a major impact on the economies, technology, and politics of nations. The impact of energy on countries around the world over the past few decades is as follows: 1954: Bell Labs publishes solar cells with 6% photoelectric conversion efficiency.

1957: The Soviet launches the first artificial satellite (Sputnik 1), using solar cells as a source of energy.

1973: The first oil crisis, the Middle East war raised oil prices from $3 per barrel to more than $13.

1979: The second oil crisis, the Iran-Iraq war caused oil prices to rise from $15 a barrel To $39.

1983: The United States establishes the world's largest solar power plant (16 MW) in California.

1990: The third oil crisis, the Gulf crisis caused crude oil to rise from $14 to $40 per barrel in three months.

1994: Japan implemented a subsidy incentive scheme to promote the "mains parallel solar photovoltaic system".

1997: Former US President Bill Clinton proposed the Million Roofs Solar Power program, which is expected to build 1 million solar power systems by 2010.

2008: Oil prices are $140 per barrel.

In the critical era of severe energy shortages and high environmental awareness, energy conservation and development of new energy sources have become an emerging industry in the global market, as the first and second generation solar cell processes need to be completed under the operation of clean rooms and vacuum equipment. Therefore, the equipment investment is relatively large, which makes the low-cost process of the third-generation solar cell widely accepted. Among them, the dye-sensitized solar cell (DSSC) has lower cost, flexibility and color. The characteristics of diversification, environmental protection, etc., have recently attracted the attention of academic research units and industrial investors. Swiss scientist Gratzel (1991) used titanium dioxide (TiO ₂ ) nanoparticles (NPs) as the anode of dye-sensitized solar cells to adsorb photosensitizing dyes and dye-sensitized solar cells with sandwich structures of conductive cathodes and electrolytes. Its photoelectric conversion efficiency is 7% (Reference 1). After more than a decade of development, the current efficiency is only 11% (References 2-4). In recent years, due to the development of nanotechnology and advanced materials, it will help to improve the conversion efficiency of solar cells. A typical dye-sensitized solar cell uses an N3 dye (LUMO=-0.71eV, HOMO=0.99eV) as an electron generating layer, and an TiO ₂ (VB=2.74eV, CB=-0.46eV) as an electron transport layer, and an electron. Separating from the hole, completing the work of the electron on the external circuit, and then passing the electron back to the electrolyte through the cathode to complete a series of complete electrochemical reactions.

The development of renewable energy characteristics and photoelectric conversion efficiency of solar cells has always been highly valued by various industrial countries. On the other hand, the cost of solar cell production and the power generated during use are even more One of the priorities of national energy policy, and environmentalists are more active in the assessment of the materials used in solar cells and the degree of environmental pollution in their production. Therefore, a solar cell that can be continuously developed should have characteristics such as low production cost, low power consumption rate, low environmental pollution materials, and low environmental pollution production process. In the various processes, the traditional anodizing process has the above characteristics, and the anodizing process is an electrolytic passivation process to increase the thickness of the oxide layer on the metal surface. This process is a mature industrial technology, between 1960 and 1990, Thompson and Wood. (References 5-9) A number of studies have been conducted on this aspect, and it has been found that an aluminum oxide surface can form a dense oxide film after electrochemical oxidation through the anode, and it is found that the oxide film can improve the corrosion resistance and wear resistance of the aluminum surface. Sex. Since 1997, Masuda (Ref. 10-12) used a secondary anodization process to prepare porous anodized aluminum with regular alignment and uniform pore shape. Later, porous alumina (Al ₂ O ₃ ) was used to prepare large areas. , self-assembled, and regularly arranged arrays of nanomaterials.

According to the previous experience in the production of Al ₂ O ₃ nanotubes, the anodic treatment of TiO ₂ nanotubes has a close relationship with the electrolyte composition, applied voltage, electrolyte stirring, and electrolyte temperature. For example, when the applied voltage is large, the anode film may have a large porous structure; when the electrolyte temperature is high, the dissolution rate of the film is faster, thereby obtaining a thinner final film thickness; and when in the electrolyte When the solute is more or less, it may have a lower growth rate of the oxide film.

The advantages of the nanotube-dye-sensitized solar cell (NT-DSSC) include: (1) Since the one-dimensional structure of the nanotube array is like a photonic crystal, it can collect light more efficiently and increase Photoelectric conversion efficiency; (2) Electron and hole shunting of the nanotube tube, the photoelectric conversion efficiency can be improved after the charge collection efficiency is improved; (3) The electrolyte solution is not easy to leak in the nanotube tube, and the durability can be increased; 4) The nanotube tube is directly formed on the Ti substrate by the anode treatment, which can shorten the process and reduce the cost; and (5) because the anode of the nanotube tube has the flexible property, it can be easily made into a large area. A flexible nanotube dye-sensitized solar cell.

Reference 1: M. Pourbaix, "Atlas of Electrochemical in Aqueous Solutions", NACE, USA, 280 (1974).

Reference 2: MKNazeeruddin, FDAngelis, S. Fantacci, A. Selloni, G. Viscardi, P. Liska, S. Ito, B. Takeru, M. Gr Tzel, J. Am. Chem. Soc. 127 (2005) 16835.

Reference 3: M. Wei, Y. Konishi, H. Zhou, M. Yanagida, H. Sugihara, H. Arakawa, J. Mater. Chem. 16 (2006) 1287.

Reference 4: N. Koide, A. Islam, Y. Chiba, L. Han, J. Photochem. Photobio. A 182 (2006) 296.

Reference 5: Spooner, R.C., J. Electrochem. Soc., 102 (1955) 156.

Reference 6: J. Brock, G. C. Wood, Electrochim. Acta, 12 (1967) 395.

Reference 7: G. C. Wood, A. J. Brock, Nature London, 209 (1968) 773.

Reference 8: G. C. Wood, J. P. O’Sullivan, Electrochim. Acta, 15 (1970) 1865.

Reference 9: G.E. Thompson, R.C. Furneanx: Corrosion Sci., 10 (1978) 4.

Reference 10: Jianling Zhao, Xiaohui Wang, Tieyu Sun, Longtu Li, Nanotechnology 16 (2005) 2450.

Reference 11: MKNazeeruddin, FDAngelis, S. Fantacci, A. Selloni, G Viscardi, P. Liska, S. Ito, B. Takeru, M. Gr Tzel, J. Am. Chem. Soc. 127 (2005) 16835.

Reference 12: M. Wei, Y. Konishi, H. Zhou, M. Yanagida, H. Sugihara, H. Arakawa, J. Mater. Chem. 16 (2006) 1287.

Flexibility is one of the main features of dye-sensitized solar cells. At present, many researches use screen printing to coat titanium dioxide (TiO ₂ ) nano particles on a flexible conductive material to form an anode of a dye-sensitized solar cell, and to form a flexible dye with a soft cathode. Sensitized solar cells. Further, according to the latest literature, a dye-sensitized solar cell element having an anode (NT, nanotube) structure has a photoelectric conversion efficiency higher than that of a dye-sensitized solar cell having a nanoparticle structure on the anode. Therefore, based on the above concept, the inventors of the present invention have proposed the present invention after conducting a series of detailed studies and experiments on dye-sensitized solar cells having large area, light weight, and flexible properties.

In view of the above problems, the technology used in the present invention is a mature anode treatment technology in the industry, and its low cost and automation characteristics will contribute to the mass production of dye-sensitized solar cell products in the future.

In order to solve the above problems, an embodiment of the present invention provides a flexible dye-sensitized solar cell comprising: a titanium (Ti) substrate whose surface is roughened, and a back surface thereof is subjected to thickness thinning; titanium dioxide ( The TiO ₂ ) nanotube is grown on the surface of the Ti substrate by anodizing and heat treatment before being subjected to thickness thinning treatment to serve as an anode of the battery; the photosensitive dye is adsorbed on the surface of the TiO ₂ nanotube a soft transparent conductive cathode disposed relative to the anode; and an electrolyte encapsulated between the cathode and the anode, wherein a surface of the transparent conductive cathode is attached with a platinum (Pt) nanocatalyst layer.

Another embodiment of the present invention provides a method for electrochemically manufacturing a flexible dye-sensitized solar cell, comprising the steps of: roughening a surface of a titanium (Ti) substrate; performing anodization on the Ti substrate, and then The heat treatment is performed, and a titanium oxide (TiO ₂ ) nanotube can be grown on the surface to serve as an anode of the battery; the photosensitive dye is adsorbed on the surface of the TiO ₂ nanotube; and the back surface of the Ti substrate is thinned; A transparent conductive oxide film and a platinum nanocatalyst layer are formed on the soft transparent material to serve as a cathode of the battery; and an electrolyte is encapsulated between the anode and the cathode.

Other objects and advantages of the present invention will become apparent from the following detailed description and appended claims.

In order to solve the above problems, according to an embodiment of the present invention, an electrochemical manufacturing method of a flexible dye-sensitized solar cell is provided, which is characterized in that the surface of the Ti substrate is roughened and anodized to increase the photosensitizing dye. The adsorption area of the anode surface is increased by the thickness reduction of the back surface of the Ti substrate to improve the flexibility of the battery element. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing the manufacture of a flexible dye-sensitized solar cell in accordance with an embodiment of the present invention. As shown in FIG. 1, in step 101, a Ti substrate is subjected to heat treatment at 600 ° C for 1 hr to eliminate stress on the Ti substrate.

In step 102, the surface of the Ti substrate is pickled with conditions of 3 vol.% H ₃ PO ₄ + 2 vol.% HF, 3 min, etc., to remove the TiO ₂ film produced by the heat treatment.

In step 103, the surface of the Ti substrate is subjected to a roughening treatment such as electrolytic etching using conditions of 3 vol.% HF + 5 wt.% NaCl, and 30 V × 1 min to obtain a roughened surface. In an embodiment of the present invention, the electrolytic solution for electrochemically etching the surface roughening may contain one of the following halogen elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), Or 砈 (At); and the electrolyte containing chlorine ions may be, for example, hydrochloric acid (HCl), sodium chloride (NaCl), or perchloric acid (HClO ₄ ), etc., and the electrolyte containing fluorine ions may be, for example, hydrogen. Fluoric acid (HF), potassium fluoride (KF), or ammonium fluoride (NH ₄ F). However, the surface roughening treatment is not limited to electrolytic etching, and in other embodiments of the present invention, the surface roughening treatment may include a plasma dry etching treatment, a mechanical grinding, or a sandblasting treatment, or the like.

In step 104, the surface of the roughened Ti substrate is anodized using an electrolyte having a concentration of 0.2% to 5% fluoride ion (F ⁻ ) and a condition of 20 to 100 V×1 to 24 hr to grow TiO _{2 .} Nano tube. The thickness of the TiO ₂ nanotubes can range between about 0.1 μm and about 100 μm.

In step 105, the TiO ₂ nanotube is subjected to a heat treatment at 450 ° C × 3 hr to obtain a TiO ₂ nanotube having an anatase structure.

In step 106, the photosensitizing dye is adsorbed onto the surface of the TiO ₂ nanotube.

In step 107, the back surface of the Ti substrate is subjected to thickness thinning treatment under conditions of 10 vol.% HF × 6 min or the like to obtain a flexible anode. In the embodiment of the present invention, the thickness thinning treatment may use a chemical etching liquid or an electrochemical electrolysis method to thin the thickness of the back surface of the Ti substrate; and the electrolyte used in the chemical etching liquid and the electrochemical electrolysis method may include: A hydrofluoric acid solution, a nitric acid solution, a hydrochloric acid solution or a mixture thereof. The thickness of the Ti substrate can range between about 30 μm and about 200 μm after the thickness reduction process. When the Ti substrate on which the TiO ₂ nanotubes are formed has the above thickness, it can be made into a roll-to-roll type solar cell material. With this configuration, it is possible to manufacture a roll-to-roll type flexible dye-sensitized solar cell. Moreover, in another embodiment, the thickness thinning process in step 107 can be performed prior to step 106.

In step 108, a transparent conductive oxide (TCO) film and a platinum nanocatalyst layer are formed on the soft transparent material to obtain a flexible cathode. In an embodiment of the present invention, the soft transparent material may be polyethylene naphthalate (PEN) or polyethylene terephthalate (PET) polymer transparent material; and transparent conductive oxidation The film may be indium tin oxide (ITO), antimony tin oxide (ATO), fluorine tin oxide (FTO), aluminum zinc oxide (AZO, aluminum zinc oxide). ), or indium zinc oxide (IZO). In addition, in order to increase the transmittance of incident light to a soft transparent material and to increase the water blocking and gas blocking rate of the soft transparent material, an anti-reflection (AR) layer may be formed on the surface of the soft transparent material.

In step 109, an acetonitrile (CH ₃ CN) electrolyte containing iodine (I ₂ ) and lithium iodide (LiI) is encapsulated between the cathode and the anode to obtain a flexible dye-sensitized solar energy using a soft encapsulant. battery. The soft encapsulant can be an ultraviolet (UV) ultra-violet or a thermoset/shrink.

In another embodiment of the present invention, the Ti substrate can be replaced by a soft transparent substrate, and a Ti film is formed on the surface of the flexible transparent substrate in advance, and then TiO ₂ is grown on the surface of the Ti film by anodizing and heat treatment. Nano tube, and the soft encapsulant is used to encapsulate the electrolyte between the cathode and the anode which are both transparent and soft, to produce a transparent flexible dye-sensitized solar cell capable of front/back illumination, wherein the front illumination refers to light. The light is incident from the anode side to the inside of the solar cell, and the back side illumination means that light is incident from the cathode side to the inside of the solar cell. Therefore, the solar cell produced by the method of Fig. 1 is a back-illuminated flexible dye-sensitized solar cell. When heat treating a soft transparent substrate having a TiO ₂ nanotube thereon, heat treatment may be performed by microwave heating, laser heating, or infrared light heating to protect a soft transparent substrate having a lower melting point.

In another embodiment of the invention, the titanium substrate can be a titanium alloy, such as a Ti-6Al-4V alloy or the like. In other embodiments of the present invention, the titanium substrate may be replaced by one of the following substrates: germanium (Si), indium (In), tungsten (W), zirconium (Zr), zinc (Zn), or tin (Sn). And the material of the oxide nanotube on the substitute substrate corresponding to the substitute substrate may be ceria (SiO ₂ ), indium trioxide (In ₂ O ₃ ), tungsten trioxide (WO ₃ ), Zirconia (ZrO ₂ ), zinc oxide (ZnO), or tin dioxide (SnO ₂ ). Further, the surface of the TiO ₂ nanotube may have TiO ₂ nanoparticles to increase the surface area of the TiO ₂ nanotubes, and these TiO ₂ nanoparticles are formed using a TiF ₄ or TiCl ₄ solution.

In order to clarify the manufacturing flow of FIG. 1, FIGS. 2A to 2E schematically show manufacturing diagrams in accordance with the embodiment of FIG. 1. In FIGS. 2A to 2E, first, a TiO ₂ nanotube 3 (as shown in FIG. 2B) is grown on the surface of the Ti substrate 1, and then a photosensitive dye (not shown) is adsorbed on the surface of the TiO ₂ nanotube 3. Upper (as shown in Fig. 2C, wherein the oblique line portion is the TiO ₂ nanotube 3 whose surface has adsorbed the photosensitizing dye), and then the thickness of the back surface of the Ti substrate 1 is thinned (as shown in Fig. 2D), and finally, The soft encapsulant 11 encapsulates the electrolyte 13 in a cathode region including the soft transparent material 5, the transparent conductive oxide film 7, and the platinum nanocatalyst layer 9, and the TiO ₂ including the Ti substrate 1 and the surface-adsorbed photosensitive dye thereon. Between the anode regions of the nanotubes 3 (as shown in Figure 2E). The thickness thinning treatment is preferably performed after the formation of the TiO ₂ nanotubes 3. If the thickness thinning treatment is performed before the formation of the TiO ₂ nanotubes 3, the TiO ₂ nanotubes 3 may be from the Ti substrate due to the action of stress. The surface of 1 is peeled off, and therefore, the thickness thinning treatment is preferably performed after the formation of the TiO ₂ nanotubes 3. The working principle of such a solar cell is that when the battery is illuminated, electrons generated by a photosensitive dye (not shown) are transferred via the TiO ₂ nanotube 3 (at the same time, the electrolyte 13 undergoes an oxidation reaction and transmits the electron to the photosensitive dye). After the external circuit (not shown), the transparent conductive oxide film 7 enters the electrolyte 13 to carry out a reduction reaction to complete the cycle of the electrochemical reaction.

(Example of implementation)

After heat treatment of a commercial Ti substrate (99.7%, 0.127 mm) at 600 ° C × 1 hr, we can obtain a uniform α phase titanium metallographic microstructure, and then pickle the surface of the Ti substrate (3 vol.% H ₃ PO ₄ +2 vol.% HF, 3 min) to remove the TiO ₂ film produced by the heat treatment, followed by electrolytic etching (3 vol.% HF + 5 wt.% NaCl, 30 V, 1 min) on the surface of the Ti substrate. For the rougher surface, the Ti substrate was anodized in the following three conditions: (1) 0.5 vol.% HF, 18V; (2) 0.58 wt.% KF+13.8 wt.% NaHSO ₄ . 2H ₂ O+5.9 wt.% C ₆ H ₅ Na ₃ O ₇ . 2H ₂ O, 25V; and (3) 0.25 wt.% NH ₄ F+ ethylene glycol solvent, 60V. By performing the anodizing treatment under the above three conditions, a TiO ₂ array having a nanotube structure can be grown on the surface of the Ti substrate. 3A to 3C respectively show microscopic images of TiO ₂ nanotube arrays obtained by anodizing with the above conditions (1), (2), and (3).

In order to improve the flexibility and reduce the weight of the dye-sensitized solar cell, the material of the dye-sensitized solar cell must have lightweight characteristics, for example, the density of the Ti substrate used in the embodiment of the present invention is about 4.5 g. Cm ^-3 , and polyethylene terephthalate (PEN) and polyethylene terephthalate (PET) soft transparent polymer material density of about 1.4 g. Cm ^-3 . Although the density of the Ti substrate is slightly larger than the density (2.5 g.cm ^-3 ) of the commonly used glass material of the conventional dye-sensitized solar cell, the thickness of the monolithic glass is about 2000 μm, and the Ti substrate and The polyethylene terephthalate (PEN) or polyethylene terephthalate (PET) material requires only about 80 μm in thickness, and therefore, a dye-sensitized solar cell made of a Ti substrate and a polymer material is used. The weight is only 4.7% of the dye-sensitized solar cells using glass materials.

A flexible dye-sensitized solar cell can be obtained by blending a dye-sensitized solar cell anode prepared according to the method of the present invention with a soft transparent conductive cathode. Figure 4A 4B is a photograph of an anode and a cathode of a flexible dye-sensitized solar cell according to an embodiment of the present invention, and FIG. 4C is a flexible type made of the anode and the cathode of FIGS. 4A and 4B, respectively. Photograph of dye-sensitized solar cells.

5 is a graph showing current density-voltage characteristics of a flexible dye-sensitized solar cell under the test conditions of a standard solar light source of an air mass of 1.5 in accordance with an embodiment of the present invention. As shown in Fig. 5, the flexible active area is 20.25 cm ² and the short circuit current density (Jsc) is 6.6 mA. Cm ^-2 , open circuit voltage (Voc) was 0.72 V, filling ratio (FF) was 0.32, and photoelectric conversion efficiency (η) was 1.51%.

Therefore, according to the method of the present invention, it is possible to manufacture a dye-sensitized solar cell having a large area, a lightweight, and a flexible property.

Although the present invention has been particularly shown and described with reference to the exemplary embodiments thereof, the invention is not limited to the embodiments. Variations in the various forms and details may be made without departing from the spirit and scope of the invention as defined by the appended claims.

1‧‧‧Ti substrate

3‧‧‧TiO ₂ nanotubes

5‧‧‧Soft transparent materials

7‧‧‧Transparent conductive oxide film

9‧‧‧Platinum catalyst layer

11‧‧‧Soft package adhesive

13‧‧‧ electrolyte

101‧‧‧ Heat treatment of Ti substrate to eliminate stress on Ti substrate

102‧‧‧Pickling the surface of the Ti substrate to remove the TiO ₂ film produced by the heat treatment

103‧‧‧Roughening the surface of the Ti substrate to obtain a rougher surface

104‧‧‧Anode treatment of the surface of the roughened Ti substrate to grow TiO ₂ nanotubes

105‧‧‧ of TiO ₂ nanotubes subjected to heat treatment to obtain a phase having anatase (Anatase) TiO ₂ nanotube structure

106‧‧‧Adsorbing photosensitizing dye on the surface of TiO ₂ nanotubes

107‧‧‧Thickening the back side of the Ti substrate to obtain a flexible anode

108‧‧‧ Forming a transparent conductive oxide film and a platinum nanocomb layer on a soft transparent material to obtain a flexible cathode

109‧‧‧Encapsulate the electrolyte between the cathode and the anode with a soft encapsulant to obtain a flexible dye-sensitized solar cell

1 shows a manufacturing flow chart of a flexible dye-sensitized solar cell according to an embodiment of the present invention; FIGS. 2A to 2E schematically show a manufacturing schematic according to the embodiment of FIG. 1; FIGS. 3A to 3C respectively show different conditions. Photomicrograph of TiO ₂ nanotube array obtained by anodizing; FIGS. 4A and 4B are photographs of an anode and a cathode of a flexible dye-sensitized solar cell according to an embodiment of the present invention; FIG. 4C is 4A and 4B are photographs of a flexible dye-sensitized solar cell made of an anode and a cathode; and FIG. 5 is a current density-voltage of a flexible dye-sensitized solar cell according to an embodiment of the present invention. Characteristic curve.

101‧‧‧ Heat treatment of Ti substrate to eliminate stress on Ti substrate

102‧‧‧Pickling the surface of the Ti substrate to remove the TiO ₂ film produced by the heat treatment

103‧‧‧Roughening the surface of the Ti substrate to obtain a rougher surface

104‧‧‧Anode treatment of the surface of the roughened Ti substrate to grow TiO ₂ nanotubes

105‧‧‧ of TiO ₂ nanotubes subjected to heat treatment to obtain a phase having anatase (Anatase) TiO ₂ nanotube structure

106‧‧‧Adsorbing photosensitizing dye on the surface of TiO ₂ nanotubes

107‧‧‧Thickening the back side of the Ti substrate to obtain a flexible anode

108‧‧‧ Forming a transparent conductive vapor film and a platinum nanocomb layer on a soft transparent material to obtain a flexible cathode

109‧‧‧Encapsulate the electrolyte between the cathode and the anode with a soft encapsulant to obtain a flexible dye-sensitized solar cell

Claims (18)

An electrochemical manufacturing method of a flexible dye-sensitized solar cell, comprising: roughening a surface of a titanium (Ti) substrate; then anodizing the Ti substrate, and then performing heat treatment, wherein the surface can be on the surface Growing a titanium dioxide (TiO ₂ ) nanotube as an anode of the battery; adsorbing a photosensitive dye on the surface of the TiO ₂ nanotube; performing thickness thinning on the back surface of the Ti substrate; A transparent conductive oxide film and a platinum (Pt) nanocatalyst layer are formed on the material to serve as a cathode of the battery; and an electrolyte is encapsulated between the anode and the cathode. The method for electrochemically manufacturing a flexible dye-sensitized solar cell according to claim 1, wherein the surface roughening treatment of the substrate is electrochemical wet etching, plasma dry etching, mechanical grinding, or sand blasting. Handle one of them. The method of electrochemically manufacturing a flexible dye-sensitized solar cell according to claim 1, wherein the electrolyte is encapsulated between the cathode and the anode with a soft encapsulant. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 3, wherein the soft encapsulant is an ultraviolet glue or a thermosetting/shrinking glue. The scope of the patent electrochemical method of manufacturing a flexible dye-sensitized solar cell of item 1, wherein TiCl ₄ or TiF ₄ to form TiO ₂ nano particles solution on the surface of the TiO ₂ nanotube. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 1, wherein the anodized electrolyte is an electrolyte containing fluoride ion (F ^- ). The method for electrochemically producing a flexible dye-sensitized solar cell according to claim 1, wherein the thickness thinning treatment is performed by using a chemical etching solution or an electrochemical electrolytic method to reduce the thickness of the back surface of the Ti substrate. The method for electrochemically manufacturing a flexible dye-sensitized solar cell according to claim 7, wherein the chemical etching solution and the electrolyte used in the electrochemical electrolysis method comprise: a hydrofluoric acid solution, a nitric acid solution, and a hydrochloric acid solution. , or a mixture thereof. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 1, wherein an antireflection layer is formed on the surface of the soft transparent material. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 1, wherein the Ti substrate can be replaced by a soft transparent material, and a Ti film is formed on the surface of the soft transparent material in advance. Anodizing and heat treatment are then performed to grow the TiO ₂ nanotubes. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 10, wherein the heat treatment can be performed by microwave heating, laser heating, or infrared light heating. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 1, wherein the Ti substrate can be substituted with a Ti alloy substrate. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 12, wherein the Ti alloy substrate is a Ti-6Al-4V alloy. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 1, wherein the Ti substrate can be replaced by one of the following substrates: germanium (Si), indium (In), tungsten (W), Zirconium (Zr), zinc (Zn), or tin (Sn); and the material of the oxide nanotube on the substitute substrate corresponding to the substitute substrate is ceria (SiO ₂ ), indium trioxide (In ₂ O ₃ ), tungsten trioxide (WO ₃ ), zirconium dioxide (ZrO ₂ ), zinc oxide (ZnO), or tin dioxide (SnO ₂ ). An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 1, wherein the substrate is subjected to heat treatment in advance and then pickled before the roughening treatment. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 1, wherein the TiO ₂ nanotube has a thickness ranging between about 0.1 μm and about 100 μm; and the thickness is thinned The thickness of the Ti substrate after the treatment can range between about 30 μm and about 200 μm. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 16, wherein the Ti substrate having the TiO ₂ nanotube thereon can be rolled-to-rolled Type of solar cell material. An electrochemical manufacturing method of a flexible dye-sensitized solar cell according to claim 2, wherein the electrochemical wet etching electrolytic solution contains one of the following halogen elements: fluorine (F), chlorine (Cl), Bromine (Br), iodine (I), or hydrazine (At); and the chlorine-containing electrolyte is one of hydrochloric acid (HCl), sodium chloride (NaCl), or perchloric acid (HClO ₄ ), and the The electrolyte of fluorine is one of hydrofluoric acid (HF), potassium fluoride (KF), or ammonium fluoride (NH ₄ F).