TW201016668A - Ruthenium complex and photoelectric component using the same - Google Patents

Abstract

The present invention relates to a ruthenium complex and a photoelectric component using the same, and the ruthenium complex is represented by the following formula (I): RuL2(NCS)2Am (I) wherein L, A and m are defined the same as the specification. The ruthenium complex of the present invention is suitable for Dye-Sensitized Solar Cell (DSSC). Hence, the photoelectric characteristics of the DSSC manufactured with the ruthenium complex of the present invention can be improved.

Description

201016668 VI. Description of the Invention: [Technical Field] The present invention relates to a base metal complex and a photovoltaic element produced using the same, in particular to a dye-sensitized solar cell 5 (Dye-Sensitized Solar) Cell, DSSC) metal complex and dye-sensitized solar cells. [Prior Art] ® With the development of human civilization, the world faces serious energy crisis and environmental pollution. The photoelectric solar cell converts solar direct electricity into electric energy, which is an important method to solve the global energy crisis and reduce environmental pollution. A dye-sensitized solar cell is a promising new type of solar cell because of its low manufacturing cost, large area, flexibility, and light transmittance for use on buildings. 15 In recent years, GrStzel et al. published a series of related literatures on dye-sensitized solar cells (eg, O'Regan, B.; Gratzel, M. Nature 1991, 353, ❹ 737), showing the utility of dye-sensitized solar cells. In general, the structure of a dye-sensitized solar cell includes a cathode/anode electrode, a nano titanium dioxide, a dye, and an electrolyte; a dye in a dye-sensitized solar cell has a critical influence on the efficiency of the battery 20, and an ideal dye has an Absorbs a wide range of solar spectrum, high absorption coefficient, high temperature stability and light stability.

Gratzel Laboratories has published a series of complexes as dyes in dye-sensitized solar cells. In 1993, Gratzel Laboratories published a dye-sensitized solar cell prepared using N3 Dye 4 201016668 with an efficiency of 10.0% (AM 1.5). The single-wave photo-current conversion efficiency (IPCE) of the N3 dye can reach 80% in the range of 400 nm to 600 nm, and hundreds of dye complexes developed thereafter cannot exceed the N3 dye. The structure of the N3 dye is as shown in the following formula (a).

2003 ίο Until 2003, Gratzel Laboratories published a dye-sensitized solar cell prepared using N719 dye, which increased its efficiency to 10.85% (AM 1.5). The structure of the N719 dye is as shown in the following formula (b).

COOTBA (b) 5 201016668 Then in 2004, the same laboratory published a dye-sensitized solar cell using Black dye, which achieved an efficiency of 11.04% (AM 1.5). The black dye enhances the spectral response of the red and infrared regions, thereby improving the performance of the dye-sensitized solar cell. The structure of the black dye is as shown in the following formula (c).

COOTBA Λ

TBAOOC

VN\

HOOC

/NCS Ru ~NCS NCS (C) 10

15 In addition to the related series of N3 dyes, N719 dyes and black dyes published by Gratzel Laboratories, other similar compounds are platinum complexes, ruthenium complexes, iron complexes, and copper complexes. ..and many more. However, after many studies, the efficiency of the ruthenium complex is still better. Dyes in dye-sensitized solar cells have a critical impact on cell efficiency. Therefore, finding dye molecules that can improve the efficiency of dye-sensitized solar cells is one of the important methods to improve the efficiency of dye-sensitized solar cells. SUMMARY OF THE INVENTION The present invention provides a novel base metal complex which is suitable for dye-sensitized solar cells and which can increase the photoelectric efficiency of dye-sensitized solar cells. 6 201016668 The present invention further provides a dye-sensitized solar cell which has a high photoelectric efficiency. The base metal complex of the present invention has the following formula (I) ·' 5 ❹ 10 15 20

RuL2(NCS)2Am (I) where is 2,2'-double. Than 4,4'-dicarboxylic acid (2,2'-1^卩>^£171-4,4'-dicarboxylic acid), 2,2,-bipyridine-4,4,-disulfonic acid (2,2-bipyridyl-4,4'-disulfonic acid) or 2,2'-bis 0-bit 4,4'-diphosphate (2,2-bipyridyl-4,4,-diphosphonic acid); A It is a quaternary cation (qUaternary ph〇Sphonium cation); m is 1, 2, 3, or 4. In the above formula (I), L may be 2,2,-bipyridine-4,4,-dicarboxylic acid, 2,2,-bispyridyl-4,4-one-pot acid or 2,2'-double Acridine _4,4'-discalic acid. Preferably, L· is a 2,2'-double ratio. _4,4'-dicarboxylic acid. In the above formula (I), Α may be a quaternary cation (quaternary Ph〇Sph〇niUm Cati〇n); preferably, A is P+RlR2R3R4, wherein Ri, R2'R3' and R4 are each independently For Ci 2. The base (4) (4)), the phenyl (10) (3) state or the benzyl group (benZyl); more preferably 'A is a tetraalkyl scale, a benzyltrialkyl scale or a phenyl trialkyl scale, wherein the radical is a heart. Burning base. In the above formula (I), m may be 2 or 3; more preferably 'm is 2. 2, 3, or 4, preferably, m specific examples of the ruthenium metal complex of the above formula (1) are: 7 201016668

(Μ)

(1-2) 8 201016668

❹ 5 (1-4) A dye-sensitized solar cell provided by the present invention contains the above-described ruthenium metal complex. Further, the dye-sensitized solar cell of the present invention comprises: a photoanode containing the above-described base metal complex; a cathode 10; and an electrolyte layer between the photoanode and the cathode. ° 9 201016668 In the dye-sensitized solar cell of the present invention, the photoanode includes: a transparent substrate, a transparent conductive film, a porous semiconductor film, and a ruthenium metal complex dye. In the dye-sensitized solar cell of the present invention, the material of the photoanode is transparent. The material of the substrate is not particularly limited, and any substrate can be used as long as it is transparent. Preferably, the material of the transparent substrate is a transparent substrate having good barrier properties, fuel solubility, weather resistance and the like for moisture or gas intruded from the outside of the dye-sensitized solar cell. Specific examples of transparent substrates include transparent inorganic substrates such as quartz and ® glass; polyethylene terephthalate (PET), poly(naphthalene dicarboxylate) (PEN), and polycarbonate (PC). ), a transparent plastic substrate such as polyethylene (PE), polypropylene (PP), or polyimide (PI), but is not limited thereto. Further, the thickness of the transparent substrate is not particularly limited, and can be freely selected in accordance with the light transmittance and the characteristics of the dye-sensitized solar cell. Preferably, the transparent substrate is made of glass. Further, in the dye-sensitized solar cell of the present invention, the material of the transparent conductive film may be indium tin oxide (ITO), fluorine-doped tin oxide (FT〇), zinc antimonide-digallium dioxide (Zn). 〇-Ga2〇3), zinc oxide-three-oxides (ΖηΟ-Α12〇3), or yttrium-based oxide materials. Further, in the dye-sensitized solar cell of the present invention, the porous semi-conductor film is made of +conductor particles. Suitable germanium conductor particles may include: dream, dioxins, tin dioxide, zinc oxide, trioxane, bismuth oxide, lithium titania, and combinations thereof; preferably, the semiconductor particles are titanium dioxide. The semiconductor fine particles have an average particle diameter of 5 to 5 nm, preferably 10 to 50 nm. The thickness of the porous semiconductor film is 5 to 25 μm. 201016668 'In the dye-sensitized solar cell of the present invention, the ruthenium metal complex dye is a ruthenium metal complex as described above. Further, the cathode material as the dye-sensitized solar cell is not particularly limited and may include any material having conductivity. Alternatively, the cathode material 5 may be an insulating material as long as a conductive layer is formed on the surface facing the photoanode. Electrochemically stable materials are useful as cathodes, and non-limiting examples of suitable cathode materials include platinum, gold, carbon, and the like. Further, the electrolyte layer as the dye-sensitized solar cell is not particularly limited and may include any substrate having electron and/or hole conductivity. [Embodiment] The base metal complex of the present invention can be synthesized in the following manner. --Dithiocyano bis(2,2'-bipyridine-4,4'-didecanoyl) ruthenium (II) (c/i-di(thiocyanato)-iV, J/V, -bis(2 , 2,-bipyridyl-4,4,-15 dicarboxylic acid)ruthenium(II), N3 dye) synthesized according to the method of Inorganic C/zewk/r;)/, Vol. 38, No. 26, 1999, 6298-6305 . Dissolve gal-dithiocyano-stupid (2,2,-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) in distilled water, and then add 10% oxytetra-n-butyl squama An aqueous solution (tetrabutylphosphonium hydroxide reagent, TCI Co. Ltd.) was added to the reaction solution until the pH of the reaction solution reached 11 and then concentrated to obtain a viscous liquid. The viscous liquid was dissolved in methanol, and then the product was precipitated by adding diethyl ether. The hygroscopic solid product was taken out and dried under vacuum for one day. The dried solid was dissolved in distilled water, and the pH was adjusted to 5 or less with a 0.1 Torr aqueous solution of nitric acid to obtain a ruthenium metal complex of the formula (1-1). 11 201016668 The method for producing the dye-sensitized solar cell of the present invention is not particularly limited and can be produced by a generally known method. The material of the transparent substrate is not particularly limited as long as it is a transparent substrate. Preferably, the material of the transparent substrate is a transparent substrate having good barrier properties, solvent resistance, weather resistance and the like for moisture or gas in which the battery is externally infiltrated by the dye sensitized sun 5 10 15 ❹ 20, specifically, There are transparent inorganic substrates such as quartz and glass, polyethylene terephthalate (PET), poly(ethylene naphthalate) (PEN) polycarbonate (PC), polyethylene (PE), and polypropylene (pp). A transparent plastic substrate such as polyimine (PI), but is not limited thereto. The thickness of the transparent substrate is not particularly limited and can be freely selected by the light transmittance and the characteristics of the dye-sensitized solar cell. In a specific example, the transparent substrate is a glass substrate. The material of the transparent conductive film may be selected from the group consisting of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), oxidized-bis-gallium trioxide (ZnO-Ga2〇3), and oxidized _ aluminum oxide (ZnO) -Al^3), and bismuth-based oxide materials. In the specific example, the transparent conductive film is tin oxide doped with fluorine. The porous semiconductor film is made of semiconductor fine particles. Suitable semiconductor particles include pulverized, dioxins, tin dioxide, zinc oxide, tungsten trioxide pentoxide, titanium oxide and combinations thereof. First, the semiconductor fine particles are first formulated into a paste, which is then applied to a transparent conductive substrate by a doctor blade, screen printing, spin coating, spray or the like or wet coating. Further, in order to obtain an appropriate film thickness, it may be applied one or more times. = The conductor film layer may be a single layer or a plurality of layers. The term "multilayer" means that the layers use semiconductor particles of different particle diameters. For example, semi-conductive 12 201016668 bulk particles having a particle diameter of 5 to 5 nanometers may be coated first, and coated with a thickness of 5 to 20 micrometers, and then coated with semiconductor particles having a particle diameter of 200 to 400 nm. The coating thickness is 3 to 5 microns. Then, after drying at 5 Torr to 100 ° C, 'more 400 to 5 〇 (TC can be sintered for 30 minutes to obtain a multilayer semiconductor film layer. 5 10 15 20 ruthenium metal complex dye can be dissolved in a suitable solvent. A dye solution. Suitable solvents include acetonitrile, decyl alcohol, ethanol, propanol, butanol, dimethylformamide, N-methylpyrrolidone or a mixture thereof, but are not limited thereto. The transparent substrate coated with the semiconductor film is immersed in the dye solution to fully absorb the dye in the dye solution, and is taken out and dried after the dye absorption is completed, thereby obtaining a photoanode of a dye-sensitized solar cell. Any material having conductivity may be included without limitation, or the cathode material may be an insulating material as long as a conductive layer is formed on the surface facing the photoanode. Further, an electrochemically stable substance can serve as a cathode, and Non-limiting examples of suitable cathode materials include: platinum, gold, carbon, and the like. The electrolyte layer is not particularly limited and may include any electron and/or hole transmission. In addition, the liquid electrolyte may be a solution containing (iv) acetonitrile solution, a moth-containing NH (four) solution, or a ruthenium-containing 3_-h-propoxypropane solution. In one embodiment, the liquid electrolyte is-containing Acetonitrile of iodine The dye-sensitized solar cell of the present invention is specifically produced as follows. First, a paste having a particle size of 2 〇 3 to 3 Å is included, which is difficult to be 々* 不* >, (nm Titanium oxide micro-twist-: man or several times of screen printing on a tin oxide (FTO) glass plate covered with fluorine doping 13 201016668 • and then sintered at 450 ° C for 30 minutes. The solution is dissolved in a mixture of acetonitrile and tri-butanol (1:1 v/v) to form a ruthenium metal complex dye solution. Next, the above-mentioned porous titanium oxide is contained. The glass plate of the film is immersed in the dye 5 solution, so that it absorbs the dye in the dye solution, and then taken out and dried to obtain a photoanode. The fluorine-doped tin oxide glass plate is drilled to have a diameter of 0.75 mm. The injection port is used for injecting electrolyte. The vaporized platinum acid (H2PtCl6) is dissolved. It is coated on a fluorine-doped tin oxide glass plate and then heated to 400 10 ° C for 15 minutes to obtain a cathode. Then, a 60 μm thick thermoplastic polymer film is disposed on the photoanode and Between the cathodes, a pressure is applied to the two electrodes at 120 to 140 ° C to bond the two electrodes. The electrolyte (0.03 Μ Ι 2/0·3 M LiI/0.5 Μ tri-butyl pyridine in an ethyl 15 nitrile solution) The dye-sensitized battery of the present invention can be obtained by injecting and sealing the injection port with a thermoplastic polymer film. The following examples are merely illustrative of the invention, and the scope of the invention is not limited thereby. Unless otherwise stated, the temperature is in degrees Celsius and the parts and percentages are by weight. The relationship between parts by weight and parts by volume is as much as the relationship between kilograms and liters. Example 1 Synthesis of 膺-dithiocyanobis(2,2,-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) bis(benzyltributylammonium) (c^-di(thiocyanato) -7V, A^-bis(2,2'-bi 25 pyridy 1-4,45-dicarboxy lie acid)ruthenium(II)bis(tetrabutyl 14 201016668 * phosphonium)) (1-1) 0.50 parts Thiocyanyl-W'·bis(2,2,-bipyridine-4,4'-dicarboxylic acid) ruthenium (II) (cz5-di(thiocyanato)-iV,^,-bis(2,2,- Bipyridyl-4,4'-dicarboxylic acid)ruthenium(II), N3 dye) (according to 5 Inorganic Chemistry, Vol. 38, No. 26, 1999, 6298-6305 ^ synthesis) and 10 parts of distilled water added to the reaction flask for stirring After mixing, a 10% tetrabutylphosphonium hydroxide reagent (TCI Co. Ltd.) was added dropwise to the reaction solution until the pH of the reaction solution was stable to 11, and then a rotary evaporator (rotary) was used. -evaporator) 10 Evaporate the solvent to give a viscous liquid. Next, the viscous liquid was dissolved in methanol, and diethyl ether was added to produce a precipitate. The hygroscopic solid product was taken out and dried under vacuum for one day. The dried solid was dissolved in 10 parts of steamed water, and the pH was adjusted to 5 or less with a 0.1 Torr aqueous solution of nitric acid, and the product was collected by filtration using a sintered glass filter 15 and used. The product was washed with 5 parts of distilled water of pH 5 to obtain 0.39 parts of a black solid product of formula (1-1), yield 75.9%. Example 2 Production of Dye-Sensitized Solar Cell 20 A paste comprising titanium oxide fine particles having a particle diameter of 20 to 30 nm is coated with fluorine by one or several screen printings. A doped tin oxide (FTO) glass plate (thickness 4 mm, resistance ΙΟ Ω / port) was applied so that the sintered porous titanium oxide film had a thickness of 10 to 12 μm, and then sintered at 45 ° C for 30 minutes. 25 The base metal complex of Example 1 was dissolved in a mixture of acetonitrile and 15 201016668 . Sanyi butanol (tetra) utanol (1) wv), and the concentration of the ruthenium metal complex was 0.5 Μ. a dye solution, and then immersing the above-mentioned glass plate containing a porous titanium oxide film in a dye solution, allowing it to absorb the dye in the dye solution for 16 to 24 hours, and then taking out and drying to obtain a photoanode 5 (photoanode) ° will cover A fluorine-doped tin oxide glass plate is drilled with a diameter of 〇·75 mm' for injection into the electrolyte, and then the vaporized acid solution (containing 2 mg of platinum in liter of ethanol) is coated on the tin oxide glass plate. Then, φ is heated to 400 ° C for 15 minutes to obtain a cathode (cath〇de). 10 A thermoplastic polymer film having a thickness of 60 μm is disposed between the photoanode and the cathode. A pressure is applied to the two electrodes at 120 to 140 ° C to bond the electrodes. The electrolyte (0.03 Μ I2/0.3 M LiI/0.5 Μ tertiary butyl b is immersed in a acetonitrile solution) is injected into the thermoplastic polymer film to seal the injection port, and the dye-sensitized solar cell of the 15th embodiment can be obtained. . ❷ 20 Comparative Example A dye-sensitized solar cell was prepared in the same manner as in Example 2 except that ruthenium 719 was used instead of the ruthenium metal complex of Example 1. Test Methods and Results Photoelectric Efficiency Test The dye-sensitized solar cells of Example 2 and Comparative Example were tested for short-circuit current (Jsc), open circuit voltage (Voc), fill factor (FF), and photoelectric conversion efficiency under illumination of AM 1.5. (η) and single-wave photocurrent conversion efficiency (Incident 16 25 201016668

Photon to Current Conversion Efficiency, IPCE). The test results are summarized as follows: Table 1 Test results of dye-sensitized solar cells Dye Jsc (mA/cm2) V〇c (V) FF η (%) Example 2 1-1 9.02 0.78 0.63 4.44 Comparative Example N719 7.36 0.76 0.61 3.38

10

15 The test results of Table 1 show that the dye-sensitized solar cell produced by the base metal complex of the embodiment of the present invention is compared with the dye-sensitized solar cell produced by the comparative example N719. The compound can improve the short-circuit current, open circuit voltage and fill factor of the dye-sensitized solar cell, thus increasing the photoelectric conversion efficiency of the dye-sensitized solar cell. In summary, the present invention exhibits characteristics that are different from conventional techniques in terms of purpose, technique, and efficacy, or in terms of its technical level and R&D design. However, it should be noted that the above-mentioned embodiments are merely illustrative for the sake of convenience of description, and are not intended to limit the invention, and that those skilled in the art can make some modifications without departing from the spirit and scope of the invention. The scope of the claims is intended to be limited to the above embodiments. The above-described embodiments are merely examples for the convenience of the description, and the scope of the claims is intended to be limited by the scope of the claims. 17 20 201016668 [Simple description of the schema] None. [Main component symbol description] 5 None.

18

Claims (1)

201016668 VII. Patent application scope: h—a ruthenium metal complex with the following structure (I): RuL2(NCS)2Am (I) 5 10 15 20 where L is 2,2'-bipyridine-4,4 , dicapric acid, 2,2'-bipyridine-4,4'-disulfonic acid or 2,2'-bipyridine-4,4'-diphosphate; A is a quaternary scale cation; and m is 1 , 2, 3, or 4. 2. The base metal complex according to claim 1, wherein L is 2,2'-double d is more than 唆4,4'-dicarboxylic acid. 3. The base metal complex according to claim 1, wherein L is 2,2'-double η than _4,4'-dicarboxylic acid. 4. The base metal complex according to claim 1, wherein L is 2,2'-bipyridine-4,4,-diphosphate. 5. The base metal complex according to claim 1, wherein A is 'R1, r2, r3, and r4 are each independently a decyl group, a phenyl group or a benzyl group. 6. The base metal complex according to claim 2, wherein A is P HH ' R], r 2 , r 3 , and r 4 are each independently a fluorene group, a phenyl group or a benzyl group. 7. The base metal complex according to claim 2, wherein A is a tetraalkyl scale, a benzyl trialkyl scale or a phenyl trialkyl scale, wherein the alkyl group is a Ci 2 anthracenyl group. 19 201016668 8. The base metal complex according to claim 2, wherein m is 2, 3, or 4. 9. The ruthenium metal complex as described in claim 3, wherein VIII is P RlR2R3R4, and R!, R2, R3, and R4 are each independently CM. 5 burnt base, stupid base or benzyl. 10. The base metal complex according to claim 3, wherein m is 2 or 3. 11. The ruthenium metal complex according to claim 4, wherein ❹ is P+R丨R2r3r4, and Ri, r2, R3, and 4 are each independently Ci ^ 10 alkyl, base or Benzyl. 12. The base metal complex according to claim 4, wherein m is 2 or 3. 13. The base metal complex according to claim 1, wherein the base metal complex is a dye compound for a dye-sensitized solar cell. 14. A ruthenium metal complex having the structure of the following formula 或) or the following formula 1.2 (1.2), 》 20 201016668 (I-l) (1-2). 5. The base metal complex according to claim 14, wherein the base metal complex is a dye compound for a dye-sensitized solar cell. 16. A dye-sensitized solar cell comprising: (a) a photoanode comprising a ruthenium metal complex of the following formula (I); 10 RuL2(NCS)2Am 〇(1) wherein L is 2, 2' -bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4'-disulfonic acid or 2,2'-bipyridine-4,4'-diphosphate; 15 A is a grade 4 a scale cation; and m is 1, 2, 3, or 4; (b) - a cathode; and (c) an electrolyte layer between the photoanode and the cathode. 21 201016668 17. A dye solution comprising: (A) - a ruthenium metal complex of the following formula (I) in an amount of 0.01 to 1 weight percent: RuL2(NCS)2Am 5 (1) wherein L is 2, 2 '-Bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4'-disulfonic acid or 2,2'-bipyridine-4,4'-diphosphate; A is a grade IV a pin cation; and • 10 m is 1, 2, 3, or 4; and (B) an organic solvent in an amount of 99.99 to 99 parts by weight, and the organic solvent is selected from the group consisting of: acetonitrile, methanol, ethanol a group consisting of propanol, butanol, dimethylformamide, and N-methylpyrrolidone. ❹ 22 201016668 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical that best shows the characteristics of the invention. 5 Formula: RuL2(NCS)2Am (I) wherein L, A, and m are as defined in the specification. 3