TW201247633A - Gelator and application therefore - Google Patents

Abstract

The present invention provides a gelator which has three amide groups and forms a gel from a liquid electrolyte of a dye-sensitized solar cell to solve the problems of volatilization and liquid leakage for the liquid electrolyte and to increase the service life of the cell.

Description

201247633 VI. Description of the Invention: [Technical Field] The present invention relates to a gel compound for use in colloidal electrolytic ruthenium and its application, particularly in the field of solar cells. [Prior technology] / The crude oil price has risen. 'Research on energy has become the research direction of scholars in various countries. The first research on solar cells in the world is the dye-sensitized solar cells. Sensitized S〇lar eell (DSSC) can complete large-area and low-cost battery production without the need for ultra-high vacuum membrane equipment. At present, the DSSC research published in the world is based on 10% of pure liquid electrolyte, but its shortcoming is that the pure liquid electrolyte is in the packaging operation or the volatilization problem, which affects the durability of the battery. In other words, one of the reasons why the stability of solar cells cannot be improved is that the organic solvent in the liquid electrolyte has high volatility, and the existing sealant is more difficult to withstand the corrosion of iodine, thereby reducing the life of the battery, and the solution method thereof. In order to improve the electrolyte's under-covering property or to develop anti-corrosion packaging technology, the time and cost of the latter may be higher than the former, so if the battery is not used, It is a preferred way for the electrolyte to be effectively coated while increasing the ionic conductivity when used. At present, a semi-solid electrolyte such as a copolymer of poly(ethylene oxide-co-epichlorohydrin), which is abbreviated as Ρ(ΕΟ·ΕΡΙ), has been developed. Molecular film. The use of the polymer to form a liquid electrolyte formed by the microporous structure formed after the film 154443.doc 201247633 can reduce the risk of liquid leaving the electrolyte to volatilize, but hinders the diffusion of r/i, and thus photoelectric conversion. The efficiency is reduced to 2 to 3%.

Hanabusa et al., 1999, published a gelling based on a low molecular weight gelatinized compound using N-carbobenzyloxy-L-isoleucine and 1-amine. A guanamine compound synthesized by the reaction of 1 aminooctadecane (Hanabusa ei a/., Chem Mater 1999, 11, 649-655). Kubo et al. published a pseudo-solid dye-sensitized solar energy in 2001. A battery, which is a gel compound of a guanamine type, is used in the electrolyte of the battery, and it has been found that a pseudo-solid solar cell using a colloidal electrolyte can improve the volatilization of the liquid electrolyte (Kubo wa/·, J. Phys. Chem. U.S. Patent No. 7,332,529 B2, the disclosure of which is incorporated herein incorporated by reference in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire disclosure The multiple intermolecular hydrogen bonding forces brought about by the diurea group in the sub-group can enhance the aggregation of such gel compounds, and the three-dimensional coating structure formed by intermolecular hydrogen bonding can be coated more effectively. Liquid solvent. However, on Conventional techniques have not yet achieved satisfactory results, so there is still a need to continuously develop colloidal electrolytes and prolong the service life of solar cells. [Inventive content] The present invention develops novel gel compounds that provide abundant intermolecular hydrogen bonds. 'Unexpectedly, it was found that the use of the gel compound for dye-sensitized solar energy 154443.do, 201247633 Battery electrolyte' can solve the problem of electrolyte volatilization and leakage, and at the same time improve the service life of the battery. The present invention provides a gel condensation a compound which is a condensate of a molecule of a triamine compound and a trisole of Ar_Ql_Q2_R, _C〇〇H, wherein the triamine compound is selected from the group consisting of:

Wherein R is a C 8 alkyl group of a long aliphatic chain; and wherein Ar-Q丨-Q2-R, _C〇〇h, Ar, q丨, q2 and R are defined as follows:

Ar is a C3.8 cycloalkyl group which is unsubstituted or substituted by one or more Ci 4 alkyl groups, an amine group, a hydroxyl group, (5:8 cycloalkenyl group, c5_1() aromatic ring or contains 1 to 3 From the c5_1G heterocycle of n, 0 and S heteroatoms. 01 is a <:|·6 extended alkyl group, Cl_6 alkyloxy group, Cl-6 alkylamine group or a bond; Q2 is -C(0) NH- or a bond; and R' is unsubstituted or one or more selected from the group consisting of an amine group, a mercapt(R), a methylthio group, an amine carbamate group, a carboxyl group, a hydrazine group Ci 6 alkyl group substituted by a group consisting of guanidino. The present invention uses one molecule of a triamine compound and three molecules of Ar Ql_ I54443.doc 201247633

QlR'-COOHAr-QLQ^R'-cooH is subjected to a condensation reaction to obtain a gel condensation compound of the present invention. According to the invention, the "triamine compound" is a compound having three amine groups. According to the invention, "(C3-C8)cycloalkyl" refers to a saturated cyclic hydrocarbon having from 3 to 8 carbon atoms. Preferred (C^C8)cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups and the like. According to the present invention, "(C5_C8)cycloalkenyl" means a cyclic non-aromatic hydrocarbon having at least one carbon-carbon double bond in the cyclic system and having 5 to 8 carbon atoms. Preferred ((Vc8 The ring includes cyclopentenyl, cyclopentanyl, cyclohexyl, hexyl, cycloheptyl, cycloheptyl, cycloheptyl, cyclooctenyl, cyclooctadiene According to the present invention, a C5-10 aromatic ring" includes a 5- to 10-membered monocyclic or bicyclic system, and examples thereof include a phenyl group and a naphthyl group. Invention, " contains 1 $ ^ _ 3 to 3 selected from Ν, 0 and S heteroatoms 〇 5, miscellaneous " represents saturated or unsaturated 5 _ to 1 u 员 、, system, including At least one hetero atom selected from the group consisting of N, hydrazine and S, wherein the aryl group can be substituted with at least one substituent selected from the group consisting of nitro, hydroxy, oxo, halogen, c. , _6 alkyl, C|_6 alkoxy, hydrazine

Cl-6 thiol, CN6 carbonyl, C| alkoxycarbonyl and phenyl. The above-mentioned chowder... ^ "The example of clothing includes P ratio. Ding, shout, pyridine, pyrrole, pyrazole, imidazole, 丨5 丨, carbazole, snail, sigma, far sputum, ρ No. oxadiazole, thiophene, ^, quinoline, isoquinoline and the likes thereof. 0. According to the present invention, the group c〇〇H compound composed of the compounds of the formulas of Ar-Qi-Q2^ is preferably. From 154443.doc 201247633

〇

NH

154443.doc 201247633

NH

NH

OH production

154443.doc 201247633

NH

NH

O eight OH

154443.doc -9- 201247633

According to a preferred embodiment of the invention, the gel condensation compound of the invention is selected from the group consisting of:

\ A3M ;

The present invention further provides a colloidal electrolyte comprising the gel compound as described above. The colloidal electrolyte can be used in a glass type dye-sensitized solar 154443.doc •10-201247633 battery, or a flexible solar cell for a winding (r〇Ut〇r〇丨丨) process. P〇lyethyiene terephthalate, 2,6 4 naphthalate (p〇ly(ethylene 2,6-naphthalate, ΕΝ) or polyethyleneimine (p〇iyethyienimine, pEI) The present invention further provides a method for gelling a liquid electrolyte by adding the above gel compound to a liquid electrolyte. In the above method of the present invention, the gel compound is dissolved in a liquid electrolyte. The method is in the range of 20 to 60 g/L, preferably 30 to 50 g/L. In the above method of the present invention, the heating temperature of the gel compound to the liquid electrolyte is between 70 and 10 ° C. The present invention also provides a method for preparing a colloidal dye-sensitized solar cell, which comprises the method of gelling a liquid electrolyte as described above. The present invention has found that a triterpenoid gel compound according to the present invention is dissolved. After organic solvent The organic solvent gels the liquid electrolyte by the hydrogen bonding force between the molecules. Compared with the prior art, since the gel compound of the present invention has a large molecular weight, the formed three-dimensional structure is also large, so Effectively coating more liquid electrolyte. In particular, because the gelled s material has rich hydrogen bonds, and the amine group and the larger steric barrier aromatic carboxyl group (Ar-C^-QkR' -COOH) When a guanamine bond is formed, it forms a π-like or sheet-like structure, and the pores in the structure can effectively coat the electrolyte. The dye-sensitized solar cell using the colloidal electrolyte of the present invention is used. After a long period of time, the present invention maintains a relatively high level of optoelectronics compared to the liquid electrolyte used in the prior art or the colloidal electrolyte using a double substituted benzinamide gel compound I54443.doc 201247633. The efficiency of the conversion, which in turn increases the useful life of the battery.The present invention is provided by the following non-limiting examples, which are not to be construed as limiting the invention. Modifications and variations of the embodiments discussed herein may be made without departing from the spirit and scope of the invention, and still fall within the scope of the invention. The compounds used in the following examples. And the instrument is as follows: 1. Conductive substrate: fluorine-doped tin dioxide conductive glass FTO, (SN02: F), manufactured by SONARONIX. 2. Titanium dioxide particles: manufactured by Degussa, model P-25. Cis-diisothiocyanato-bis (2,2,-bipyridyl-4,4'-dicarboxylato) ruthenium (II) bis (tetrabutylammonium) » abbreviated as "N719 dye" · manufactured by SOLARONIX. 4. Acetyl acetone: manufactured by Acros, with a purity greater than 99%. 5. Triton X-100 Nonionic Surfactant: manufactured by Roche. 6. Iodine: Made by Merck, with a purity of 99.8%. 7. Potassium iodide: Made by Merck, with a purity greater than 98%. 8. 3-Methoxypropionitrile (MPN): manufactured by Aldrich, with a purity of 99.5%. 154443.doc 12 201247633 9 · 4-tert-butylpyridine: manufactured by Acros, with a reagent grade of 96% purity. 10. l, 2-dimethyl-3-propylimidazoliumiodide (DMPImI): manufactured by Aldrich, with a purity greater than 97%. 11. N-carbobenzyloxy-L-isoleucine (abbreviated as a): Made by Sigma, the purity was 99.5%. 12. 1,12-Diaminododecane (abbreviated as c): Made by TCI, the purity is 99%. 13. N,N-Di-N-dicyclohexylcarbodiimide (DCC): Made by Acros, the purity is 99%. 14. Melamine (M): manufactured by Changchun Chemical Company. 15. Surlyn 1702 encapsulant film: manufactured by DuPont 16. Dimethyl sulfoxide (DMSO): manufactured by Acros, HPLC grade purity 99.9%. 17. Tris(2-aminoethyl)amine (abbreviated as T): manufactured by Acros Corporation, purity 980/〇. 18. Solar light source simulation test equipment: xen〇n Short Arc, Model YSS-100A Specifications, Simulator class A, AM 1.5, 100mW/cm2 Comparative Example 1 The cleaning method of the solar cell conductive glass containing the conventional liquid electrolyte is: use Ionized water: Ammonia: The volume ratio of hydrogen peroxide is 5:1 : 1 is prepared as a cleaning solution for conductive glass, and the conductive glass of 154443.doc 13 201247633 is placed in the cleaning solution 'and heated to 5 〇 ° C ' Ultrasonic shock cleaning for 20 minutes, rinse with deionized water, and dry the conductive glass with nitrogen.

The Ti〇2 slurry was prepared by adding 6 g of P_25 titanium dioxide to 14 ml of deionized water, 0.2 ml of Trit〇n X-100, and U ml of acetonitrile. The mixture was stirred with a magnet for 2 hours and then placed. Ultrasonic shock! A titanium dioxide slurry is available in an hour. Take the cleaned FTO glass, first apply the Ti〇2 slurry to the FTO glass with a spin coater, set the rotation speed to 5 rpm, the coating time is 2 〇 seconds, and then apply the coated conductive glass. Place in a high temperature furnace to bake 12 (rc for 15 minutes, then heat up to 450 ° C at a heating rate of 20 ° C / min for 3 〇 minutes, repeat the second layer, and repeat the sintering process, and finally get 1 〇 Μιη thick Ti〇2 working electrode. The preparation method of electrolyte is: 0.1MiLiI, 0.05MiI2, 0.6M DMPII and 0.5M TBP MPN solution. Platinum electrode is made by using clean conductive glass drilled hole as The injection hole of the electrolyte is coated on the FTO conductive glass with a 0.05 M solution of hydrogenplatinic acid isopropanol, and is sintered in a high temperature furnace at 4 ° C for 15 minutes to form a platinum catalyst layer. The N3 dye is dissolved in absolute ethanol and MPN (the volume ratio of ethanol to MPN is 1: 丨) to prepare a N3 dye solution of 005.005M, and the Ti〇2 electrode is immersed in the N3 dye for 24 hours to complete the production of the Ti02 working electrode. Place Dupont surly η 1702 as spacer in platinum counter electrode and Ti02 electrode Heating to 120 °C, the platinum counter electrode and the TiO2 working electrode can be 154443.doc 14 201247633 Attached 'the liquid electrolyte is poured into the small hole of the counter electrode, and the electrolyte perfusion hole of the platinum electrode is sealed with the Surlynl702 encapsulation film. Then, cover the cover glass and heat it to 80 °C to seal the electrolyte injection hole. Then seal the edge around the cover glass and the electrode with epoxy resin to complete the battery fabrication. Table (1) AM 1.5 Photoelectric quality before and after aging of the liquid electrolyte. Open circuit voltage Voc(V) Current density Jsc(mA/cm2) Fill factor Photoelectric conversion efficiency (%) Efficiency maintenance percentage (%) 0.69 before aging 12.33 0.59 5.04 60°C, aging After two weeks, 0.68 7.03 0.60 2.88 57 60 °C, battery leakage after aging for four weeks, battery leakage, battery leakage, battery leakage 0 Example 2 Known solar cells containing AcA colloidal electrolyte

The disubstituted bis-amine-based gel compound AcA of the following formula

AcA, the synthesis method is · 1 mole of N-oxide carbon-L-isoleucine (a) dissolved in ethyl acetate, adding 1 mole of N, N-dicyclohexylcarbodiimide (DCC) The reaction was carried out at 〇 ° C for 1 hour, and then 〇·5 mol of ι, ΐ2-diaminododecane (c) was reacted at 〇 ° C for 3 hours and then at room temperature for 18 hours. Then, the temperature was raised to 6 〇c>c. The reaction was terminated for 12 hours to 'filter' and the solvent in the liquid was dried to remove the product AcA. AcA was added to the electrolyte to raise the temperature to 80 ° C. Stirring was carried out to completely dissolve the AcA into 40 g/L. After the electrolyte was cooled, it became an aca colloidal electrolyte. The battery assembly method is the same as that of the first embodiment. 154443.doc -15- 201247633 Table (b) AM 1.5-time double-substituted colloidal electrolyte Photoelectric mass measurement before and after aging Open circuit voltage Voc(V) Current density•y Jsc(mA/cm) Fill factor Photoelectric conversion efficiency (% % Efficiency maintenance (%) 0.69 before aging 11.67 0.52 4.21 - 60 °C, after aging for two weeks 0.67 7.69 0.56 2.90 69 60 °C, after aging for 0.67 5.7 0.59 2.23 53 Example 3 Solar cell containing A3M colloidal electrolyte a tertiary triammine-based gel compound A3M of the following formula,

Human 0 \ Α3Μ The synthesis method is as follows: 3 moles of hydrazine is dissolved in DMSO, 3 moles of DCC and 1 mole of melamine (M) are added and heated to 90 ° C, and after 72 hours of reaction, anhydrous ethanol is added to decompress. After concentration, most of the DMSO was extracted, then anhydrous ethanol was added, and the magnet was stirred for one hour, and the filter residue was filtered and dried to obtain A3M. Add A3M to the electrolyte and warm it up to 90 ° C to stir it to dissolve completely into 40 g / L. After cooling the electrolyte, it becomes A3M colloidal electrolyte. The battery assembly method is the same as in the first embodiment. 154443.doc •16·201247633 Table (III) AM 1.5 when the tri-terpene colloidal electrolyte A3M is photo-electrically measured before and after aging. Open circuit voltage Voc(V) Current density Λ Jsc(mA/cm) Fill factor Efficiency (%) Efficiency maintenance percentage (%) 0.68 before aging 11.58 0.58 4.61 ... 60 °C, after aging for two weeks 0.68 8.08 0.64 3.52 76 60 °C, after aging for 0.65 8.72 0.61 3.48 75 Example 4 Colloidal electrolyte containing A3T Solar cell

A tertiary triterpenoid gel compound A3T of the following formula

The synthesis method is as follows: 3 moles of A is dissolved in ethyl acetate, and 3 moles of DCC is added to react at 0 ° C for 1 hour, and then 1 mole of tris(2-aminoethyl) is added. The amine (T) is reacted at 0 ° C for 3 hours, then at room temperature for 18 hours, and then heated to 60 ° C for 12 hours to complete the reaction, filtered and the solvent in the filtrate is dried to obtain the product. A3T. A3T was added to the electrolyte and warmed to 80 ° C to stir to completely dissolve A3T into 40 g / L. After the electrolyte was cooled, it became an A3T colloidal electrolyte. The battery assembly method is the same as that of the first embodiment. 154443.doc -17- 201247633 Table (IV) AM 1.5 when the triterpene colloidal electrolyte A3T before and after aging photoelectricity quality measurement open circuit voltage Voc (V) current density Jsc (mA / cm2) Fill factor photoelectric conversion efficiency (%) Efficiency maintenance percentage (%) 0.72 before aging 11.82 0.56 4.76 ... 60 ° C, after aging for two weeks 0.66 9.80 0.60 3.92 82 60 ° C, after four weeks of aging 0.64 8.32 0.58 3.11 65 The present invention can be proved by the above examples The weathering properties of the tertiary triterpene colloidal electrolytes A3M and A3T in the formation of battery components are better than those in liquid electrolyte batteries. Taking A3M as an example, from the perspective of photoelectric conversion efficiency, although the photoelectric conversion efficiency of liquid electrolyte (LE) is 0.43% higher than that of A3M, the efficiency of A3M after 60 °C two-week aging test. Can maintain the original 76%, while the efficiency of LE only maintains the original 57 ° /. After the aging test at 60 ° C for four weeks, the A3M efficiency can maintain the original 75%, and the LE cannot measure the efficiency because the electrolyte leaks out. Comparing the results of AcA and A3M, the efficiency of AcA before aging was 4.21%, and that of A3M was 4.61%. After two weeks of aging test at 60 °C, AcA was 2.9%, the efficiency was maintained at 69% before aging, and A3M was At 3.52%, the efficiency is maintained at 76% before aging; after 60 °C four weeks of aging test, AcA is 2.23%, the efficiency is maintained at 53% before aging; A3M is 3.48%, and the efficiency is maintained at 75% before aging, The reason is that the molecular structure of A3M is larger than AcA, so more liquid electrolyte can be coated. A3M contains three guanamine groups, so the hydrogen bond is more than that of Ac A, so it can be coated more effectively. The electrolyte is therefore well tolerated and the photoelectric conversion efficiency is much less. 154443.doc -18- 201247633 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a device for use in a dye-sensitized solar cell of the present invention. [Main component symbol description] 101 Conductive glass 102 Titanium dioxide porous film 103 Dye 104 Electrolyte 105 Platinum catalytic layer 106 Conductive glass 107 Encapsulation film 154443.doc - 19-

Claims (1)

201247633 VII. Patent Application Range: 1. A gel condensation compound which is a condensate of a molecule of a triamine compound and a trisole of Ar-Qi-Q^R'-cooH, wherein the triamine compound is selected from the following group : 'where R is an alkyl group of a long aliphatic chain; and Ar, Q, Q2 and R in Ar-Qi-QlRi-COOH are defined as follows: Ar is unsubstituted or burned by one or more ci. a base, an amine group, a thiol group substituted with a ruthenium group, a C5.8 cycloalkenyl group, a C5-1() aromatic ring or a C5_1G heterocyclic ring having 1 to 3 hetero atoms selected from N, anthracene and S. . (^ is a heart, 6 alkyl, C, 6 alkyloxy, cU6 alkyl or a bond; Q is -C(〇)NH- or a bond; and R· is unsubstituted Or an alkyl group substituted by one or more groups selected from the group consisting of an amine group, a mercapt(R), a methylthio group, a carbamyi group, a carboxyl group, and a guanidino group. 2. The gel condensation compound of claim 1, wherein Ar is cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl or phenyl; Ql is ^ to extend I54443.doc 201247633 The alkyl group; and Q2 is -C(0)NH-. 3. The gel condensation compound according to claim 1, wherein Ar-i^-QlR'-COOH is selected from the group consisting of the following formulas: human °V ^〇H〇ΌΗ /v I 1 NH O Oc .OH ,Λ 154443.doc 201247633 154443.doc Ο Ο NH OH NH OH 201247633 154443.doc ·4· 201247633 4. 5. 6· A colloidal electrolyte 'which contains as requested! a gel compound. A colloidal electrolyte according to claim 3, which is used in a vitrified solar cell. Their colloidal electrolytes are used in pull-to-wire (%) gb batteries for winding processes. To the dye-sensitive type of the above-mentioned type _ item 7. ^ please = the colloidal electrolysis f of item 6, wherein the flexible solar cell is ★ 笨 一 一 ethylene glycol, poly 2, 6 • naphthalene A solar cell of ethylene diformate or polyethyleneimine. 8. A method of gelling a liquid electrolyte, which comprises adding a gel compound as claimed in claim (4) to a liquid electrolyte. The method of Month Length 8, wherein the gel compound is dissolved in the liquid electrolyte in a solid content ranging from 20 to 60 g/L. The method of claim 8 or 9, wherein the heating temperature of the gel compound to the liquid electrolyte is in the range of 70 to 100t. A method of producing a colloidal dye-sensitized solar cell, comprising the step of preparing a colloidal dye-sensitized solar cell using the method of any one of claims 8-10. 154443.doc