TWI404707B - Electrolyte additive of dye-sensitized solar cell and method of making the same - Google Patents

Electrolyte additive of dye-sensitized solar cell and method of making the same Download PDF

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TWI404707B
TWI404707B TW099111064A TW99111064A TWI404707B TW I404707 B TWI404707 B TW I404707B TW 099111064 A TW099111064 A TW 099111064A TW 99111064 A TW99111064 A TW 99111064A TW I404707 B TWI404707 B TW I404707B
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electrolyte additive
electrolyte
dye
compound
sensitized solar
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TW201134815A (en
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Sheng Tung Huang
Chung Kuang Yang
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Univ Nat Taipei Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

This invention provides an electrolyte additive which is selected from N-alkyl benzimidazole derivatives and applicable to dye-sensitized solar cells. Accordingly, the electrolyte additive of this invention can be added to electrolyte at low concentration, and loss of function due to crystallization after long-term use can be prevented; in addition, short circuit photocurrent density and solar energy-to-electricity conversion efficiency of solar cells incorporating this invention can be increased.

Description

染料敏化太陽能電池之電解質添加劑及其製造方法Electrolyte additive for dye-sensitized solar cell and manufacturing method thereof

本發明係關於一種電解質添加劑，尤指一種可增加染料敏化太陽能電池(dye-sensitized solar cells，DSSCs)之光電轉換效率之電解質添加劑。The present invention relates to an electrolyte additive, and more particularly to an electrolyte additive which can increase the photoelectric conversion efficiency of dye-sensitized solar cells (DSSCs).

由於石化能源日漸枯竭以及環境問題日益惡化，太陽能的開發利用受到世界各國的高度重視。太陽能電池可直接將光能轉化電能，按其使用的材料體系的不同可大致分為：矽太陽能電池、化合物半導體太陽能電池、染料敏化太陽能電池以及有機物太陽能電池。其中單晶矽太陽能電池、多晶矽太陽能電池與化合物半導體太陽能電池具有成本高、環境負荷重等問題；而有機物太陽能電池之光電轉換效率極低，不利於大規模商業化應用。因此，全球主要的研究單位，均致力於開發替代性材料及其相關技術的研究，以降低製作成本及提升光電轉換效率。Due to the depletion of petrochemical energy and the deterioration of environmental problems, the development and utilization of solar energy has been highly valued by countries all over the world. Solar cells can directly convert light energy into electrical energy, which can be roughly divided into: solar cells, compound semiconductor solar cells, dye-sensitized solar cells, and organic solar cells. Among them, single crystal germanium solar cells, polycrystalline germanium solar cells and compound semiconductor solar cells have the problems of high cost and heavy environmental load; and the organic photoelectric solar cells have extremely low photoelectric conversion efficiency, which is disadvantageous for large-scale commercial applications. Therefore, the world's major research units are committed to the development of alternative materials and related technologies to reduce production costs and improve photoelectric conversion efficiency.

染料敏化太陽能電池由於具有成本低、高效能、組裝容易等優勢，其已成為發展新一代太陽能電池之主流。染料敏化太陽能電池係於1991年由O’Regan及Grtzel所發表，其利用奈米級二氧化鈦(TiO2 )的多孔性薄膜作為工作電極，其上吸附釕金屬之聯吡啶錯合物(如N719)作為光敏染料；而含有碘離子/三碘根離子(iodide/triodide,I- /I3 - )的氧化還原電解液作為電解質；濺鍍鉑金屬(platinum，Pt)的導電玻璃作為對應電極。Dye-sensitized solar cells have become the mainstream of the development of a new generation of solar cells due to their advantages of low cost, high efficiency, and easy assembly. Dye-sensitized solar cells were manufactured in 1991 by O'Regan and Gr Tzel, which uses a porous film of nano-titanium dioxide (TiO 2 ) as a working electrode, which adsorbs a bipyridyl complex of ruthenium metal (such as N719) as a photosensitizing dye; and contains iodide/triiodide ions. A redox electrolyte of (iodide/triodide, I - /I 3 - ) is used as an electrolyte; a conductive glass of platinum (Pt) is sputtered as a counter electrode.

染料敏化太陽能電池的工作原理，首先是做為吸光材料的釕金屬染料中，價電層電子受光激發，躍昇至高能階態，迅速傳到奈米級二氧化鈦半導體的導電層，經由工作電極導引至外部線路。被氧化的染料，則經由電池中電解質得到電子，還原至初始態。電解質再自外部線路由對應電極提供電子，完成迴路。The working principle of the dye-sensitized solar cell is firstly used as a ruthenium metal dye as a light absorbing material. The electrons in the valence layer are excited by light, jump to a high energy state, and rapidly pass to the conductive layer of the nano-sized titanium dioxide semiconductor, and are guided through the working electrode. Lead to the external line. The oxidized dye is then electron-reduced through the electrolyte in the battery and reduced to the original state. The electrolyte is then supplied from the external line by the corresponding electrode to complete the circuit.

傳統的電解質為含有碘離子/三碘根離子的有機溶液，但由於有機溶劑之沸點低、易揮發、流動性大，不利於電池的密封及長期使用。另外，有研究採用聚合物電解質替換液態電解質，組裝成固態染料敏化太陽能電池，電池穩定性大幅提高。然而，聚合物電解質具有電導率低、與電極界面浸潤差等缺點，造成固態電池的光電轉換效率遠不及液態電池。近年來以離子液體取代有機溶劑作為染料敏化太陽能電池中的電解質被廣泛的研究。離子液體具有導電力強、不易揮發、物理和化學性質穩定、液態工作範圍寬、介電常數高等優點，將離子液體作為電解質應用於染料敏化太陽能電池，克服了液態電解質易揮發的缺點。Grtzel等將離子液體作為染料敏化太陽能電池的電解質，光電轉換效率達到7%(光子通量(photon flux) 100mW/cm2 )，但其電解質的流動性很大，近乎流體，不利於電池的密封。The conventional electrolyte is an organic solution containing iodide ions/triiodide ions, but the organic solvent has a low boiling point, is volatile, and has high fluidity, which is disadvantageous for battery sealing and long-term use. In addition, studies have used polymer electrolytes to replace liquid electrolytes and assembled into solid-state dye-sensitized solar cells, which have greatly improved battery stability. However, the polymer electrolyte has disadvantages such as low electrical conductivity and poor wettability with the electrode interface, and the photoelectric conversion efficiency of the solid battery is far less than that of the liquid battery. In recent years, the replacement of organic solvents by ionic liquids has been extensively studied as an electrolyte in dye-sensitized solar cells. The ionic liquid has the advantages of strong electrical conductivity, low volatilization, stable physical and chemical properties, wide liquid working range and high dielectric constant. The ionic liquid is used as an electrolyte in dye-sensitized solar cells, which overcomes the shortcomings of liquid electrolytes. Gr Tzel et al. used ionic liquids as electrolytes for dye-sensitized solar cells with a photoelectric conversion efficiency of 7% (photon flux 100 mW/cm 2 ), but the fluidity of the electrolyte was large, nearly fluid, and was not conducive to the battery. seal.

近年來，液態電解質之染料敏化太陽能電池，其光電轉換效率已達到7%至12%，而影響染料敏化太陽能電池之光電轉換性能的原因之一，為穩定及有效的氧化還原反應，使得電子與電洞在電池內各膜層間穩定平衡存在。有鑑於此，改善電解質材料之組成結構，以提升染料敏化太陽能電池之光電轉換效率，成為全球研究人員亟需解決的問題之一。In recent years, the dye-sensitized solar cell of liquid electrolyte has a photoelectric conversion efficiency of 7% to 12%, and one of the reasons that affects the photoelectric conversion performance of the dye-sensitized solar cell is a stable and effective redox reaction. Electrons and holes are stably balanced across the layers of the cell. In view of this, improving the composition of the electrolyte material to improve the photoelectric conversion efficiency of the dye-sensitized solar cell has become one of the problems that researchers around the world need to solve.

目前許多研究著重於在電解質中加入添加劑(additives)，例如：4-三級丁基吡啶(4-tert-butyl pyridine，4-TBP)、苯并咪唑(benzimidazole)、N-甲基苯并咪唑(N-methyl benzimidazole，NMBI)等，以提高光電轉換效率(solar energy-to-electricity conversion efficiency，η%)。上述習知之電解質添加劑，雖能提升開路電壓(open circuit voltage，Voc)，進而提升光電轉換效率，但所需添加的量非常高，長期使用後會導致結晶產生於電池內，失去原有功能而使光電轉換效率不穩定。此外，上述習知之添加劑也會降低電池之短路光電流密度(short circuit photocurrent density，Jsc)，使得光電轉換效率無法達到最佳化。Many studies have focused on the addition of additives to the electrolyte, such as 4-tert-butyl pyridine (4-TBP), benzimidazole, N-methylbenzimidazole (N-methyl benzimidazole, NMBI) or the like to improve solar energy-to-electricity conversion efficiency (η%). Although the above-mentioned electrolyte additive can increase the open circuit voltage (Voc), thereby improving the photoelectric conversion efficiency, the amount of addition required is very high, and the long-term use causes crystals to be generated in the battery and loses the original function. The photoelectric conversion efficiency is unstable. In addition, the above-mentioned conventional additives also reduce the short circuit photocurrent density (Jsc) of the battery, so that the photoelectric conversion efficiency cannot be optimized.

因此，如何提出一種電解質添加劑可低濃度添加於電解液，長期使用亦不致產生結晶而失去原有功能，且提高太陽能電池之短路電流密度及光電轉換效率，將是本發明所欲積極揭露之處。Therefore, how to propose an electrolyte additive can be added to the electrolyte at a low concentration, and the original function is not caused by crystallization for a long period of time, and the short-circuit current density and photoelectric conversion efficiency of the solar cell are improved, which will be actively exposed by the present invention. .

有鑑於上述習知電解質添加劑之缺憾，發明人有感其未臻於完善，遂竭其心智悉心研究克服，憑其從事該項產業多年之累積經驗，進而研發出一種電解質添加劑，以期達到提高太陽能電池之短路電流密度及光電轉換效率的目的。In view of the shortcomings of the above-mentioned conventional electrolyte additives, the inventors felt that they were not perfected, exhausted their mental research and overcome them, and based on their accumulated experience in the industry for many years, developed an electrolyte additive to achieve solar energy improvement. The purpose of short-circuit current density and photoelectric conversion efficiency of the battery.

本發明之主要目的在提供一種電解質添加劑，其藉著可低濃度添加於電解液，致使長期使用亦不致產生結晶而失去原有功能，進而達到提高太陽能電池之短路電流密度及光電轉換效率的目的。The main object of the present invention is to provide an electrolyte additive which can be added to the electrolyte at a low concentration, so that the long-term use does not cause crystallization and loses the original function, thereby achieving the purpose of improving the short-circuit current density and photoelectric conversion efficiency of the solar cell. .

為達上述目的，本發明之一種電解質添加劑，其係選自下述式(1)化合物、式(2)化合物或其組合：式(1)化合物：To achieve the above object, an electrolyte additive of the present invention is selected from the group consisting of a compound of the following formula (1), a compound of the formula (2) or a combination thereof: a compound of the formula (1):

式(2)化合物：Compound of formula (2):

其中，n、l、m各自獨立為0至20，且l及m不同時為0；R表示氫、烷基、烷氧基、烯基、炔基、烷氧基-烷基、聚醚基或苯基之取代基，各取代基之碳原子數為0至20，且為線性或分枝；A表示亞甲基或CH2 OCH2 。Wherein n, l, m are each independently from 0 to 20, and l and m are not 0 at all; R represents hydrogen, alkyl, alkoxy, alkenyl, alkynyl, alkoxy-alkyl, polyether Or a substituent of a phenyl group, each of which has a carbon number of from 0 to 20 and is linear or branched; and A represents a methylene group or a CH 2 OCH 2 group .

上述之電解質添加劑，其中R表示氫或CH(OH)CH3 。The above electrolyte additive wherein R represents hydrogen or CH(OH)CH 3 .

上述之電解質添加劑，其係用於染料敏化太陽能電池。The above electrolyte additive is used in a dye-sensitized solar cell.

上述之電解質添加劑，其中A表示亞甲基，且n為1至10。The above electrolyte additive wherein A represents a methylene group and n is from 1 to 10.

上述之電解質添加劑，其可提高太陽能電池之短路電流密度及/或光電轉換效率。The above electrolyte additive can improve the short circuit current density and/or photoelectric conversion efficiency of the solar cell.

上述之電解質添加劑，其添加量為0.01M至0.5M，較佳為0.01M至0.25M。The above electrolyte additive is added in an amount of from 0.01 M to 0.5 M, preferably from 0.01 M to 0.25 M.

本發明另提供一種電解質添加劑的製造方法，其步驟包含：The invention further provides a method for manufacturing an electrolyte additive, the steps of which comprise:

(a)提供下述式(3)化合物；以及(a) providing a compound of the following formula (3);

(b)加入有效量之鹵化物以與式(3)化合物進行反應，前述鹵化物係選自烷基鹵化物、烷基二鹵化物、烷氧基鹵化物、烷氧基二鹵化物或其組合，且其碳原子數為0至20；式(3)化合物：(b) adding an effective amount of a halide to react with a compound of formula (3) selected from the group consisting of alkyl halides, alkyl dihalides, alkoxy halides, alkoxy dihalides or Combination, and its carbon number is 0 to 20; compound of formula (3):

其中，R表示氫、烷基、烷氧基、烯基、炔基、烷氧基-烷基、聚醚基或苯基之取代基，各取代基之碳原子數為0至20，且為線性或分枝。Wherein R represents a substituent of hydrogen, alkyl, alkoxy, alkenyl, alkynyl, alkoxy-alkyl, polyether or phenyl, each substituent having from 0 to 20 carbon atoms and being Linear or branched.

上述之方法，其中反應時間至少12小時，反應溫度至少70℃。The above process wherein the reaction time is at least 12 hours and the reaction temperature is at least 70 °C.

上述之方法，其中步驟(b)中進一步加入甲基三辛基氯化銨(methyltrioctylammonium chloride)。In the above method, in step (b), methyltrioctylammonium chloride is further added.

上述之方法，其中步驟(a)中進一步加入二甲基亞碸(dimethyl sulfoxide,DMSO)。In the above method, in the step (a), dimethyl sulfoxide (DMSO) is further added.

上述之方法，其中該鹵化物為寡(乙二醇)二氯化物(oligo(ethyleneglycol) dichloride)。The above method, wherein the halide is oligo (ethyleneglycol) dichloride.

藉此，本發明之一種電解質添加劑，可低濃度添加於電解液，長期使用亦不致產生結晶而失去原有功能，且提高太陽能電池之短路電流密度及光電轉換效率。Thereby, an electrolyte additive of the present invention can be added to the electrolyte at a low concentration, and the original function is not caused by crystallization during long-term use, and the short-circuit current density and photoelectric conversion efficiency of the solar cell are improved.

為充分瞭解本發明之目的、特徵及功效，茲藉由下述具體之實施例，並配合所附之圖式，對本發明做一詳細說明，說明如後：In order to fully understand the objects, features and advantages of the present invention, the present invention will be described in detail by the following specific embodiments and the accompanying drawings.

合成例：化學式1~12之苯并咪唑衍生物的合成方法Synthesis Example: Synthesis Method of Benzimidazole Derivatives of Chemical Formulas 1 to 12

將100mmol苯并咪唑或2-(1-羥乙基)苯并咪唑溶於80mL甲苯中，再加入足量(約13mL) DMSO，於80℃加熱溶解。之後加入溶於5mL甲苯之甲基三辛基氯化銨(2.2g，5.5mmol)，且加入寡(乙二醇)二氯化物(55mmol)及15mL 18N氫氧化鈉溶液。上述混合物於80℃回流反應至少12小時，反應完成後冷卻至室溫，藉由再結晶或萃取純化，最後使用管柱層析(SiO2 ，CH2 Cl2 ：乙醇為95:5或90:10)。100 mmol of benzimidazole or 2-(1-hydroxyethyl)benzimidazole was dissolved in 80 mL of toluene, and a sufficient amount (about 13 mL) of DMSO was added thereto, and dissolved by heating at 80 °C. Methyltrioctyl ammonium chloride (2.2 g, 5.5 mmol) dissolved in 5 mL of toluene was then added, and oligo(ethylene glycol) dichloride (55 mmol) and 15 mL of 18N sodium hydroxide solution were added. The above mixture is refluxed at 80 ° C for at least 12 hours, after completion of the reaction, cooled to room temperature, purified by recrystallization or extraction, and finally subjected to column chromatography (SiO 2 , CH 2 Cl 2 : ethanol 95:5 or 90: 10).

化學式1~12之苯并咪唑衍生物，產率約在36-63%，各化合物經NMR分析如下：The benzimidazole derivatives of Chemical Formulas 1 to 12 have a yield of about 36 to 63%, and each compound was analyzed by NMR as follows:

1,5 -Bis(1’-benzimidazolyl)-3-oxapentane( 1 ) .1 H NMR(DMSO-d6)δ3.72(t,4H,J=5.05Hz),4.35(t,4H,J=5.03Hz),7.19-7.23(m,4H),7.51-7.56(m,2H),7.64-7.68(m,2H),8.11(s,2H);13 C NMR(DMSO-d6)δ44.2,69.0,110.6,119.5,121.5,122.3,134.0,143.5,144.4. 1,5 - Bis(1'-benzimidazolyl)-3-oxapentane( 1 ) . 1 H NMR (DMSO-d6) δ 3.72 (t, 4H, J = 5.05 Hz), 4.35 (t, 4H, J = 5.03) Hz), 7.19-7.23 (m, 4H), 7.51-7.56 (m, 2H), 7.64-7.68 (m, 2H), 8.11 (s, 2H); 13 C NMR (DMSO-d6) δ 44.2, 69.0 , 110.6, 119.5, 121.5, 122.3, 134.0, 143.5, 144.4.

1,8-Bis(1’-benzimidazolyl)-3,6-dioxaoctane( 2 ) .1 H NMR(DMSO-d6 )δ3.41(s,4H),3.65(t,4H,J=5.0Hz),4.32(t,4H,J=5.0Hz),7.20-7.28(m,4H),7.57(d,2H,J=7.6Hz),7.68(d,2H,J=7.6Hz),8.19(s,2H);13 C NMR(DMSO-d6 )δ44.3,68.9,69.7,110.6,119.5,121.5,122.3,134.1,143.5,144.5. 1,8-Bis(1'-benzimidazolyl)-3,6-dioxaoctane( 2 ) . 1 H NMR (DMSO-d 6 ) δ 3.41 (s, 4H), 3.65 (t, 4H, J = 5.0 Hz) , 4.32 (t, 4H, J = 5.0 Hz), 7.20-7.28 (m, 4H), 7.57 (d, 2H, J = 7.6 Hz), 7.68 (d, 2H, J = 7.6 Hz), 8.19 (s, 2H); 13 C NMR (DMSO-d 6 ) δ 44.3, 68.9, 69.7, 110.6, 119.5, 121.5, 122.3, 134.1, 143.5, 144.5.

1,11-Bis(1’-benzimidazolyl)-3,6,9-trioxaundecane ( 3 ).1 H NMR(DMSO-d6 )δ3.35-3.40(m,4H),3.40-3.47(m,4H),3.73(t,4H,J=5.03Hz),4.38(t,4H,J=5.01Hz),7.18-7.27(m,4H),7.59-7.67(m,4H),8.19(s,2H);13 C NMR(DMSO-d6 )δ44.3,68.9,69.8,110.7,119.5,121.5,122.3,134.1,143.5,144.5 1,11-Bis(1'-benzimidazolyl)-3,6,9-trioxaundecane ( 3 ). 1 H NMR (DMSO-d 6 ) δ 3.35-3.40 (m, 4H), 3.40-3.47 (m, 4H) ), 3.73 (t, 4H, J = 5.03 Hz), 4.38 (t, 4H, J = 5.01 Hz), 7.18-7.27 (m, 4H), 7.59-7.67 (m, 4H), 8.19 (s, 2H) 13 C NMR (DMSO-d 6 ) δ 44.3, 68.9, 69.8, 110.7, 119.5, 121.5, 122.3, 134.1, 143.5, 144.5

1-[1-(2-{2-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-ethoxy}-ethyl)-1H-benzoimidazol-2-yl]-ethanol( 4 ) .1 H NMR:(500MHz,CDC13 ):δ=7.72(dd,J =3.0.8.1Hz,2H),7.25-7.21(m,6H),5.03(q,J =6.5Hz,2H),4.27(t,J =5.1Hz,1H),4.26(t,J =5.1Hz,1H),4.24(t,J =5.1Hz,1H),4.23(t,J =5.1Hz,1H),3.74-3.67(m,4H),1.66(d,J =6.5HZ,6H,).13 C-NMR:(125MHz,CDCl3 ):δ=156.4,141.9,135.2,122.9,122.3,119.9,109.4,69.7,63.0,43.6,22.2. 1-[1-(2-{2-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-ethoxy}-ethyl)-1H-benzoimidazol-2-yl]-ethanol( 4 ) . 1 H NMR: (500MHz, CDC1 3 ): δ = 7.72 (dd, J = 3.0.8.1 Hz, 2H), 7.25-7.21 (m, 6H), 5.03 (q, J = 6.5 Hz, 2H), 4.27 (t , J = 5.1 Hz, 1H), 4.26 (t, J = 5.1 Hz, 1H), 4.24 (t, J = 5.1 Hz, 1H), 4.23 (t, J = 5.1 Hz, 1H), 3.74 - 3.67 (m) , 4H), 1.66 (d, J = 6.5HZ, 6H,). 13 C-NMR: (125MHz, CDCl 3 ): δ = 156.4, 141.9, 135.2, 122.9, 122.3, 119.9, 109.4, 69.7, 63.0, 43.6 , 22.2.

1-{1-[2-(2-{2-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-ethoxy}-ethoxy)-ethyl]-1H-benzoimidazol-2-yl}-ethanol( 5 ) .1 H-NMR:(500MHz,CDCl3 ,ppm):δ=7.75-7.74(m,2H),7.27-7.25(m,2H),7.24-7.20(m,4H),5.11(q,J=6.5,2H),4.39(t,J =3.8Hz,1H),4.36(t,J =3.8Hz,1H),4.30-4.29(m,1H),4.28-4.27(m,1H),3.64-3.60(m,2H),3.56-3.55(m,2H),3.33(s,4H),1.71(d,6H,J =6.5HZ).13 C-NMR:(125MHz,CDCl3 ,ppm):δ=156.6,142.0,135.0,122.6,122.2,119.9,109.6,70.1,69.0,62.0,43.6,21.3. 1-{1-[2-(2-{2-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-ethoxy}-ethoxy)-ethyl]-1H-benzoimidazol-2-yl}- Ethanol( 5 ) . 1 H-NMR: (500MHz, CDCl 3 , ppm): δ=7.75-7.74 (m, 2H), 7.27-7.25 (m, 2H), 7.24-7.20 (m, 4H), 5.11 ( q, J=6.5, 2H), 4.39 (t, J = 3.8 Hz, 1H), 4.36 (t, J = 3.8 Hz, 1H), 4.30-4.29 (m, 1H), 4.28-4.27 (m, 1H) , 3.64-3.60 (m, 2H), 3.56-3.55 (m, 2H), 3.33 (s, 4H), 1.71 (d, 6H, J = 6.5HZ). 13 C-NMR: (125MHz, CDCl 3 , ppm ): δ = 156.6, 142.0, 135.0, 122.6, 122.2, 119.9, 109.6, 70.1, 69.0, 62.0, 43.6, 21.3.

1-(1-{2-[2-(2-{2-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-ethoxy}-ethoxy)-ethoxy]-ethyl}-1H-benzoimidazol-2-yl)-ethanol( 6 ) .1 H NMR:(500MHZ,CDCl3 ):δ=7.69(dd,J =3.8,7.1Hz,2H),7.24-7.22(m,2H),7.20-7.16(m,4H),5.17(q,J =6.5Hz,2H),4.49(t,J =4.0Hz,1H),4.45(t,J =4.0Hz,1H),4.35-4.29(m,2H),3.73-3.66(m,4H),3.35-3.21(m,8H),1.68(d,J =6.5Hz,6H).13 C-NMR:(125MHz,CDCl3 ,ppm):δ=156.9,141.8,134.8,122.5,122.0,119.5,70.3,68.0,68.9,62.2,43.7,21.6. 1-(1-{2-[2-(2-{2-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-ethoxy}-ethoxy)-ethoxy]-ethyl}-1H-benzoimidazol -2-yl)-ethanol( 6 ) . 1 H NMR: (500MHZ, CDCl 3 ): δ=7.69 (dd, J = 3.8, 7.1 Hz, 2H), 7.24-7.22 (m, 2H), 7.20-7.16 (m, 4H), 5.17 (q, J = 6.5 Hz, 2H), 4.49 (t, J = 4.0 Hz, 1H), 4.45 (t, J = 4.0 Hz, 1H), 4.35-4.29 (m, 2H) , 3.73-3.66 (m, 4H), 3.35-3.21 (m, 8H), 1.68 (d, J = 6.5 Hz, 6H). 13 C-NMR: (125MHz, CDCl 3 , ppm): δ = 156.9, 141.8 , 134.8, 122.5, 122.0, 119.5, 70.3, 68.0, 68.9, 62.2, 43.7, 21.6.

1,1-(1,5-Pentanediyl)bis[benzimidazole]( 7 ) .1 H NMR(CDCl3 )δ=7.83(s,2H),7.81(m,2H),7.30(m,6H),4.12(t,4H,J )7.2Hz),1.89(quintet,4H,J )7.2Hz),1.35(quintet,2H,J )7.2Hz);13 C NMR(CDCl3 )δ=143.84,142.78,133.66,123.02,122.23,120.51,109.52,44.78,29.49,24.27. 1,1-(1,5-Pentanediyl)bis[benzimidazole]( 7 ) . 1 H NMR (CDCl 3 ) δ=7.83 (s, 2H), 7.81 (m, 2H), 7.30 (m, 6H), 4.12 (t, 4H, J ) 7.2 Hz), 1.89 (quintet, 4H, J ) 7.2 Hz), 1.35 (quintet, 2H, J ) 7.2 Hz); 13 C NMR (CDCl 3 ) δ = 143.84, 142.78, 133.66, 123.02, 122.23, 120.51, 109.52, 44.78, 29.49, 24.27.

1,1-(1,8-Octanediyl)bis[benzimidazole]( 8 ) .1 H NMR(CDCl3 )δ=7.85(s,2H),7.80(m,2H),7.36(m,2H),7.28(m,4H),4.13(t,4H,J )7.2Hz),1.84(broad quintet,4H,J )7.2Hz),1.28(broad,8H);13 C NMR(CDCl3 )δ=143.78,142.89,133.74,122.80,122.02,120.29,109.65,44.98,29.62,28.81,26.59. 1,1-(1,8-Octanediyl)bis[benzimidazole]( 8 ) . 1 H NMR (CDCl 3 ) δ=7.85 (s, 2H), 7.80 (m, 2H), 7.36 (m, 2H), 7.28 (m, 4H), 4.13 (t, 4H, J ) 7.2 Hz), 1.84 (broad quintet, 4H, J ) 7.2 Hz), 1.28 (broad, 8H); 13 C NMR (CDCl 3 ) δ = 143.78, 142.89 , 133.74, 122.80, 122.02, 120.29, 109.65, 44.98, 29.62, 28.81, 26.59.

1-(1-{5-[2-(1-Hydroxy -ethyl)-benzoim i dazol-1-yl]-pen tyl}-1H-benzoimidazol-2 -y1)-ethanol ( 9 ) . 1 H NMR(500MHz,CDCl3 )δ=7.68(dd,J =3.7,8.6Hz,2H),7.25-7.20(m,6H),5.05(q,J =6.5Hz,2H),4.25-4.21(m,2H),4.14-4.08(m,2H),1.90-1.82(m,4H,),1.79(d,J =6.5Hz,6H),1.45(quintet,2H,J =7.6HZ).13 C-NMR:(125MHz,CDCl3 )δ=156.1,149.1,141.8,135.2,122.8,122.2,119.7,63.2,43.7,29.2,24.3,22.6. 1-(1-{5-[2-(1-Hydroxy- ethyl)-benzoim i dazol-1-yl]-pen tyl}-1H-benzoimidazol-2 -y1)-ethanol ( 9 ) . 1 H NMR( 500MHz, CDCl 3 ) δ = 7.68 (dd, J = 3.7, 8.6 Hz, 2H), 7.25-7.20 (m, 6H), 5.05 (q, J = 6.5 Hz, 2H), 4.25 - 4.21 (m, 2H) , 4.14 - 4.08 (m, 2H), 1.90 - 1.82 (m, 4H,), 1.79 (d, J = 6.5 Hz, 6H), 1.45 (quintet, 2H, J = 7.6HZ). 13 C-NMR: ( 125MHz, CDCl 3 ) δ = 156.1, 149.1, 141.8, 135.2, 122.8, 122.2, 119.7, 63.2, 43.7, 29.2, 24.3, 22.6.

1-(1-{8-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-octyl}-1H-benzoimidazol-2-yl)-ethanol (10) .1 H NMR(500MHz,CDCl3 )δ=7.72-7.70(m,2H),7.30-7.27(m,2H),7.25-7.21(m,4H),5.05(q,J =6.4Hz,2H),4.22-4.18(m,2H),4.13-4.07(m,2H),1.83-1.73(m,4H,),1.70(d,J =6.4Hz,6H),1.30-1.25(m,8H,).13 C-NMR(125MHz,CDCl3 )δ=156.2,134.5,123.5,123.1,123.1,118.5,110.2,62.9,44.4,29.7,29.6,28.7,26.5,22.7. 1-(1-{8-[2-(1-Hydroxy-ethyl)-benzoimidazol-1-yl]-octyl}-1H-benzoimidazol-2-yl)-ethanol (10) . 1 H NMR (500MHz, CDCl 3 ) δ=7.72-7.70 (m, 2H), 7.30-7.27 (m, 2H), 7.25-7.21 (m, 4H), 5.05 (q, J = 6.4 Hz, 2H), 4.22-4.18 (m, 2H) ), 4.3-4.07 (m, 2H), 1.83-1.73 (m, 4H,), 1.70 (d, J = 6.4 Hz, 6H), 1.30-1.25 (m, 8H,). 13 C-NMR (125 MHz, CDCl 3 ) δ = 156.2, 134.5, 123.5, 123.1, 123.1, 118.5, 110.2, 62.9, 44.4, 29.7, 29.6, 28.7, 26.5, 22.7.

2-[2-(2-Benzoimidazol-1-yl-ethoxy)-ethoxy]-ethanol(11). 1 H-NMR:(500MHz,CDCl3 )δ=8.02(s,1H),7.74(dd,J =2.1.6.2Hz,1H),7.34(dd,J =2.1. 6.2Hz,1H),7.26-7.20(m,2H),4.26(t,J =5.2Hz,2H),3.75(t,J =5.2Hz,2H),3.66(t,J =4.7Hz,2H),3.50-3.45(m,7H).13 C-NMR(125MHz,CDCl3 )δ=143.9,143.1,133.5,122.7,122.0,119.9,109.4,72.5,70.5,70.0,69.0,61.2,44.7. 1-[2-(2-Benzoimidazol-1-yl-ethoxy)-ethoxy]-ethanol(11). 1 H-NMR: (500MHz, CDCl 3 ) δ=8.02 (s, 1H), 7.74 (dd, J =2.1.6.2 Hz, 1H), 7.34 (dd, J = 2.1. 6.2 Hz, 1H), 7.26-7.20 (m, 2H), 4.26 (t, J = 5.2 Hz, 2H), 3.75 (t, J = 5.2 Hz, 2H), 3.66 (t, J = 4.7 Hz, 2H), 3.50-3.45 (m, 7H). 13 C-NMR (125MHz, CDCl 3 ) δ = 143.9, 143.1, 133.5, 122.7, 122.0, 119.9 , 109.4, 72.5, 70.5, 70.0, 69.0, 61.2, 44.7.

1-(1-{2-[2-(2-Hydroxy-ethoxy)-ethoxy]-ethyl}-1H-benzoimidazol-2-yl)-ethanol(12) .1 H-NMR(500MHZ,CDCl3 )δ=7.75-7.73(m,1H),7.25-7.20(m,3H),5.14(q,J =6.5Hz,1H),4.44-4.42(m,2H),3.82-3.77(m,2H),3.62-3.59(m,2H),3.53-3.40(m,6H),1.72(d,3H,J =6.5Hz).13 C-NMR:(500MHz,CDCl3 )δ=156.4,142.1,136.9,134.6,122.7,122.3,120.0,109.2,74.0,73.0,70.4,69.3,68.8,61.5,61.3,43.7,30.3,20.5. 1-(1-{2-[2-(2-Hydroxy-ethoxy)-ethoxy]-ethyl}-1H-benzoimidazol-2-yl)-ethanol(12) . 1 H-NMR(500MHZ, CDCl 3 )δ =7.75-7.73(m,1H), 7.25-7.20(m,3H), 5.14(q, J =6.5Hz,1H),4.44-4.42(m,2H),3.82-3.77(m,2H),3.62 -3.59 (m, 2H), 3.53 - 3.40 (m, 6H), 1.72 (d, 3H, J = 6.5 Hz). 13 C-NMR: (500 MHz, CDCl 3 ) δ = 156.4, 142.1, 136.9, 134.6, 122.7, 122.3, 120.0, 109.2, 74.0, 73.0, 70.4, 69.3, 68.8, 61.5, 61.3, 43.7, 30.3, 20.5.

化學式1~12之苯并咪唑衍生物的化學結構Chemical structure of benzimidazole derivatives of Chemical Formulas 1-12

化學式1~12之苯并咪唑衍生物的合成反應概述Summary of the Synthesis of Benzimidazole Derivatives of Chemical Formulas 1~12

實施例1~12及對照例1~3：Examples 1 to 12 and Comparative Examples 1 to 3:

將吸附N719染料之奈米TiO2 電極及鉑對應電極，組裝至一三明治密封型之電池，藉由加熱熱熔性離聚物薄膜作為間隔物(25微米厚，Solaronix)。將一滴電解質溶液，包含：0.1M LiI、0.05M I2 、0.5M PMII(1-propyl-3-methylimidazolium iodide)、0.6M溶於3-甲氧基丙腈(3MPN)之4-三級丁基吡啶，及化學式1~12之苯并咪唑衍生物(0.01M~0.5M)，注入該對應電極之孔洞中，再以熱熔性離聚物薄膜及玻璃密封。該電極之工作區域為0.25cm2 。另外，以相同實施例1~12之實驗方式，將化學式1~12之苯并咪唑衍生物更換為其他添加物或不添加，作為3組對照例。其實驗結果如表1所示，其中光電轉換效率(η%)可由下式計算而得：The nano TiO 2 electrode adsorbed with N719 dye and the platinum counter electrode were assembled into a sandwich-sealed battery by heating the hot-melt ionomer film as a spacer (25 μm thick, Solaronix). A drop of electrolyte solution containing: 0.1 M LiI, 0.05 MI 2 , 0.5 M PMII (1-propyl-3-methylimidazolium iodide), 0.6 M 4-trimethoxybutyl dissolved in 3-methoxypropionitrile (3MPN) Pyridine, and the benzimidazole derivatives of Chemical Formulas 1 to 12 (0.01 M to 0.5 M) are injected into the pores of the corresponding electrode, and then sealed with a hot melt ionomer film and glass. The working area of the electrode is 0.25 cm 2 . Further, the benzimidazole derivatives of Chemical Formulas 1 to 12 were replaced with other additives or not added in the same manner as in the experimental examples 1 to 12, and were used as three sets of comparative examples. The experimental results are shown in Table 1, in which the photoelectric conversion efficiency (η%) can be calculated by the following formula:

其中，I0 為光子通量(100mW/cm2 for AM 1.5)，Jsc為短路光電流密度，Voc為開路電壓，ff表示填充因子(fill factor)。Where I 0 is the photon flux (100 mW/cm 2 for AM 1.5), Jsc is the short-circuit photocurrent density, Voc is the open circuit voltage, and ff is the fill factor.

由表1可以觀察到，光電轉換效率及填充因子分別位於2.63~6.63%及0.433~0.669的範圍，而短路光電流密度及開路電壓則分別位於5.39~14.47mA/cm2 及0.71~0.81V的範圍。其中化合物9之光電轉換效率達到6.63%最高，甚至高於習知添加劑4-三級丁基吡啶或2-(1-羥乙基)苯并咪唑。另外，化合物9亦具有最高之短路光電流密度，而在低濃度0.02M不但能使短路電流密度上升，且比習知添加劑(0.5M)提升10%以上之電池光電轉換效率。顯示化學式1~12之苯并咪唑衍生物確實可實際應用於染料敏化太陽能電池，並且具有良好之添加劑表現。It can be observed from Table 1 that the photoelectric conversion efficiency and fill factor are in the range of 2.63~6.63% and 0.433~0.669, respectively, while the short-circuit photocurrent density and open circuit voltage are respectively located at 5.39~14.47mA/cm 2 and 0.71~0.81V. range. Among them, the photoelectric conversion efficiency of the compound 9 was 6.63%, which was even higher than the conventional additive 4-tris-butylpyridine or 2-(1-hydroxyethyl)benzimidazole. In addition, the compound 9 also has the highest short-circuit photocurrent density, and the low-concentration 0.02 M not only increases the short-circuit current density, but also increases the photoelectric conversion efficiency of the battery by 10% or more over the conventional additive (0.5 M). The benzimidazole derivatives of Chemical Formulas 1 to 12 can be practically applied to dye-sensitized solar cells and have good additive performance.

如上所述，本發明完全符合專利三要件：新穎性、進步性和產業上的可利用性。以新穎性和進步性而言，本發明係藉著一次性步驟合成苯并咪唑衍生物，作為染料敏化太陽能電池之電解質添加劑時，致使可低濃度添加於電解液，長期使用亦不致產生結晶而失去原有功能，進而達到提高太陽能電池之短路電流密度及光電轉換效率的效用；就產業上的可利用性而言，利用本發明所衍生的產品，當可充分滿足目前市場的需求。As described above, the present invention fully complies with the three requirements of the patent: novelty, advancement, and industrial applicability. In terms of novelty and advancement, the present invention synthesizes a benzimidazole derivative by a one-time step, as an electrolyte additive for a dye-sensitized solar cell, so that a low concentration can be added to the electrolyte, and long-term use does not cause crystallization. The original function is lost, thereby achieving the effect of improving the short-circuit current density and photoelectric conversion efficiency of the solar cell; in terms of industrial availability, the products derived from the present invention can fully satisfy the current market demand.

本發明在上文中已以較佳實施例揭露，然熟習本項技術者應理解的是，該實施例僅用於描繪本發明，而不應解讀為限制本發明之範圍。應注意的是，舉凡與該實施例等效之變化與置換，均應設為涵蓋於本發明之範疇內。因此，本發明之保護範圍當以下文之申請專利範圍所界定者為準。The invention has been described above in terms of the preferred embodiments, and it should be understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations equivalent to those of the embodiments are intended to be included within the scope of the present invention. Therefore, the scope of the invention is defined by the scope of the following claims.

Claims (9)

一種電解質添加劑，其係為下述式(1)化合物：式(1)化合物： 其中，n為0至20；R表示CH(OH)CH3 ；A表示亞甲基或CH2 OCH2 。An electrolyte additive which is a compound of the following formula (1): a compound of the formula (1): Wherein n is from 0 to 20; R represents CH(OH)CH 3 ; A represents methylene or CH 2 OCH 2 . 如申請專利範圍第1項所述之電解質添加劑，其中A表示亞甲基，且n為1至10。 An electrolyte additive according to claim 1, wherein A represents a methylene group and n is from 1 to 10. 如申請專利範圍第2項所述之電解質添加劑，其可提高太陽能電池之短路電流密度及/或光電轉換效率。 The electrolyte additive according to claim 2, which can improve the short-circuit current density and/or photoelectric conversion efficiency of the solar cell. 如申請專利範圍第3項所述之電解質添加劑，其添加量為0.01M至0.5M。 The electrolyte additive according to claim 3, which is added in an amount of from 0.01 M to 0.5 M. 一種如申請專利範圍第1至4項中任一項所述之電解質添加劑的製造方法，其步驟包含：(a)提供下述式(3)化合物；以及(b)加入有效量之鹵化物以與式(3)化合物進行反應，前述鹵化物係選自C2-C20烷基二鹵化物、C2-C20烷氧基二鹵化物或其組合；式(3)化合物： 其中，R表示CH(OH)CH3 。A method of producing an electrolyte additive according to any one of claims 1 to 4, wherein the step of: (a) providing a compound of the following formula (3); and (b) adding an effective amount of a halide The reaction with the compound of the formula (3) is selected from the group consisting of a C2-C20 alkyl dihalide, a C2-C20 alkoxy dihalide or a combination thereof; a compound of the formula (3): Wherein R represents CH(OH)CH 3 . 如申請專利範圍第5項所述之方法，其中反應時間至少12小時，反應溫度至少70℃。 The method of claim 5, wherein the reaction time is at least 12 hours and the reaction temperature is at least 70 °C. 如申請專利範圍第5或6項所述之方法，其中步驟(b)中進一步加入甲基三辛基氯化銨(methyltrioctylammonium chloride)。 The method of claim 5, wherein the step (b) further comprises methyltrioctylammonium chloride. 如申請專利範圍第5或6項所述之方法，其中步驟(a)中進一步加入二甲基亞碸(dimethyl sulfoxide)。 The method of claim 5, wherein the dimethyl sulfoxide is further added to the step (a). 如申請專利範圍第5或6項所述之方法，其中該鹵化物為寡(乙二醇)二氯化物(oligo(ethyleneglycol)dichloride)。 The method of claim 5, wherein the halide is oligo (ethyleneglycol) dichloride.
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