TW201141816A

TW201141816A - Photochemical cell including semiconductor fine particles sensitized by binuclear ruthenium complex dye, and electrolyte solution that contains ammonium salt compound or phosphonium salt compound

Info

Publication number: TW201141816A
Application number: TW100101440A
Authority: TW
Inventors: Soh Aoki; Takafumi Iwasa; Yoshihisa Kakuta
Original assignee: Ube Industries
Priority date: 2010-01-15
Filing date: 2011-01-14
Publication date: 2011-12-01
Also published as: WO2011087099A1; JPWO2011087099A1; JP5682574B2

Abstract

This invention relates to photochemical cell including semiconductor fine particles sensitized by binuclear ruthenium complex dye, and electrolyte solution that contains ammonium salt compound or phosphonium salt compound.

Description

201141816 六、發明說明：【發明所屬之技術領域】本發明侧於-祕化學魏’其具有:包含由高電子_優_雙《了 #合體色素補料導财錄子的光換元件，及含有叙鹽化合物或鱗鹽化合物的電解質溶液。【先前技術】太陽f池當作清潔的再生型能較龍大+麟，已有石夕系、多晶衫、非晶衫的太陽電池或由碲化錦、德姻鋼^ 化合物構成的太陽電池的實用化為目標的研究。但是，為了並及成為家庭用躲’各個電池均必需克服製造成本高、原材料二困難、回收的問題，還有大面積化困難等許多問題。以目標為大面積化或低價化為目標，有人提蚊财機材制太陽電池，但是變換效率均約1% ’距離實用化相當遙遠。於此狀況中，1991年Gratzel等人於Nature揭示使用經色素 ^感的半導體微粒子的光電賴元件及太陽電池，以及製作該太 1%電/也必要的材料及製造技術(例如，Na^re，第m3卷，737頁， =υ、日本特開平1-綱8()號公報(專利文獻/) 騎色素概的纽質二氧顿祕當作作用阮電池。該太陽電池的優點為’廉價材料不需要精 i成尚純度便可使用，因此能提供廉價的光電變換元件，再者， 2的色，的，收廣，可跨越廣可見光的波長範圍將太陽光變換為屯。但疋，為了要實用化，仍需進一步提高變換效率，能開發吸光係數更高且能於更高波長域吸收光的色素。在本案申請人的日本特㈤湖.536號公報(專利文獻幻 t ^不可用於當作光電變換元件的含有為金屬錯合體色素的聯吡σ疋基配位子的金屬單核錯合體。又於色素增感太陽電池的最新技術(CMc公司(股），2〇ό1 iif i5日發行，117頁)(非專利文獻2)中，揭示多核β·二酮錯合體色常。 201141816 ㈣二本ϊ開2004-359677號公報(專利文獻3)中，揭示-錯5體’其係接受鮮活性I線的能量而取出 k換機能優異的_複核錯合體，具有多 ^位 ==ί=嶋断㈣位構及不具共扼雜壤的配位構造。俜可i得T^H8587(專利文獻4)揭示一種雙核金屬錯合體，素’具有共_環的配位構造。 μ *屬錯口體色【先前技術文獻】【專利文獻】【專利文獻1】曰本特開平丨_22〇380號公報【專利文獻2】曰本特開2〇〇3_261536號公報【專利文獻3】日本特開2004-359677號公報【專利文獻4】國際公開第2006/038587號小冊【非專利文獻】【非專利文獻1】Nature，第353卷，737頁，1991年 W獻2】色麵献㈣池的最難術(CMC公司 ⑻，2001年5月25日發行，117頁）【發明内容】【發明欲解決的課題】學電^發0⑽課題在於提供光電變換效率高而且耐久性高的光化【解決課題的方式】本發明係關於以下事項。 ’具有:轉式⑴表示的藉由雙鑛錯合體鐘趟半導體微粒子，及包含以通式(2)表示的銨鹽化合物或鱗鹽化合物的電解質溶液；；通式(1) 201141816 n201141816 VI. Description of the invention: [Technical field to which the invention pertains] The present invention has a light-replacement element comprising a high-electron _ _ _ double "a conjugated pigment feeding guide", and An electrolyte solution containing a salt compound or a scale salt compound. [Prior Art] The solar f pool is a clean regenerative type that can be compared with Longda + Lin, a solar cell with a Shi Xi system, a polycrystalline shirt, an amorphous shirt, or a sun composed of 碲化锦, 德姻钢^ compound. The practical use of batteries is the goal of research. However, in order to prevent the use of household batteries, it is necessary to overcome the problems of high manufacturing costs, difficulty in recycling raw materials, and recycling, as well as difficulties in large-area. With the goal of large-area or low-cost targets, some people use mosquito-repellent materials to make solar cells, but the conversion efficiency is about 1%. In this case, in 1991, Gratzel et al., Nature, disclose a photo-electric element and a solar cell using a pigmented semiconductor microparticle, and a material and a manufacturing technique (for example, Na^re). , m3, 737 pages, = υ, Japanese special Kaiping 1-class 8 () bulletin (patent literature /) riding color pigments, the new type of dioxin is used as a battery. The advantage of this solar cell is ' Cheap materials can be used without the need for precision, so they can provide inexpensive photoelectric conversion elements. Furthermore, the color of 2 can be converted into 屯 across the wavelength range of wide visible light. In order to be practical, it is still necessary to further improve the conversion efficiency, and it is possible to develop a pigment having a higher absorption coefficient and capable of absorbing light in a higher wavelength region. In the case of the applicant of the Japanese Special (5) Lake No. 536 (patent document illusion t ^ It is not applicable to metal mononuclear complexes containing a bipyridyl sulfhydryl ligand which is a metal complex dye as a photoelectric conversion element. It is also the latest technology for dye-sensitized solar cells (CMc Co., Ltd., 2〇) Ό1 iif i5 issued, 117 pages) ( Patent Document 2) discloses a polynuclear β-diketone complex coloring. In the case of Japanese Patent Publication No. 2004-359677 (Patent Document 3), it is disclosed that the body is subjected to the energy of the fresh active I line. And the k-replacement machine is excellent in the _reconstruction complex, and has a multi-position == ί=嶋(4) positional structure and a coordination structure without symmetry. 俜可i得得 T^H8587 (Patent Document 4) discloses a A dinuclear metal complex, a 'coordinated structure with a common_ring. μ * is a staggered body color [Prior Art Document] [Patent Document] [Patent Document 1] 曰本特开平丨_22〇380号 [Patent [Patent Document 3] Japanese Laid-Open Patent Publication No. 2004-359677 [Patent Document 4] International Publication No. 2006/038587 [Non-Patent Document] [Non-Patent Document 1] 】Nature, Vol. 353, 737, 1991, W 2] The most difficult thing in the color (4) pool (CMC Company (8), issued on May 25, 2001, 117 pages) [Summary of the Invention] Problem: The problem of learning electricity 0 (10) is to provide photochemical conversion with high photoelectric conversion efficiency and high durability. The present invention relates to the following matters: 'There are: an electrolyte solution containing a double-mine complex clock crystal semiconductor microparticle represented by the formula (1), and an ammonium salt compound or a scale salt compound represented by the general formula (2) ;; General formula (1) 201141816 n

HOOC HOOC HOOCHOOC HOOC HOOC

COOHCOOH

(XN')p Ο)(XN')p Ο)

(式卞，XN-為係相對離子的^賈陰離子(惟，N HOOC COOH ^ ^z;(Formula, XN- is a relative ion of the gia anion (only, N HOOC COOH ^ ^ z;

N N 為具有2個羧基的含氮二牙配位子，N N is a nitrogen-containing bidentate ligand having two carboxyl groups,

N NN N

N人N 為含氮四牙配位子，N human N is a nitrogen-containing tetradentate ligand,

N N 為^氮牙配位子，n表示〇〜2的整數;P表示中和錯人體的電通式(2) R1 A' R2—2+—p4N N is a nitrogen-dentate ligand, n is an integer of 〇~2; P is an electric formula of a neutralized human body (2) R1 A' R2—2+—p4

I R3 一體而與此等所鍵_氮原子或 (2) 201141816 環，A_表示陰離子）。離子2: ΐ酸1離f XN•為六__子、四氟硼酸I R3 is integrated with these bonds _ nitrogen atom or (2) 201141816 ring, A_ represents anion). Ion 2: ΐ1 1 from f XN• is __子, tetrafluoroboric acid

Wit以為f，、 ' ^2，^4 為中具有2個_含氮二牙配位子 5.如1.之光化學電池，其中含氣四 2,2，-聯苯并咪唑。仙卞馬次2 .-秘味唑或詩i如化學電池，其中半導體微粒子為氧化鈦、氧化鋅、氧化錫、或此等的混合物。机⑴砰么I ί 5光化學電池’*令録鹽化合物或鱗鹽化合物中的A-^亂齡軒、四_酸聽料、六__陰離子或雙(二氟甲基磺醯基)亞胺基陰離子。 8.如1.之光化學電池，其中電解質溶液含有氧化還原對。、9:如1·之光化學電池，具有係為將藉由前述雙核釕錯合體素增感的半導體微粒刊定於電極上的光賴換元相及對極，且在此之間具有含有前述銨鹽化合物或鳞鹽化合物的電解質溶液層0 【發明之效果】本發明的光化學電池，具有:由吸光係數高之電子移動優異的雙核釕錯合體色素增感的半導體微粒子，及含有銨鹽化合物^鱗鹽化合物的電解質溶液。該光化學電池的光電變換效率高，而且比起不含銨鹽化舍物或鱗鹽化合物著，可獲得高耐久性。【實施方式】【實施發明的形態】本發明的藉由雙核釕錯合體色素增感的半導體微粒子，可藉 201141816 由使釕錯合顯半導·錄子_而獲得。古h )中代表為相對離子的]^價陰離子(惟，N A 1 * ，例如六氟磷酸離子、過氯酸離子、四苯; =，、f氣甲燒侧子、硫氮酸離子= 二 ⑽化物離子、碟化物離子等_化物離子等，作較佳為上 ^酉夂離子、四__子、_離子、鹵化物離四_酸離子、硝酸離子、视物離子又5: “it 1:子、硫代硫酸離子、碳酸離子、磷酸-虱離千#，較佳為硫酸離子。，敗又’通式(1)中，Wit assumes that f,, '^2, ^4 is a photochemical battery having two _ nitrogen-containing bidentate ligands, such as 1. It contains gas tetra-2,2,-bibenzimidazole.仙卞马次2.-Mimesazole or poetry i such as a chemical battery, wherein the semiconductor microparticles are titanium oxide, zinc oxide, tin oxide, or a mixture thereof. Machine (1) 砰 I I ί 5 photochemical battery '* 令录 salt compound or squama salt compound in A-^ 乱龄轩, tetra-acid listener, hexa-anion or bis(difluoromethylsulfonyl) Imino anion. 8. The photochemical cell of 1. wherein the electrolyte solution contains a redox couple. 9. The photochemical battery of claim 1, wherein the semiconductor microparticles sensitized by the dinuclear conjugated voxel are reported on the electrode and the opposite phase, and have a content therebetween. The electrolyte solution layer of the ammonium salt compound or the scale salt compound [Effect of the invention] The photochemical battery of the present invention has semiconductor microparticles sensitized by a binuclear ruthenium complex dye having excellent electron absorption coefficient, and ammonium. An electrolyte solution of a salt compound. The photochemical battery has high photoelectric conversion efficiency and high durability compared to the case of not containing an ammonium salt or a scale salt compound. [Embodiment] [Embodiment of the Invention] The semiconductor fine particles sensitized by the dinuclear ruthenium complex dye of the present invention can be obtained by making a 半显显半、、、、、、、、. In ancient h), it is a relative ion of the valence anion (only, NA 1 *, such as hexafluorophosphate ion, perchlorate ion, tetraphenyl; =, f gas azone, sulfuric acid ion = two (10) a compound ion, a dish ion, or the like, preferably as an upper electrode, a tetra-ion, a _ ion, a halide, a tetra-acid ion, a nitrate ion, and an apparent ion 5: "it 1: a child, a thiosulfate ion, a carbonate ion, a phosphoric acid-phosphonium, and preferably a sulfate ion, and a failure, in the formula (1),

HOOC COOH >^<HOOC COOH >^<

N N 早2倾基的含氮二牙崎子。麟(C(X)H)可脱去質子，传ΐ^ίίί^00') °該具有2麵基的含氮二牙配^ 係在錯&體内含有2個，但是此等可相同也可不同。配位^含有2健基的含氮二牙配位子，例如以下式㈣表示的N N is 2 basal nitrogen-containing dentate. Lin (C(X)H) can remove protons, pass ΐ^ίίί^00') ° The nitrogen-containing two-dentate system with 2-sided base contains 2 in the wrong & body, but these can be the same It can also be different. Coordination ^ containing a nitrogen-containing bidentate ligand of 2, such as represented by the following formula (d)

(1-Α) 如式中’ -COOH的Η也可脱離，把、R22、r23、r24、r25及獨立表示氫軒、或取代或無取韻直鏈或分支烧基，或專虽中的-個以上成為-體而與此等所鍵結的碳原子一起形成取代或無取代的芳香族烴環。战烧基以碳數6以下者較佳，曱基、乙基更佳。又，R22與R23、R24與R25、r21與r26成為一體而與此等所 201141816 佳。員芳香族煙環(也可具有取代基)亦為較氧基、2乙氧iig基，例如燒基(甲基、乙基等〉、燒氧基(甲 R24 ϋ6 原子，或R21與R26為氫原子且R22與R23、烴環較佳，r;; 等所鍵結的碳原子一起形成6員芳香族均為氣原子尤佳。酸、的二牙配位子’例如2,2, ♦岭4,4，-二羧聯桃舰—等哇琳、仏 =的一)，也可脱再者，通式(1)中， Ν…Ν(1-Α) As in the formula, -COOH can also be detached, R22, r23, r24, r25 and independently represent hydrogen hydrazine, or substituted or unnatural rhombohedral or branched alkyl, or One or more of them become a body and form a substituted or unsubstituted aromatic hydrocarbon ring together with these bonded carbon atoms. It is preferred to use a carbon number of 6 or less, and a mercapto group or an ethyl group is more preferable. Further, R22 and R23, R24 and R25, r21 and r26 are integrated, and these are better than 201141816. The aromatic aromatic ring (which may also have a substituent) is also a relatively oxy, 2 ethoxy iig group, such as a ketone group (methyl, ethyl, etc.), an alkoxy group (a R24 ϋ6 atom, or R21 and R26 are A hydrogen atom and R22 and R23, a hydrocarbon ring is preferred, r;; such as a carbon atom bonded together to form a 6-membered aromatic is preferably a gas atom. An acid, a second-dentate ligand 'for example, 2, 2, ♦ Ling 4,4,-dicarboxylian peach ship - such as wow, 仏 = one), can also be removed, in the general formula (1), Ν...Ν

Ν 'Ν 表示含氮四牙配位子。該含氮四牙配位子例如以下式(剛表示的配位子 R31 Ν~~； >_// Ν=< R33 e1、r32 及 R33 4 r36 >^N M-^ R32 取代的直_分支錄，或此或取代或無等戶錢子-細彡成取代或無取“ 基，或此等當中的二個以上成為的直鏈或分支燒起形成取代或無取代的芳香族烴環。-/、寻所鍵結的碳原子一 201141816 烧基以^數^町者較佳，甲基、乙基更佳。原子=形丄===二與 =所鍵結的碳 =取代基’例如燒基(甲基、乙基等)、以較氧佳基= 為氫原子或甲基較佳，R31~R36的在 ‘四牙配位子例如以了如原子尤佳 1 〜T?36Ν 'Ν indicates a nitrogen-containing tetradentate ligand. The nitrogen-containing tetradentate ligand is, for example, the following formula (the ligand R31 Ν~~; >_// Ν=< R33 e1, r32 and R33 4 r36 > ^N M-^ R32 Straight_branch, or this substitution or no-household money - finely substituted or not taken "base, or two or more of these straight chains or branches are burned to form a substituted or unsubstituted aromatic Hydrocarbon ring.-/, find the carbon atom to be bonded to a 201141816. The base is preferably a ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ The substituent 'for example, a calcinyl group (methyl, ethyl, etc.), a preferred oxygen group = a hydrogen atom or a methyl group, and the R31 to R36 in the 'tetradentate ligand, for example, such as an atom is particularly preferred 1~ T?36

(1-B2) 式中，R及R42各自獨立而表的直鏈或分支燒基，或此等成為_體此所===代 :，細戈或無取代的芳香族烴環，r43及:4f 原子表氫原子、或取代或無取代的直鏈或分 A 而代而與其所鍵結的碳原子一起几土或此#成為—體烧基以碳數=者=成; 子一起形成6員可ί碳原起形成6員芳香族烴與此等所鍵結的碳原子-下式(1-B3)表示的配位子較Ί -有取代基)亦為尤佳，例如以 201141816(1-B2) wherein R and R42 are each independently a straight or branched alkyl group, or such a group is === generation: fine or unsubstituted aromatic hydrocarbon ring, r43 and : 4f atomic hydrogen atom, or substituted or unsubstituted straight chain or sub-A and substituted with the carbon atom to which it is bonded, or this # becomes a body-burning group with carbon number = = =; 6 members can form a 6-membered aromatic hydrocarbon from the carbon to form a carbon atom to which these bonds are bonded - a ligand represented by the following formula (1-B3) is more preferred than a ruthenium-substituted substituent, for example, 201141816

R 58R 58

R 57 R 56 R、式中，R51，R52、R53 54 代或無減_或分ωs= 而表ίΐίί數f取代或無取代的直鏈或分支烧基 ”6以下者較佳，甲基、乙基更佳。 R52、R53 較佳，W8全為氫原子，或 R R R 及R7 為甲基&R51、r54、r55 58 尤佳，R51〜R58全為氫原子更佳。及R為虱原子、〜含，四牙配位子，例如、2,2，_聯射、2,2，_聯咪唾、2,2,_聯苯 ^米唾等，較佳為2,2’_聯咪唾、2,2，_聯苯并咪唾，更聯苯并咪唑。 .. 通式⑴中，R 57 R 56 R, wherein R51, R52, R53 54 generation or no reduction _ or fraction ωs = and the number of the linear or branched alkyl group substituted or unsubstituted is preferably less than 6 or less, methyl, Preferably, ethyl group is preferred. R52 and R53 are preferred, and W8 is all hydrogen atom, or RRR and R7 are methyl & R51, r54, r55 58 are preferred, and R51 to R58 are all hydrogen atoms. And R is a halogen atom. , ~ containing, tetradentate ligand, for example, 2, 2, _ _, 2, 2, _ _ _ _ _, 2, 2, _ biphenyl ^ rice saliva, etc., preferably 2, 2 ' _ joint Sodium saliva, 2,2, _biphenylpyrene, more bibenzimidazole.. In the formula (1),

N 表示含氮二牙配位子。該含氮二牙配位子，在錯合體内含有2 個，但是此等可相同也可不同。該含氮二牙配位子例如以下式(1-C)表示的配位子。 10 201141816N represents a nitrogen-containing bidentate ligand. The nitrogen-containing bidentate ligand contains two in the conjugated body, but these may be the same or different. The nitrogen-containing bidentate ligand is, for example, a ligand represented by the following formula (1-C). 10 201141816

R 16 (1-C) 式令，R11、R12 13 立而表示氫原子、戈、R 、R 、R17及R18各自獨令的二個以上—起無取代的直鏈或分支絲，或此等當取代的芳香族烴環。〃等所鍵結合的碳原子一起形成取代或無烧基較佳為碳數如& 第三十二燒基又ΐ佳更佳為碳數18以下者’甲基、此等所鍵結的碳原子一 2個。ϋ 一與mRi8成為一體而與亦為較佳。芳香族烴環的也^具2代基） R〜R為虱原子或甲基、第二 π〜π均為氫原子，或r12及弟RTd基笛一十兮基較佳，十二烷基，S RU、R"〜R“二ί =二丁基、壬基、 r18成為-體而與此等所鍵結的碳原子二起开與 (甲基等也可具鋒錄），r12〜r17環 if;十；7烧基，更佳為氫原子亦為尤佳。再者’ R1产盘Rii R與尺成為-體而與此等所鍵結的碳原子：丄族烴環(f基等也可具有取絲），Rn、Rl f、Rl 7 i貝芳香或甲基、第三丁基、壬基、十二烧基，更mu'子含氮二牙酿子，风2,令岭、22佳。一十二烧基普比咬、1,10-啡琳、2-(2-。比咬基)啥琳，二-等，較佳為2,2,♦比咬、2,2，-4,4，-二甲基.比)唆琳，次:圭2 三丁基-聯岭2’2M,4’.二壬基.聯，、2,2，.4,4，二忙工基第 11 201141816 聯吡啶、1，1〇-σ非啉。又，η表示陽離子的價數，通常為0〜2的整數，較佳為1或2，更佳為1。又，ρ表示為了中和錯合體的電荷所必要的相對離子的數目。如上所述，本發明使用的雙核釕錯合體的具體化合物，例如以下(D-1)至(D-18)的化合物，較佳為使用(D-4)、（D-5)、（D-9)、 (D-10)、(D-11)、(D-13)、(D-16)、(D-17)及(D-18)。又，式(D-1)〜(D-18) 中的-COOH的Η也可脱離。 12 201141816 lR 16 (1-C) formula, R11, R12 13 represents two or more hydrogen atoms, ge, R, R, R17 and R18, each of which is unsubstituted or straight or branched, or such When substituted aromatic hydrocarbon rings. The carbon atom to which the bond or the like is bonded together forms a substituted or non-burning group, preferably a carbon number such as & the thirty-second alkyl group is preferably a carbon number of 18 or less, and the methyl group is bonded. One carbon atom. ϋ One is integrated with mRi8 and is also preferred. The aromatic hydrocarbon ring also has a 2nd generation group. R to R are a ruthenium atom or a methyl group, and the second π to π are each a hydrogen atom, or r12 and a cyclodextrin are preferably a decyl group. , S RU, R " ~ R "two ί = dibutyl, fluorenyl, r18 become - body and the carbon atoms bonded with these two open and (methyl can also be recorded), r12 ~ R17 ring if; ten; 7 alkyl group, more preferably hydrogen atom is also preferred. In addition, 'R1 production disk Rii R and ruler become body - and these bonded carbon atoms: steroid hydrocarbon ring (f The base may also have a wire), Rn, Rl f, Rl 7 i aroma or methyl, tert-butyl, fluorenyl, dodecapine, more mu' sub nitrogen-containing second-handed fermenter, wind 2, Lingling, 22 good. Twelve burning Kip than biting, 1,10-Calline, 2-(2-. than biting base) Yulin, two-etc., preferably 2, 2, ♦ than bite, 2,2,-4,4,-Dimethyl. Ratio) Yu Lin, Times: Gui 2 Tributyl-Lianling 2'2M, 4'. Diterpenoid. Union, 2,2,.4, 4, two busy basis 11 201141816 bipyridyl, 1,1 〇-σ phenoline. Further, η represents the valence of the cation, usually an integer of 0 to 2, preferably 1 or 2, more preferably 1. Also, ρ means in order to The number of relative ions necessary for the charge of the mismatched body. As described above, specific compounds of the binuclear ruthenium complex used in the present invention, for example, the following compounds (D-1) to (D-18) are preferably used ( D-4), (D-5), (D-9), (D-10), (D-11), (D-13), (D-16), (D-17) and (D- 18) Further, the enthalpy of -COOH in the formulas (D-1) to (D-18) can also be detached. 12 201141816 l

(cicvh (pf6·) (pf6·) (D-3) coo*(cicvh (pf6·) (pf6·) (D-3) coo*

(PFe) (D4> 13 201141816(PFe) (D4> 13 201141816

BF. (BPh4)BF. (BPh4)

HOOC HOOCHOOC HOOC

(0S02CF3)(0S02CF3)

(CI04) 14 201141816(CI04) 14 201141816

(Ν〇3·) (|·(Ν〇3·) (|·

HOOC HOOCHOOC HOOC

(PF6*)(PF6*)

(PF4) 15 201141816(PF4) 15 201141816

(pf6) (D-13)(pf6) (D-13)

16 20114181616 201141816

(D-15)(D-15)

+ (D-16) (pf6+ (D-16) (pf6

(PFg) (D-17) 17 201141816(PFg) (D-17) 17 201141816

+ (PFe) (D-18) 又二該等雙核釕錯合體可單獨使用或混合二種以上使該等雙核釕錯合體可利用公知太、本人士、, 灸用 2006/038587號）。方法合成(例如參照國際公開第本發明錢料導雜粒子，例如氧化鈦、氧、氧化鶴、氧化飢等金屬氧化物類；鈦酸銷鈦金細化物；舰辩金射錄化鎵^ 錫。又，半導體微粒子的初級粒徑無你爾^ 為使用1〜5GGGnm，更佳為使用2〜5GGnm，尤佳為〜nm者。該等半導體微粒子可單獨使用或混合二種以上 18 201141816 使用。、曾。使雙核金屬錯合體色素吸附於半導體微粒子的方法，例如在 V電性支持體上形成含有半導體微粒子的半導體半導 ^後，將其浸泡於含有雙核金屬錯合體色素的溶液(的方法 …國際公開第2006/038587號）。半導體層，可在導電性支持體上塗佈半導體微粒子的糊劑並加熱煅燒而形成。並且，浸泡色素溶液後，將該形成有半導體層的導電性支持體清洗、 ^ 色素溶液的溶劑，例如曱醇、乙醇、/丙m醇、乙等義；乙腈、丙腈等腈類；N，N-二甲基乙蕴胺、耶_二曱胺類;N_曱基吡咯啶，等脲類;二曱基亞颯等亞砜 i使用異丙醇或第三丁醇、乙腈。該等有機溶劑可單獨使用也可混合2種以上使用。干辛吸素濃度可適當決定，係高濃度者能於短時間使色素吸附故為較佳，飽和溶液較佳。 m匕 20〜的溫度，通常定為0〜8〇°C即可，較佳為定:約的iff泡於色素溶液的時間)可適當決長，則色素吸附旦=itf為約5〜20小時。吸附時間若較此更低。、。、里不大ό、交化’反而有時光電變換效率有時會降本發明的光電變換元件，含有藉由雔人半導體微粒子，呈體而士，如‘及，，又核釕錯合體色素增感的半導體微粒子固“上ί如係騎由該対錯合體色素增感的極。導電性為形成在透明基板上的透明電錫系化合物、魏料賊表的氧化本發明的光化學電池，可傕感的半導體微粒子製造。'处猎由又核釕錯合體色素增本發明的光化學電池，且妒士換元件與對極當作電極，並^ 1二帝f有上述本發明的光電變嫌X具間具有電解質溶液層。又，本發明 201141816 的光電 <，元件使用的電極與對極至少其中之—為透明電極。伽f光電變換元件組合成光化學電池時作用為正極者。上述導電性電極同樣具有導電層的基板，但若使用 ί:ίίί時’不一定需要基板。對極使用的導電劑，例如可使用翻專金屬、碳、摻雜_氧化錫料電性金屬氧化物。光化學電池的電解質係使用含有銨鹽化合物或鱗笛電ΐ質溶液。該電解質溶液係含有銨鹽化合物或鱗鹽 < δ物”氧化還原對(redoxpair)者。銨鹽化合物或鱗鹽化合物可也可組合2触上使用。也可組合1種以上録鹽化合物與1種以上鱗鹽化合物使用。口视本發明使帛的健化合物或_化合物，伽x通式(2)表示 R1 R2—；!+—r4 R3 A' (2) 一（式中，Z+表示N+或P+，且R1、圮、¥及汉4可相同也可不同、’各自獨立地表示氫原子、或直鏈或分支烷基，或此等當中二個X上成為體而與此等所鍵結的氮原子或麟原子一起形成飽和，不飽和雜環，A-表示陰離子。），但較佳為以四氰基硼酸鹽、四 $糊酸鹽:六氟磷酸鹽或雙(三氟曱基石黃喊)亞胺基作秘離子的鹽’更佳為使用輯式(E)表示的四減鄉酸鹽作為陰離子的鹽。+ (PFe) (D-18) In addition, these two-core anamorphic complexes may be used singly or in combination of two or more. The dinuclear scorpion conjugates may be used by the well-known person, the person, and moxibustion No. 2006/038587). Method synthesis (for example, refer to the international publication of the invention for the introduction of impurity particles, such as titanium oxide, oxygen, oxidized crane, oxidized hunger and other metal oxides; titanium titanate titanium fines; ship defense gold recording gallium ^ tin Further, the primary particle diameter of the semiconductor fine particles is not used in the range of 1 to 5 GGGnm, more preferably 2 to 5 GGnm, and particularly preferably ~ nm. The semiconductor fine particles may be used alone or in combination of two or more 18 201141816. For example, a method of adsorbing a dinuclear metal-aligned body dye to a semiconductor fine particle, for example, forming a semiconductor semiconductor containing semiconductor fine particles on a V-electron support, and immersing it in a solution containing a dinuclear metal-conjugated dye ...International Publication No. 2006/038587. The semiconductor layer can be formed by coating a paste of semiconductor fine particles on a conductive support and heating and calcining. Further, after the dye solution is immersed, the conductive support formed with the semiconductor layer is supported. Body cleaning, ^ solvent of pigment solution, such as decyl alcohol, ethanol, / propanol, B, etc; nitrile such as acetonitrile, propionitrile; N, N-dimethyl acetylamine, yeah _ Amidoxime; N_decylpyrrolidinium, etc.; sulfoxide i such as dimercaptopurine i uses isopropanol or tert-butanol or acetonitrile. These organic solvents may be used alone or in combination of two or more. The concentration of dry octospermone can be appropriately determined, and those with high concentration can better absorb the pigment in a short time, and a saturated solution is preferred. The temperature of m 匕 20 〜 is usually set to 0 〜 8 〇 ° C, Preferably, it is determined that the time of the iff bubble in the dye solution can be appropriately determined, and the dye adsorption denier = itf is about 5 to 20 hours. The adsorption time is lower than this. ,. In the meantime, the photoelectric conversion efficiency sometimes degrades the photoelectric conversion element of the present invention, and contains a semiconductor semiconductor microparticle, which is a kind of body, such as 'and, and a nuclear complex dye. The sensitized semiconductor microparticles are solidified by the sensitization of the erbium complex dye. The conductivity is the transparent tin-based compound formed on the transparent substrate, and the oxidation of the thief table of the present invention. Manufacture of semiconductor microparticles with sensation of sensation. 'The photochemical battery of the invention is added by the nucleus and the nucleus pigment, and the gentleman-changing element and the counter electrode are used as electrodes, and the two-dimensional f has the above-mentioned invention. The photoelectric conversion layer has an electrolyte solution layer. Further, the photoelectricity of the invention 201141816, the electrode and the counter electrode used in the element are at least a transparent electrode. The gamma-f photoelectric conversion element is combined into a photochemical battery to function as a positive electrode. The above-mentioned conductive electrode also has a substrate of a conductive layer, but if ί: ίίί, the substrate is not necessarily required. For the conductive agent used for the pole, for example, metal, carbon, doping_oxidation can be used. . A metal oxide electrolyte material-based electrically photochemical batteries containing ammonium salt compound or scales the flute electrically ΐ substance solution-based electrolytic solution containing an ammonium salt or a phosphonium salt compound <. Δ was "redox pair (redoxpair) persons. The ammonium salt compound or the scale salt compound may also be used in combination with 2 contacts. It is also possible to use one or more kinds of salt-recording compounds and one or more kinds of scale salt compounds. According to the present invention, a health compound or a compound of 帛, gamma x (2) represents R1 R2 —; !+—r4 R3 A′ (2) (wherein Z+ represents N+ or P+, and R1, 圮, ¥ and Han 4 may be the same or different, 'each independently represents a hydrogen atom, or a linear or branched alkyl group, or a nitrogen atom or a lining atom bonded to two of these X atoms and bonded thereto. Together, a saturated, unsaturated heterocyclic ring is formed, and A- represents an anion.), but is preferably a tetracyanoborate, a tetra-picrose salt: a hexafluorophosphate or a bis(trifluoromethyl sulfhydryl) anthracene group. The salt of the secret ion is more preferably a tetra-n-acid salt represented by the formula (E) as a salt of an anion.

CN NC—Β·—CN ' R1 (E)CN NC—Β·—CN ' R1 (E)

CN R2—|+—R4 . R3 (式(E)中’ Z+表示N+或p+，且R1、R2、R3及R4可相同也可不同，各自獨立地表示氫原子、或直鏈或分支烷基，或此等當 201141816 申一個以上成為一體而與此等所鍵结飽和或不飽和雜環）。、付原子或&原子-起形成 R1、R2、R3及R4，為氫原子，或碳 18以下，尤佳為碳數】〜8的絲。又，Rl、r2、r3及更數體而與此等所鍵結的氮原子或磷原子-起开佳為形成6員的飽和或不飽和雜環，狀為子、四己基銨離子、四庚其銨離早、lit 四戊基敍離銨離子、二甲其辛美餘齙；望四辛土錢離子、三甲基己基二丁基麵義子、了奸縣^子、級錄離 +子更佳，四丁基銨離子尤佳。卞寺展疋鏑離子較佳，四鱗鹽化合物的鱗陽離子，以鱗離子 r四乙，離子、四丙基鱗離子、四丁基鱗子、四己基鱗離子、四庚基鱗離子、四辛基_子、鱗離ί1二？基辛基鱗離子等四級鱗離子較佳，四級鱗離子1佳1 四丁基鱗離子尤佳。久吻雕于旯佳本發明使_銨合物及/_鹽化至飽和濃度的細較佳，almd== 的视圍更佳，〇.5mol/l至5mol/l尤佳。田^發！的電㈣溶液，理想為含有氧化還原對㈣〇x_)。使用的氧化還原對無特殊限制，例如： (1) 破與埃化物(例如蛾化链、硬化卸等金屬破化物；姨化四丁碘化四丙基銨、碘化吡啶鑌鹽（pyridinium i〇dide)、碘化咪唑Cimidazoliumiodide)等四級銨化合物的織化物)的組合；’、’、 (2) 溴與溴化物(例如溴化鋰、溴化鉀等金屬溴化物；漠’化四丁土銨、>臭化四丙基銨、漠化。比啶鑌鹽、漠化咪唑等四級録化的溴化物)的組合； σ (3) 氯與氯化物(例如氯化鋰、氣化鉀等金屬氯化物；.氣化四丁 201141816 基銨、氯化四丙基銨、氯化吡啶鏽鹽、氣化味唑等四級按化合物的氯化物)的組合； (4) 烷基紫精（alkylviologen)與其還原體的組合； (5) 苯醌/氫醌、鐵(Π)離子/鐵(jn)離子、銅①離子/銅(π)離子、錳(II)離子/鐘(III)離子、鈷離子(11)/鈷離子(m))等過渡金屬離子對； ⑹氰化鐡(II)/氰化鐵(III)、四氣化钻(II)/四氣化銘(ΠΙ)、四漠化鈷(II)/四溴化鈷(ΙΠ)、六氯化銥(IIy六氣化銥(111)、六氰化釕 =化_1)、六氣錢(Π)/六氯化尋1}、六氯化銖_六氯化 =v)、六氣化銶(IV)/六氣化銖(V)、六氯化餓(111)/六氯化餓(IV)、六虱化餓(IV)/六氯化餓(V)等錯離子的組合；铷⑺tit釘、猛、錦、鍊等過渡金屬，與聯吼咬或其衍生形成&=類衍生物、倾或其衍生物等共娜環及其衍生物 —(8)二茂鐵/二茂鐵鹽離子、二茂鈷/二茂鈷二贿鹽離子轉戊二烯及其衍生倾金屬的錯ς體類；一 (9)外琳系化合物類； ’ 較佳為使用前述⑴列舉的氧化還原 Ϊ單獨或齡二_上制。轉植觀對電解質溶液的溶劑，例如.皮、趟類、鏈狀_、環狀_類、^魏胺g腈^鏈，類、環狀類、環狀石風類、鏈狀脲類、環妝日論、:被狀醯胺類、鏈狀石風的溶^限於此等，可單獨使用或混合電解質溶液燒而製作轉體絲二以鱗半導體錄子的_，加熱锻 400〜55(TC锻燒粒子的賴為二氧化欽時’以溫度 ⑶將獲得的附有薄膜的透明電極浸泡於色素溶液，戴持雙核 22 201141816 釕錯合體色素而製作光電變換元件。獲得ί光電題元件與當作趣的蒸财_碳的透明電極疊合’於制放人電解質溶液。 ^職月【實施例】CN R2—|+—R4 . R3 (In the formula (E), 'Z+ represents N+ or p+, and R1, R2, R3 and R4 may be the same or different, each independently represents a hydrogen atom, or a linear or branched alkyl group. , or such as 201141816, one or more of them become integrated with such a saturated or unsaturated heterocyclic ring. The atom or the atom is formed into a filament of R1, R2, R3 and R4 which is a hydrogen atom or a carbon number of 18 or less, particularly preferably a carbon number of -8. Further, R1, r2, r3, and a higher number of the nitrogen atoms or phosphorus atoms bonded to these groups are preferably formed into a 6-membered saturated or unsaturated heterocyclic ring, which is a sub, tetrahexylammonium ion, or a tetrad. Gengqi ammonium is early, lit tetrapentyl quarantine ammonium ion, dimethyl octyl sulphate; Wang Si xin soil money ion, trimethyl hexyl dibutyl surface progeny, rape county ^ son, grade record away + More preferred, tetrabutylammonium ion is preferred.卞疋镝疋镝疋镝疋镝较佳 , , , , , 较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳较佳辛基_子, scales away from ί1 two? It is preferred that the quaternary squamous ions such as the sinusoidal cations are better, and the quaternary squamous ions of the quaternary ionic ions are particularly preferred. The long-kissing eagle in the 旯本本本本本本本本 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Tian ^fa! The electric (iv) solution is ideally containing a redox pair (tetra) 〇x_). The redox pair to be used is not particularly limited, for example: (1) Broken and etchant (e.g., moth chain, hardened unloading, etc.; tetramethylammonium iodide, pyridinium iodide) a combination of 织dide), a quaternary ammonium compound such as imidazolium iodide); ', ', (2) bromine and bromide (eg, metal bromide such as lithium bromide or potassium bromide; Ammonium, > stinyl tetrapropylammonium, desertification. Combination of four-staged bromide such as pyridinium salt and desert imidazole; σ (3) Chlorine and chloride (such as lithium chloride, gasification) a metal chloride such as potassium; a combination of gasification of tetrabutyl 201141816 ammonium, tetrapropylammonium chloride, chlorinated pyridine salt, gasified oxazole, etc. according to the chloride of the compound; (4) alkyl violet Combination of alkylviologen and its reducing body; (5) Benzoquinone/hydroquinone, iron (Π) ion/iron (jn) ion, copper 1 ion/copper (π) ion, manganese (II) ion/clock (III) ) transition metal ion pairs such as ions, cobalt ions (11) / cobalt ions (m)); (6) cerium (II) cyanide / iron (III) cyanide, four gasification drills (II) / four gasification Ming (ΠΙ ), four deserts Cobalt (II) / cobalt tetrabromide (ruthenium), ruthenium hexachloride (IIy hexahydrate ruthenium (111), hexacyanohydride = _1), six gas (Π) / hexachloride 1 , hexachlorophosphonium hexachloride = hexachlorinated = v), six gasified hydrazine (IV) / six gasified hydrazine (V), hexachlorinated (111) / hexachlorinated (IV), six sputum hunger ( IV) / hexachloroheptidation (V) and other combinations of wrong ions; 铷 (7) tit nails, fierce, brocade, chain and other transition metals, and the joint bite or its derivatives to form & = derivatives, dump or its derivatives, etc. Zenitrocyclic ring and its derivatives—(8) ferrocene/ferrocene salt ion, ferrocene/ferrocene broth salt ion pentadiene and its derived metal mitochondria; The outer-lining compound; 'It is preferred to use the redox oxime listed in the above (1) alone or in the same manner. A solvent for the electrolyte solution, for example, a skin, a quinone, a chain _, a ring _ class, a sulphamine g sonitrile chain, a class, a ring type, a ring stone type, a chain urea, The ring makeup theory, the dissolution of the scorpion amides and the chain-like stone winds is limited to these, and can be used alone or in combination with an electrolyte solution to produce a spheroidal semiconductor recording _, heating forging 400~55 (When the TC calcined particles are dioxins), the obtained transparent electrode with a film is immersed in a dye solution at a temperature (3), and a photoelectric conversion element is produced by wearing a double-core 22 201141816 钌合体体体. It is superimposed with the transparent electrode of carbon as a fun carbon to make a human electrolyte solution.

，，實施例具體說明本發明’但本發明的範圍不限於此專。又，絲學電池的光電賴效率，翻射太陽模機(股)公司製)的模擬太陽光而測定。又，雙合^(素;^ 照國際公開第2〇_觀7號合成。。邮常係I 實施例1 (多孔質二氧化鈦電極的製作）使用網版印刷機於透明導電性玻璃電極(旭硝，子(股)公司上塗佈二氧化鈦糊劑PST-18NR(曰揮觸媒化成(股)公司製)合& 明層、抓4〇0(：(曰揮觸媒化成(股)公司製)當作擴散層。將^得的膜於25C、相對濕度60%的氣體氛圍下熟成5分鐘，並將該已熟成的膜於440〜460°C烺燒30分鐘。反複該操作，製作16mm2多、孔質二氧化鈦電極。 (吸附有色素的多孔質二氧化鈦電極的製作）於第三丁醇/乙腈(=1 : 1(容量比))的混合溶劑中加入雙核釕錯合體色素（D-4)，製備該釕錯合體色素的飽和色素溶液 (O.lmmol/1)。其次’在内溫3(rC的恆溫器中，將多孔質二氧化鈦電極浸泡於前述飽和色素溶液20小時，製作吸附有色素的多孔質二氧化鈦電極。 (光化學電池的製作）將以如上方式獲得的色素吸附多孔質二氧化鈦電極與鉑板(對極)重疊。其次，將由表1所示組成構成的電解質溶液利用毛細管現象滲入兩電極的間隙，藉此製作光化學電池。又，表1中的Ui、 MPI-I、I2、TBP、TBA-B(CN)4、及 GBL 各代表碘化鋰、碘化 μ 曱基-3-丙基咪唾（l-methyl-3-propylimidazolium iodide)、蛾、第二丁基°比°定、四丁基錢四氰基侧酸鹽、及γ-丁内酉旨。 (光電變換效率的測定） 23 201141816 $用^弘精機(股)公司製太陽模擬機，照射l〇〇mW/cm2的模擬太陽光並測定獲得的光化學電池的光電變換效率。 (耐久性評價） ^將獲，的光化學電池於暗處於60¾靜置既定時間後返回室 ^用英弘精機(股)公司製太陽模擬機，照射100mW/cm2的模擬太陽光並測定光電變換效率(η)。表i表示於暗處於6〇(5(：放置】 I後的光電變換效率定為100%時，5日後光電變換效率的維持率。實施例2〜6、比較例1〜2 、改變雙核釕錯合體色素、色素溶液濃度、及電解質溶液中的添加物種類或濃度，除此以外與實施例丨以同樣方式製作光化學，池^並測定光電變換效率。又，雙核釕錯合體色素(D_18)的色素溶液濃度定為0.3mm〇l/l。其結果一併顯示於表丨。又，4_第三丁基吼。定(TBP)是已知可獲最良好結果的當作添加物的化合物。【表1】The embodiments illustrate the invention in detail, but the scope of the invention is not limited thereto. Further, the photoelectric efficiency of the silk-based battery was measured by the simulated sunlight of a solar molding machine. In addition, the double-combined compound (the first one is synthesized according to the International Publication No. 2). The postal system I Example 1 (Production of porous titania electrode) A screen printing machine is used for a transparent conductive glass electrode (Asahi Nitrogen, a company (shared company) coated with titanium dioxide paste PST-18NR (曰曰媒化化 ( 公司公司合合明明明、、、、、、、、、、、、、、、、 ( ( ( ( ( ( ( ( ( ( ( The film was made into a diffusion layer, and the obtained film was aged for 5 minutes in a gas atmosphere of 25 C and a relative humidity of 60%, and the cooked film was calcined at 440 to 460 ° C for 30 minutes. 16mm2, porous TiO2 electrode. (Preparation of porous titanium dioxide electrode with pigment adsorption) Addition of dinuclear ruthenium complex dye (D- in a mixed solvent of t-butanol/acetonitrile (=1: 1 (capacity ratio)) 4) Preparation of a saturated dye solution (0.1 mmol/1) of the ruthenium complex dye. Secondly, in the internal temperature 3 (rC thermostat, the porous titania electrode was immersed in the saturated dye solution for 20 hours to prepare adsorption. Porous titanium dioxide electrode with pigment. (Production of photochemical battery) The color obtained in the above manner The adsorbed porous titania electrode was overlapped with the platinum plate (opposite pole). Secondly, the electrolyte solution having the composition shown in Table 1 was infiltrated into the gap between the two electrodes by capillary action, thereby producing a photochemical battery. Further, Ui in Table 1, MPI-I, I2, TBP, TBA-B (CN) 4, and GBL each represent lithium iodide, iodinated μ-methyl-3-propylimidazolium iodide, moth, Dibutyl group ratio, tetrabutyl quaternary tetracyano side acid salt, and γ-butane side acid. (Measurement of photoelectric conversion efficiency) 23 201141816 $Solar machine (share) company solar simulator, The simulated sunlight of l〇〇mW/cm2 was irradiated and the photoelectric conversion efficiency of the obtained photochemical battery was measured. (Durability evaluation) ^ The photochemical battery to be obtained was returned to the chamber after the dark time was 603⁄4, and it was returned to the room. A solar simulator manufactured by Seiki Co., Ltd. irradiated 100 mW/cm2 of simulated sunlight and measured the photoelectric conversion efficiency (η). Table i shows that the photoelectric conversion efficiency after the darkness is 6 〇 (5 (: placement) I is set to 100. %, the retention rate of photoelectric conversion efficiency after 5 days. Examples 2 to 6 and Comparative Examples 1 to 2 The photochemistry was prepared in the same manner as in Example 丨, and the photoelectric conversion efficiency was measured in the same manner as in the case of the dinuclear conjugated dye, the concentration of the dye solution, and the type or concentration of the additive in the electrolyte solution. The concentration of the dye solution of (D_18) was set to 0.3 mm 〇 l / l. The results are shown together in the table. Further, 4_t-butyl fluorene (TBP) is known to give the best results. Additive compound. [Table 1]

Lil MPI-I h TBP TBA-B(CN)4 ------ 而规麻色素 mol/L mol/L mol/L mol/L mol/L 溶劑 J人丨王叶價 5曰後的維實施例1 D-4 - 0.6 0.1 - 0.5 GBL~ 比較例1 D-4 - 0.6 ’ 0.1 0.5 GBL^ 實施例2 D-18 - 0.6 0.1 - 0.5 GBL 實施例3 實施例4 D-18 D-18 0 1 0.6 0 5 0.1 0.5 0.5 GBL 實施例5 D-18 A 0.1 0.5 0.1 0.5 ~~ 0.5 GBL 0.1 0.5 GBL 實施例6 D-18 - 0.6 0.1 - 1 GBI 比較例2 D-18 - 0.6 0.1 0.5 GRT — 將電解質>谷液中的添加物（即四丁基錢四氰基侧酸鹽）改為如表2所示之添加物，除此以外與實施例2同樣製作光化學電池’、、，並測定光電變換效率。其結果一併顯示如表2。于'’ 【表2】 24 201141816Lil MPI-I h TBP TBA-B(CN)4 ------ and the pigment is mol/L mol/L mol/L mol/L mol/L solvent. Example 1 D-4 - 0.6 0.1 - 0.5 GBL~ Comparative Example 1 D-4 - 0.6 ' 0.1 0.5 GBL^ Example 2 D-18 - 0.6 0.1 - 0.5 GBL Example 3 Example 4 D-18 D-18 0 1 0.6 0 5 0.1 0.5 0.5 GBL Example 5 D-18 A 0.1 0.5 0.1 0.5 ~~ 0.5 GBL 0.1 0.5 GBL Example 6 D-18 - 0.6 0.1 - 1 GBI Comparative Example 2 D-18 - 0.6 0.1 0.5 GRT - A photochemical battery was prepared in the same manner as in Example 2 except that the additive in the electrolyte solution (i.e., tetrabutyl cyano cyano side acid salt) was changed to the additive shown in Table 2. And measure the photoelectric conversion efficiency. The results are shown together in Table 2. On '' [Table 2] 24 201141816

添加物(錢鹽化合物）基銨四氛基硼醅鹱基銨四氮基硼酸_ 三辛基銨四氰某硼酴_ —争基銨四氰基硼醢鹽丁基曱基略'定鏽四氰基硼酸鹽實施例9 實施例10 添加物濃度Additives (money salt compounds), quaternary ammonium, tetracyclyl, borodecyl ammonium, tetrazoboronic acid, trioctyl ammonium, tetracyano, borax, arsenic, tetracyanoboron, butyl sulfhydryl Tetracyanoborate Example 9 Example 10 Additive Concentration

mol/L 0.5 0.5 0.5 0.5 0.5 5 曰後的維揞率~ΤοΓ 99ΊοΓ 100 102 實施例11〜172電解質溶液中的碘化物，即碘化小曱基_3_丙基咪唑忠几级+改為如表3所示蛾化物，除此以外與實施例6同樣製作先化t池並測定光換效率。其結果-併顯示如表3Mol/L 0.5 0.5 0.5 0.5 0.5 5 揞的的 Τ Τ 102 102 102 100 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 102 A pre-t pool was prepared in the same manner as in Example 6 except that the moth compound shown in Table 3 was used, and the light conversion efficiency was measured. The result - and shown in Table 3

之/ 版Ϊ刷機，在透明導電性玻璃電極(旭石肖子(股)公司製) 作i明ί pi氧化鈦糊劑pst-18nr(日揮觸媒化成(股)公司製)當得的膜(曰ΐ觸媒化成(股)公司製)當作擴散層。將獲過心二目巧又6°%的氣體氛圍下熟成5分鐘，將該經 30 ^ ° ^ (吸附有色素的多孔質二氧化鈦電極的製作）於異丙醇巾加人雙_錯合體色抑_18)，製釕錯合體色 25 201141816 3〇°C的恆溫器中，將多小時’製作吸附有色素素的色素溶液(0.3mmol/l)。其次’於内溫孔質二氧化鈦電極浸泡於前述色素溶液5 的多孔質二氧化鈦電極。 (光化學電池的製作）極)曹1 如ϋ方式獲*的色素吸附多孔質二氧化鈦電極與銘板(對規)象心，將如表4所示組成構成的電解質溶液利用毛細管現象滲入兩電極的間隙，藉此製作光化學 MPM > Ι2 λ ΤΒρ Λ TRp 衣肀的石装吐也 B(CN)4、及G L，各代表埃化甲基； ^ 土 ^坐、蛾、第三丁基喊、四丁基鱗四氰基赚鹽、及円酷。 ^ (光電變換效率的測定）的模擬 a使用英弘精機(股)公司製太陽模擬機照射l〇0mW/cm2 太陽光並測定獲得的光化學電池的光電變換 (耐久性評價）手溫，池於暗4於攸靜置既定_後返回室二股1公司製太陽模擬機，照射1GGmW/em2的模日德的弁雪二變換效率⑻。表4顯示於暗處於6〇°C放置1 比較例3〜Ϊ艾換效率定為1〇〇%時，5日後光電變換效率的維持率。 is同的添加__度，除灿外與實施例樣予電池並败光輕換效率。其絲衣4。又你—一u 加物的化合t红了基简ΤΒΡ)為已知可€最良好結果的當作添【表4】 ΜΡΙ-Γ ----1 L h TBP /«|| 色素 mol/L mol/L mol/L TBP-B(CN )4 mol/L 溶劑财久性評價 5曰後的維持；ίί ίΌ/Λ 貝 18 D-18 0.6 0.1 • 0.5 GBL 午<y〇) 102 比較例3 D-18 ~~〇T~ -----— 0.1 —---- 0.1 比較例4 xh D-18 ι：2 μ ^ 0.6 Γ 里.τ: 0.5 - GBL GBL 94 95 .....^~---~—~L - GBL 95 由乂上、、..果’可知藉由使關鹽化合物當作電解質溶液的添 26 201141816 加物’比起未添加_化合物的射彡，維持高麵變換且耐久性提高。 ' 【產業利用性】依照本發明，可提供-種耐久性高的光化學電池，南吸光係數之電子鑛優異的雙触錯合觀素的丰·=由粒子;及含有銨鹽化合物或鱗鹽化合物的電解質溶液^^牛導體微 .【圖式簡單說明】無。【主要元件符號說明】無0 27/ The Ϊ Ϊ , 在在在在透明透明透明透明透明透明透明透明旭旭旭旭旭旭旭旭旭旭旭旭旭旭旭旭旭旭旭旭旭 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (曰ΐVisitization into a company (share) company) as a diffusion layer. The mixture was aged for 5 minutes in a gas atmosphere of 6°%, and the 30 ^ ° ^ (manufactured by the porous titanium dioxide electrode adsorbed with the pigment) was added to the isopropyl alcohol towel. _ _ 18), 钌钌合体 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 Next, the porous titania electrode of the dye solution 5 was immersed in an internal temperature porous titania electrode. (Preparation of photochemical battery) C. 1 The pigment-adsorbed porous titanium dioxide electrode and the nameplate (pair) of the image obtained by the method of ϋ1, the electrolyte solution composed of the composition shown in Table 4 is infiltrated into the two electrodes by capillary action. Gap, by making photochemical MPM > Ι2 λ ΤΒρ Λ TRp 肀 stone 吐也 also B (CN) 4, and GL, each represents Ai methyl; ^ soil ^ sitting, moth, third butyl shout , tetrabutyl quaternary tetracyano earned salt, and 円 cool. ^ (The measurement of the photoelectric conversion efficiency) The sunlight was irradiated with a solar simulator of the company, and the photoelectric conversion (durability evaluation) of the obtained photochemical battery was measured using a solar simulator manufactured by Hideo Seiki Co., Ltd. Dark 4 攸攸既既既 _ 返回返回返回返回二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二Table 4 shows the retention rate of the photoelectric conversion efficiency after 5 days when the darkness was placed at 6 ° C and 1 was compared with Comparative Example 3 to when the efficiency was changed to 1%. Is the same as the addition of __ degrees, in addition to the inc. and the example to the battery and lose light and light efficiency. Its silk is 4. And you--the combination of a u-additive t-red base is simply added as a known good result [Table 4] ΜΡΙ-Γ ----1 L h TBP /«|| Pigment mol/ L mol/L mol/L TBP-B(CN)4 mol/L Solvent for long-term evaluation after 5曰; ίί ίΌ/Λ 贝 18 D-18 0.6 0.1 • 0.5 GBL 午<y〇) 102 Compare Example 3 D-18 ~~〇T~ -----0.1 0.1---- 0.1 Comparative Example 4 xh D-18 ι: 2 μ ^ 0.6 Γ 里.τ: 0.5 - GBL GBL 94 95 ... ..^~---~~~L - GBL 95 From the top, and the .. fruit, it can be seen that the salt compound is used as the electrolyte solution. 2011 20111616 Additives are compared to the un-added compound. Maintain high surface change and improve durability. 'Industrial Applicability】 According to the present invention, it is possible to provide a photochemical battery having high durability, an electron absorbing coefficient of the south electron absorption coefficient of the double-touching spectroscopy, a particle, and an ammonium salt compound or scale. Electrolyte solution of salt compound ^^ Bull conductor micro. [Simple description of the diagram] None. [Main component symbol description] None 0 27

Claims

201141816 七、申請專利範圍： 1.-種光化學電池^具有藉由以通式⑴表示的雙色素增感的半導體微粒，’及包含以通式⑺表示的鱗鹽化合物的電解質溶液； 1化口物$ 通式⑴201141816 VII. Patent application scope: 1. A photochemical battery having a double dye-sensitized semiconductor fine particle represented by the general formula (1), and an electrolyte solution containing a scale salt compound represented by the general formula (7); Oral material $ general formula (1)

η (ΧΝ·)Ρ (1) (式中，ΧΝ_為相對離子的Ν價陰離子(惟，ν為1或2) HOOC COOH Ν Ν 表示具有2個羧基的含氮二牙配位子， Ν Ν Ν人Ν 表示含氮四牙配位子， Ν Ν 荷所iitrr子;η表示G〜2的整數;ρ表示中和錯合體的電為目也可脱去質子(h+ )而成通式(2) 28 201141816 R1 A· (2) R2 — Z+— I R3 (式中’ Z+表示N+或，且尺1、R2、R3及R4可相同也可不同’各自獨立地表示氫原子或烷基，或此等當中的二個以上成為二體而與此等所鍵結的氮原子或磷原子一起形成飽和或不飽和雜環，A_表示陰離子）。 + 2_如申請專利範圍第1項之光化學電池，其中χΝ_為六氣攝酸離子、四氟硼酸離子、硝酸離子或碘化物離子。、3·如申請專利範®第1項之光化學電池，其中含氮二牙配位子為 2,2 -聯《比唆（bipyridine)、2,2，-(4,4，-二曱基)聯口比咬、2,2，-(4,4，-一-第二丁基)聯吡啶、2,2，_(4,4，-二-正壬基)聯吡啶、2,2，-(4,4，-二-正十二烷基)聯吡啶或1，10_啡啉（phenanthr〇line)。产4.如申請專利範圍第丨項之光化學電池，其中具有2個羧基的含氮二牙配位子為2,2，-聯吼咬_4,4，-二緩酸。 5·如申請專利範圍第1項之光化學電池，其中含氮四牙配位子為 2,2’-聯咪唑（biimidaz〇le)或 2,2，_聯苯并咪唑（benzimidaz〇ie)。 # 6.如專利範圍第〗項之光化學電池’其中半導體微粒子為氧化欽、氧化辞、氧化錫、或此等的混合物。 7.如申請專利範圍第丨項之光化學電池，其中銨鹽化合物，化合物中的A_為四氰基概鹽陰離子、四a砸鹽陰離子六 1鹽陰離子或雙（三氟甲基磺醯基）亞胺基 lbis(tnfluoromethylsulfonyl)imido)陰離子。氧化1狀_魏，其巾_溶液含有 9.如申請專利顧第1項之絲學電池，具树胖由兮雙核總體色素增感的半導體微粒子固定在電極 29 201141816 元件與對極，且其間具有包含該銨鹽化合物或鱗鹽化合物之電解質溶液的層。八、圖式· 為〇 30η (ΧΝ·)Ρ (1) (wherein ΧΝ is a valence anion of a relative ion (only, ν is 1 or 2) HOOC COOH Ν Ν represents a nitrogen-containing bidentate ligand having two carboxyl groups, Ν Ν Ν Ν Ν 含 Ν Ν Ν Ν 含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含含 ; 含含 ; ; ; ; ; ; (2) 28 201141816 R1 A· (2) R2 — Z+— I R3 (wherein Z+ represents N+ or , and scales 1, R2, R3 and R4 may be the same or different 'each independently represent a hydrogen atom or an alkyl group Or two or more of these become a dimer and form a saturated or unsaturated heterocyclic ring together with such a bonded nitrogen atom or a phosphorus atom, and A_ represents an anion.) + 2_ as claimed in the first item Photochemical battery, wherein χΝ_ is a six-gas acid ion, a tetrafluoroboric acid ion, a nitrate ion or an iodide ion. 3. A photochemical battery as claimed in Patent No. 1, wherein the nitrogen-containing two-dentate coordination The sub is 2,2-linked "bipyridine, 2,2,-(4,4,-didecyl)), 2,2,-(4,4,-one-second Base) bipyridine, 2, 2 _(4,4,-di-n-decyl)bipyridine, 2,2,-(4,4,-di-n-dodecyl)bipyridine or 1, phenanthr〇line. 4. A photochemical battery according to the scope of the patent application, wherein the nitrogen-containing bidentate ligand having two carboxyl groups is 2,2,-linked bite _4,4,-di-hypo-acid. The photochemical battery of claim 1 wherein the nitrogen-containing tetradentate ligand is 2,2'-biimidazolium or 2,2,-benzimidaz〇ie. # 6 The photochemical battery of the patent scope of the invention, wherein the semiconductor microparticles are oxidized, oxidized, tin oxide, or the like. 7. The photochemical battery according to the scope of the patent application, wherein the ammonium salt compound, A_ in the compound is a tetracyano salt anion, a tetra-a salt anion hexa-anion anion or a bis(trifluoromethylsulfonyl)imido) anion. Oxidized 1 shape _ Wei, its towel _ solution contains 9. As claimed in the patent of the first item of the silk cell, with a tree fat due to the dual-core overall dye sensitized semiconductor particles fixed at the electrode 29 201141816 component and the pole, and A layer having an electrolyte solution containing the ammonium salt compound or the scale salt compound. Eight, schema · for 〇 30