本文關(guān)鍵詞：新型無碘準(zhǔn)固態(tài)電解質(zhì)的研制及其在染料敏化太陽能電池中的應(yīng)用　出處：《武漢大學(xué)》2014年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 染料敏化太陽能電池 準(zhǔn)固態(tài)電解質(zhì) 離子液體 塑晶 光電轉(zhuǎn)化效率

【摘要】：二十世紀(jì)九十年代誕生的染料敏化太陽能電池(DSSCs)以其成本低廉、性能優(yōu)越的特點(diǎn)成為硅基光伏器件最具競爭力的替代產(chǎn)品。但傳統(tǒng)的含I-/13-氧還電對的有機(jī)液態(tài)電解質(zhì)存在易揮發(fā)、有毒、吸光、侵蝕金屬電流收集極和封裝困難等缺陷,影響DSSC的規(guī)�；a(chǎn)和長期穩(wěn)定性。為此,本論文研發(fā)了一些新型不含碘單質(zhì)(12)的準(zhǔn)固態(tài)電解質(zhì),并探討了電解質(zhì)組分對其結(jié)晶行為、粘度、離子電導(dǎo)率及由其組裝的DSSCs的光電化學(xué)性能的影響。獲得的主要實(shí)驗(yàn)現(xiàn)象和研究結(jié)論歸納如下： 1.采用聚氧化乙烯(PEO)為膠凝劑,CuI為p-型空穴傳輸材料,LiC104為電荷傳輸助劑制備了CuI凝膠電解質(zhì)。該電解質(zhì)中的PEO能有效地抑制CuI的快速結(jié)晶,促進(jìn)TiO2/CuI電解質(zhì)形成良好的界面接觸；而LiC104能將PEO轉(zhuǎn)化為無定形基質(zhì)以利于電荷傳輸。在含20wt%PEO的CuI凝膠電解質(zhì)中摻雜3wt%LiClO4時(shí)獲得了最高的離子電導(dǎo)率(8.7×10-3S cm-1),且吸附在Ti02表面的Li+能改善電子從激發(fā)態(tài)染料到Ti02的注入效率,極大地提高了DSSC的效率(2.81%)。與未加PEO(1.46%)或LiClO4(1.30%)的CuI電解質(zhì)組裝的DSSC相比,效率提高了96-116%。這種CuI凝膠電解質(zhì)具有成本低、操作簡便、環(huán)保高效等特點(diǎn),為固態(tài)空穴傳輸材料在DSSC中的應(yīng)用開辟了新的途徑。 2.采用PEO為膠凝劑,離子液體1,2-二甲基-3-丙基咪唑碘(DMPⅡ)為電荷傳輸介質(zhì)和碘源制備了離子液體凝膠電解質(zhì)。由含20wt%PEO的離子液體凝膠電解質(zhì)組裝的DSSC能在不含12的情況下正常工作,并達(dá)到4.05%的效率,表明在電解質(zhì)中去除12以規(guī)避其對DSSC困擾的思路是可行的。摻雜5wt%KI可極大地提高電解質(zhì)的離子電導(dǎo)率(1.63×10-2S cm-1),且K+能抑制PEO的結(jié)晶、促進(jìn)電子在TiO2/染料/電解質(zhì)界面的遷移,從而將電池的效率提高到5.87%,效率改善了45%。這種離子液體凝膠電解質(zhì)具有成分簡單、操作簡便和無毒不泄漏等特點(diǎn),可為準(zhǔn)固態(tài)DSSC提供新的高效電解質(zhì)材料。 3.以1-丁基-3-甲基咪唑碘(BMⅡ)為電荷傳輸介質(zhì)和碘源,雙三氟甲磺酰亞胺鋰(LiTFSI)為電荷傳輸助劑,采用低粘度的離子液體1-丁基-3-甲基咪唑硫氰酸鹽(BMISCN)調(diào)節(jié)其流變性制備了二元離子液體電解質(zhì)。由BMⅡ組裝的DSSC能在不含12的情況下正常工作但僅獲得了2.66%的效率,添加低粘度的BMISCN可降低電解質(zhì)的粘度并提高電解質(zhì)中的電荷交換反應(yīng),由其組裝的DSSC獲得了更高效率(4.33%)。LiTFSI不僅能提高電解質(zhì)的離子電導(dǎo)率,還能改善DSSC中電荷載流子的傳輸并抑制電荷復(fù)合,從而獲得了5.55%的效率(與未摻雜相比提高了28%)。這種二元離子液體電解質(zhì)具有流變性好、無揮發(fā)和腐蝕性等特點(diǎn),為離子液體電解質(zhì)的研發(fā)與應(yīng)用提供了新思路。 4.為克服離子液體電解質(zhì)的流動性問題,以丁二腈作為固態(tài)溶劑和基質(zhì),離子液體BMⅡ和1-丙基-3-甲基咪唑碘(PMⅡ)為電荷傳輸介質(zhì)和碘源制備了新型塑晶離子液體電解質(zhì)。摻雜5wt%LiClO4到塑晶電解質(zhì)中時(shí),Li+與丁二腈能通過配位作用將結(jié)晶性基質(zhì)轉(zhuǎn)化為無定形含鹽基質(zhì),改善了電解質(zhì)的離子電導(dǎo)率,還能通過靜電作用力吸引-和形成的13-以促進(jìn)其電荷交換反應(yīng),進(jìn)而將DSSC的效率提高到5.50%(與未摻雜相比提高了157%)。這種不含12的塑晶離子液體電解質(zhì)具有機(jī)械性能好、便于封裝以及無揮發(fā)和腐蝕性等特點(diǎn),在柔性或固態(tài)DSSC的規(guī)模化生產(chǎn)方面具有較好的應(yīng)用前景。 5.為驗(yàn)證不含I2的離子液體凝膠電解質(zhì)在染料共敏化DSSC中應(yīng)用的可行性,采用分步共敏化方法將光譜響應(yīng)范圍互補(bǔ)的有機(jī)染料OD-8與D149或SQ2聯(lián)合對Ti02光陽極進(jìn)行共敏化并組裝成準(zhǔn)固態(tài)DSSC,利用OD-8和D149或SQ2的吸收光譜匹配互補(bǔ)的特性提高電池的光捕獲效率。OD-8/D149(6.21%)或OD-8/SQ2(6.10%)共敏化DSSC的效率均遠(yuǎn)高于OD-8(4.53%),D149(5.46%)和SQ2(2.86%)單一染料敏化的DSSC此外,不含I2的離子液體凝膠電解質(zhì)在共敏化DSSC中能成功發(fā)揮電解質(zhì)的功能,且表現(xiàn)出比傳統(tǒng)有機(jī)液態(tài)電解質(zhì)組裝的共敏化DSSC更高的短路電流、開路電壓和電池效率,表明不含I2的離子液體凝膠電解質(zhì)在共敏化DSSC中具有顯著的應(yīng)用前景,也為替代價(jià)格昂貴的釕聯(lián)毗啶類染料和發(fā)展寬光譜響應(yīng)、高效環(huán)保的DSSCs提供了一些新的思路。
[Abstract]:The dye-sensitized solar cell (DSSCs) was born in 1990s with its low cost, superior performance characteristics of silicon based photovoltaic devices become the most competitive alternative products. But the traditional I-/13- oxygen also of organic liquid electrolyte are volatile, toxic, light absorption, corrosion of metal current collector and encapsulation difficulty effect of large-scale production and long-term stability of DSSC. Therefore, this thesis developed some new elemental iodine (12) of the quasi solid electrolyte, and discusses the viscosity of electrolyte component on the crystallization behavior, and effects of photoelectrochemical properties and conductivity of DSSCs by its sub assembly. The main conclusions obtained by experimental phenomena and study are summarized as follows:
1. using poly ethylene oxide (PEO) as gelling agent, CuI p- as hole transport materials, LiC104 prepared CuI gel electrolyte for charge transfer. The electrolyte additives for rapid crystallization of PEO can effectively inhibit CuI and promote TiO2/CuI electrolyte to form a good interface contact; while LiC104 PEO can be transformed into amorphous in order to obtain the charge transfer matrix. The highest ionic conductivity of 3wt%LiClO4 doped in CuI gel electrolyte containing 20wt%PEO in (8.7 * 10-3S cm-1), and can improve the adsorption of electrons from the excited dye to Ti02 injection efficiency on the surface of Ti02 Li+, which greatly improves the efficiency of DSSC (2.81%) and not. PEO (1.46%) or LiClO4 (1.30%) compared to the CuI electrolyte DSSC, to improve the efficiency of the 96-116%. CuI gel electrolyte has the advantages of low cost, simple operation, environmental protection, etc., for the application of solid hole transport material DSSC in the open A new way is made.
2. using PEO as gelling agent, ionic liquid 1,2- two -3- methyl propyl iodide (DMP II) prepared by ionic liquid gel electrolyte for charge transfer medium and source of iodine. Assembled by ionic liquid gel electrolyte containing 20wt%PEO DSSC can work normally in excluding 12 cases, and achieved 4.05% efficiency, that in the electrolyte removal of 12 to avoid the idea of DSSC problem is feasible. The doping of 5wt%KI can greatly improve the ionic conductivity of the electrolyte (1.63 * 10-2S cm-1), K+ and PEO can inhibit the crystallization, promote the electron migration in TiO2/ dye / electrolyte interface, which will improve the efficiency of the battery to 5.87%, improve the efficiency of the 45%. of this ionic liquid gel electrolyte has simple components, easy operation and non-toxic, leakage and other characteristics, can provide efficient new electrolyte for quasi solid state DSSC.
3. to 1- butyl -3- methylimidazolium iodine (BM II) as charge transfer medium and a source of iodine, double three fluorine methyl sulfonyl imide lithium (LiTFSI) charge transfer agent, the low viscosity of ionic liquid 1- butyl -3- methylimidazolium thiocyanate (BMISCN) ionic liquid electrolyte two yuan adjustment of its rheology system the preparation of DSSC assembled by BM. In the case with 12 under normal work but only got 2.66% of the efficiency, add a low viscosity BMISCN can reduce the viscosity of the electrolyte and improve the charge in the electrolyte exchange reaction by the assembly of the DSSC obtained a higher efficiency (4.33%).LiTFSI can not only improve the ionic conductivity of electrolyte the charge carriers can improve the transmission of DSSC and suppress the charge recombination, to obtain a 5.55% efficiency (compared with the undoped increased 28%). This two yuan of ionic liquid electrolyte has good rheology, no volatilization and corrosion resistance, for A new idea for the development and application of ionic liquid electrolytes is provided.
4. to overcome the liquidity problems of ionic liquid electrolytes, with two as the solvent and solid butyl nitrile matrix, ionic liquid BM and 1- II -3- propyl methyl imidazole iodine (PM II) to prepare a new plastic crystal ionic liquid electrolyte for charge transfer medium and source of iodine doped 5wt%LiClO4 system. To the plastic crystal electrolyte at Li+ and two D by coordination function to various crystalline matrix into amorphous salt matrix, improve the ionic conductivity of the electrolyte, but also through the electrostatic force to promote the charge exchange reaction attraction and the formation of 13-, which will improve the efficiency of DSSC to 5.50% (compared with the undoped increased by 157%). This does not contain 12 plastic crystal ionic liquid electrolyte has good mechanical properties, easy package and no volatilization and corrosion resistance and other characteristics, and has good application prospects in large scale production of flexible or solid DSSC.
5. for the feasibility of the application of ionic liquid gel electrolyte without I2 verification in dye sensitized DSSC in the step by step cosensitized methods spectral response range of complementary organic dyes OD-8 and D149 or SQ2 on Ti02 photoanode were sensitized and assembled into a quasi solid state DSSC, complementary characteristics to improve battery efficiency of light capture the.OD-8/D149 absorption spectra of OD-8 and D149 or SQ2 (6.21%) or OD-8/SQ2 (6.10%) of the total efficiency of sensitized DSSC were much higher than that of OD-8 (4.53%), D149 (5.46%) and SQ2 (2.86%) single dye sensitized DSSC in ionic liquid gel electrolyte containing I2 electrolyte can not play in the cosensitization successfully in DSSC, and shows the short-circuit current than the traditional organic liquid electrolyte co sensitization of DSSC high efficiency, open circuit voltage and battery, showed that the ionic liquid gel electrolyte without I2 significantly in CO sensitization in DSSC The application prospect also provides some new ideas to replace the expensive ruthenium dyestuff dyes and to develop the wide spectrum response and the efficient and environmentally friendly DSSCs.

【學(xué)位授予單位】：武漢大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：O646;TM914.4

【共引文獻(xiàn)】

相關(guān)期刊論文 前9條

1 劉世利;陳守臻;趙倩;徐政虎;李玉;賈繼輝;郭良宏;;光電化學(xué)競爭法檢測生物素[J];分析化學(xué);2013年10期

2 徐長志;肖斌;柳清菊;;染料敏化太陽能電池的研究進(jìn)展[J];材料導(dǎo)報(bào);2014年07期

3 吳一萍;郭良宏;;DNA損傷的光電化學(xué)傳感器檢測[J];化學(xué)進(jìn)展;2014年01期

4 唐鵬;沙作良;楊立斌;;具有高活性能量{001}晶面銳鈦礦TiO_2的進(jìn)展研究[J];科學(xué)技術(shù)與工程;2014年08期

5 賈冬玲;王夢亞;李順;黃建國;;天然纖維素物質(zhì)模板制備功能納米材料研究進(jìn)展[J];科學(xué)通報(bào);2014年15期

6 朱英;張學(xué)俊;;卟啉類染料敏化劑的研究進(jìn)展[J];山西化工;2013年05期

7 常建立;王珂瑋;徐倩倩;高素梅;任鐵真;;石墨烯包裹P25在染料敏化太陽能電池對電極中的應(yīng)用[J];石油學(xué)報(bào)(石油加工);2014年02期

8 任銀霞;顧承志;代斌;馬曉偉;;3,4-二芳基吡咯的合成[J];石河子大學(xué)學(xué)報(bào)(自然科學(xué)版);2014年02期

9 王桂強(qiáng);王德龍;況帥;禚淑萍;;染料敏化太陽能電池用過渡金屬化合物對電極的研究進(jìn)展[J];無機(jī)材料學(xué)報(bào);2013年09期

相關(guān)博士學(xué)位論文 前8條

1 吳永真;基于D-A-π-A型純有機(jī)太陽能電池敏化染料設(shè)計(jì)、合成及光伏性能研究[D];華東理工大學(xué);2013年

2 王金果;多級結(jié)構(gòu)單晶TiO_2的制備、修飾與光催化性能研究[D];華東師范大學(xué);2013年

3 Zafar Iqbal（成遠(yuǎn)高）;雙向/三向共軛延長鏈吩噻嗪染料的合成及其光伏性能研究[D];華南理工大學(xué);2013年

4 楊燕珍;染料敏化太陽電池電解質(zhì)材料的制備與性能研究[D];合肥工業(yè)大學(xué);2013年

5 金玲;八羧基酞菁染料用于染料敏化太陽能電池的研究[D];東華大學(xué);2013年

6 應(yīng)偉江;D-A-π-A結(jié)構(gòu)芳胺類染料的合成及其性能研究[D];華東理工大學(xué);2013年

7 郭福領(lǐng);TiO_2光陽極優(yōu)化及其吡咯并吡咯二酮和聯(lián)噻唑類敏化劑性能研究[D];華東理工大學(xué);2013年

8 岳根田;基于異質(zhì)結(jié)和導(dǎo)電聚合物對電極的染料敏化太陽能電池研究[D];華僑大學(xué);2013年

相關(guān)碩士學(xué)位論文 前10條

1 范其龍;聯(lián)吡啶釕配合物的制備、表征及可見光產(chǎn)氫性能研究[D];鄭州大學(xué);2013年

2 張亞萍;酞菁/MCM-41負(fù)載催化劑的制備及其催化氧化有機(jī)硫化合物的活性研究[D];西北大學(xué);2013年

3 劉新平;N，N-二苯腙類染料和二茚并吡嗪類共軛聚合物的合成及其光伏性質(zhì)的研究[D];湘潭大學(xué);2012年

4 蔡志霞;納米晶TiO_2及其復(fù)合結(jié)構(gòu)的制備和光伏性能研究[D];湘潭大學(xué);2012年

5 韓麗娟;用于染料敏化太陽電池的新型低成本高性能對電極[D];華南理工大學(xué);2013年

6 董淼;染料敏化太陽能電池電極材料的性能研究[D];電子科技大學(xué);2013年

7 李梅;纖維鋅礦Cu_2ZnSnS_4納米晶的合成及其光電性能研究[D];河南大學(xué);2013年

8 徐春玲;TiO_2納米棒陣列的制備、性質(zhì)及在染料敏化太陽能電池中的應(yīng)用研究[D];重慶大學(xué);2013年

9 焦杰;硫?qū)侔雽?dǎo)體的制備及在太陽能電池上的應(yīng)用[D];河南大學(xué);2013年

10 相薇;DSSC負(fù)載型納米TiO_2薄膜電極的制備及性能研究[D];東北林業(yè)大學(xué);2013年

，

本文編號：1396390