結合染料敏化太陽能電池(Dye-sensitized solar cells, DSSCs)與電致色變元件(Electrochromic devices, ECDs)於單一元件中的光驅動電致色變元件(Photoelectrochromic device, PECD)為一種可直接轉換太陽能並驅動電化學元件的永續自供電系統(Self-powered systems)。然而，現今PECD仍受限於光陽極穿透度、電致色變材料選擇、電解質種類、濃度與結構上差異的緣故，無法達到如同電致色變元件兼具高光學對比與快速的響應時間。為了要解決上述議題，本研究有系統性地從材料設計與反應機制著手，開發一種具有全新結構的混合型光驅動電致色變元件並進一步首度提出及實現具有光學互補特性的互補式PECD。
Pt為DSSC中最常使用於催化I3-還原反應之電催化材料，但其具備不透光的性質影響了整體光學穿透度。有鑒於此，本研究擬導入具備高穿透度的還原氧化石墨烯(reduced graphene oxide, rGO)於PEDOT-MeOH薄膜(rGO/PEDOT-MeOH)中做為PECD的電致色變與電催化之雙功能對電極。由於PEDOT-MeOH本身為一種具還原著色特性的導電高分子材料且對I3-具有出色的電催化能力，因此相當適合應用於PECD中來實現兼具有電催化與電致色變能力的雙功能對電極。為了進一步提升PEDOT-MeOH的電催化能力，本研究導入具有良好導電性與高透光特性的rGO來增加PEDOT-MeOH的導電性與電化學活性面積，提升電極對於電解液中I3-的電催化能力來強化PECD的光伏效能，進而提高元件的光學表現。然而，本研究結果顯示藉由導入rGO於PEDOT-MeOH雖然能提升雙功能電極的電催化能力進而提升光伏效能，但卻無法連帶增強其光學性能，反而適得其反。推測其原因可能為導入rGO增加了PEDOT-MeOH對電極的電催化能力將導致I3-的還原反應與PEDOT-MeOH的還原著色反應產生競爭反應，使得導入rGO/PEDOT-MeOH的PECD光學穿透度(ΔT)在特徵波長610 nm從25.2%降低至20.8%。
因此，本研究擬將PEDOT-MeOH之電致色變與電催化功能獨立出來以避免產生競爭反應，為了實現此目的而設計了一種新型結構之混和型光驅動電致色變元件(Hybrid type PECD, H-PECD)，其整合了分離式光驅動電致色變元件(Separated type PECD, S-PECD)與組合式光驅動電致色變元件(Combined type PECD, C-PECD)的結構設計與元件優勢。從循環伏安分析與可見光光譜結果來看，PEDOT-MeOH不僅展現了與Pt相近的I3-還原能力，且具有相當高的穿透特性(~70%)。於光陽極下方使用PEDOT-MeOH作為電致色變層並搭配PEDOT-MeOH對電極所組成的H-PECD與搭配Pt對電極所組成的C-PECD在特徵波長610 nm下的ΔT分別為31.7與8.3%，顯示H-EPCD相較於傳統C-PECD具備更高的光學對比，充分展現出了此新型結構在光學對比上的優勢。另一方面，將H-PECD與傳統S-PECD相比，H-PECD的著色時間(coloring time, τc)與去色時間(bleaching time, τb)分別為5.5與3.3秒，遠快於S-PECD的33.1與18.1秒，充分展現出了此新型結構在響應時間上的優勢，並連帶使得H-PECD的光著色效率(Photo coloring efficiency, PhCE)於照光初期可高達約160 W-1 min-1 cm2，明顯地高於S-PECD的20 W-1 min-1 cm2。
在上述研究過程中還發現到H-PECD在短路/照光下操作具有疑似光學互補的特性，因此本研究進一步嘗試導入氧化著色材料-普魯士藍(Prussian blue, PB)於H-PECD中，並搭配原有的還原著色材料-PEDOT-MeOH。由於PB與PEDOT-MeOH的氧化還原峰電位分別位於0/-1.0與+0.1/-0.6 V (vs.Ag/Ag+) ，顯示兩種材料之氧化還原區間非常接近。除此之外，PB與PEDOT-MeOH的特徵波長也十分相近，分別位於波長700與610 nm，因此適合導入於PECD中實現光學互補。根據電致色變層在PECD的位置不同，可分為結構為氧化著色材料於光陽極且還原著色材料於對電極的α-混合式光驅動電致色變元件(α-H-PECD)與結構為還原著色材料於光陽極且氧化著色材料於對電極的β-混合式光驅動電致色變元件(β-Hybrid type-PECD, β-H-PECD)。於照光/短路時，觀察α-H-PECD於700與610 nm下的穿透度與時間的變化，發現兩波長的穿透度有交叉的現象，此現象說明了PB與PEDOT-MeOH的著色在-H-PECD此種結構下具有時間差而無法實現光學互補。為了解決上述問題，更改操作條件並且調整元件的結構為β-H-PECD。從光譜的曲線來看，β-H-PECD在使用0.5 M LiI/0.005 M I2於PC溶劑的電解液，於特徵波長642 nm下有25.1 %的光學對比，高於非互補式PECD於611 nm下20.2 %的光學對比。從特徵波長的偏移與光學對比的上升，β-H-PECD確實實現了光學互補的概念，首度實現具有光學互補特性的“互補式光驅動電致色變元件”(Complamentary photoelectrochromic device, Cm-PECD)。藉由特定的操作條件，β-H-PECD所實現的Cm-PECD可具有記憶效應與快速去色響應時間(9.3秒)。

Nowadays, the progress of solar-driven photoelectrochromic devices (PECDs) is restricted by lower optical contrast and sluggish response time, which limited its potential application to further replacing the conventional electrochromic devices (ECDs). To solve the problem described above, a novel structure of PECD with different materials were developed in this research.
In this study, PEDOT-MeOH was selected as bifunctional material with electrochromic and electrocatalytic characteristics in the counter electrode (CE) of PECD. To enhance the optical performance of PECD by improving the photovoltaic performance, highly transparent reduced graphene oxide (rGO) with good conductivity and promising electrocatalytic activity for reducing I3- was introduced into the PEDOT-MeOH film. However, the PECD with PEDOT-MeOH/rGO CE had the lowest optical performance either in optical contrast (ΔT610nm) of 20.8% or in response time (τc/τb) of 30.4/32.3 s, compared to PECD with pristine PEDOT-MeOH CE (ΔT610nm=25.2%, τc/τb= 26.1/25.3 s). This result may be caused by competition of redox reaction of I3- and coloring reaction of PEDOT-MeOH on the CE with PEDOT-MeOH/rGO film.
To solve the above problem, a new structure of hybrid type PECD (H-PECD) with separated electrochromic layer and photoactive layer on the photoelectrode was developed. Compared to other structures of PECD, the electron transfer path was shortened for accelerating the coloring process in the case of H-PECD. As for the bleaching process, the CE with highly transparent PEDOT-MeOH can act as electrocatalyst material to accelerate I3- reduction for facilitating the bleaching process in the condition of short circuit. The H-PECD with excellent coloring and bleaching characteristics exhibited a fast response time of τc/τb (5.5/3.3 s), which significantly faster than the separated type PECD (S-PECD) with τc and τb of 33.1 and 18.1 s, respectively. Therefore, photo coloration efficiency (PhCE) of H-PECD was around ≌160 W-1min-1cm2 at the initial state, which was much higher than that of S-PECD (20 W-1min-1cm2). This result indicated that H-PECD could achieve similar optical contrast efficiently by consuming the same solar energy. Moreover, H-PECD under illumination with the condition of short circuit showed higher optical contrast of 31.3% than that with the condition of open circuit (28.3%), which implied the phenomenon of optical complementary could be achieved by the architecture of H-PECD.
To realize the complementary PECD (Cm-PECD), Prussian blue (PB) was introduced as secondary electrochromic materials into the various combination of coloring materials of H-PECD, namely α-H-PECD and β-H-PECD. For the UV-Vis spectrum of
α-H-PECD, there was a prominent absorption peak at the wavelength of 700 nm under illumination/short circuit (I/SC) at initial. After a while, the absorption peak was shifted from 700 nm to 610 nm, represented the reduction of PEDOT-MeOH happened. Due to the potential difference between PEDOT-MeOH and PB are approached to zero, the reduction of PEDOT-MeOH was always accompanied by the oxidation of PB. Therefore, there was a time lag in the coloring order between PEDOT-MeOH and PB under I/SC since both electrodes will be reduced simultaneously. To avoid this problem, β-H-PECD was proposed to change the operating type of coloring and bleaching processes. β-H-PECD was derived from α-H-PECD because of the PB in CE would react with I-/I3- automatically, which means the PB could color and bleach without receiving electrons from TiO2/dye. To investigate the complmentary phenomenon in β-H-PECD, the characteristic wavelength of combined type PECD (C-PECD) with PEDOT-MeOH was included to compare with that of β-H-PECD. In the electrolyte of 0.5 M LiI/0.005 M I2/PC, β-H-PECD and C-PECD showed the optical contrast of 25.1 % at 642 nm and 18.8% at 611 nm, respectively, which implied that Cm-PECD was successfully realized by β-H-PECD with PEDOT-MeOH and PB. Moreover, β-H-PECD had the memory effect to maintain the colored states under the specific operating condition and fast response of bleaching.

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