Wang Hongxia, Liu Xizhe, Wang Zhaoxiang, Li Hong, Li Dongmei, Meng Qingbo, Chen Liquan
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080, China.
J Phys Chem B. 2006 Mar 30;110(12):5970-4. doi: 10.1021/jp057121b.
It was observed that the ionic conductivity of the solid-state electrolyte LiI/3-hydroxypropionitrile (HPN) = 1:4 (molar ratio) decreased dramatically with increasing iodine (I(2)) concentration, which differs from the conduction behavior of the Grotthuss transport mechanism observed in liquid or gel electrolytes. The short-circuit photocurrent density (J(sc)) of the dye-sensitized solar cell (DSSC) based on this electrolyte system increases with increasing I(2) concentration until LiI/I(2) is 1:0.05 (molar ratio). Beyond this limitation, the J(sc) decreases. At low I(2) concentrations (I(2)/LiI < or = 0.05), the J(sc) is mainly affected by the diffusion of I(3)(-). An increase of the I(2) concentration leads to the enhancement of the diffusion of I(3)(-) and an increase of the J(sc). At high I(2) concentrations (I(2)/LiI > 0.05), the factors, including the increased light absorption by the I(3)(-), the increased recombination of electrons at the photoanode with I(3)(-), and the reduced ionic conductivity of the electrolyte, lead to a decrease of J(sc). At the same time, the open-circuit voltage (V(oc)) of the DSSC decreases monotonically with the ratio of I(2)/LiI due to increased dark current in the DSSC. The increased absorption of visible light by the electrolyte, the enhanced dark current, and the reduced ionic conductivity of the electrolyte contribute to the performance variation of the corresponding solid-state DSSC with increasing I(2) concentration.
据观察,固态电解质LiI/3-羟基丙腈(HPN)=1:4(摩尔比)的离子电导率随碘(I₂)浓度的增加而急剧下降,这与在液体或凝胶电解质中观察到的Grotthuss传输机制的传导行为不同。基于该电解质体系的染料敏化太阳能电池(DSSC)的短路光电流密度(Jsc)随I₂浓度的增加而增加,直至LiI/I₂为1:0.05(摩尔比)。超过此限制,Jsc下降。在低I₂浓度(I₂/LiI≤0.05)下,Jsc主要受I₃⁻扩散的影响。I₂浓度的增加导致I₃⁻扩散增强和Jsc增加。在高I₂浓度(I₂/LiI>0.05)下,包括I₃⁻对光吸收增加、光阳极处电子与I₃⁻复合增加以及电解质离子电导率降低等因素,导致Jsc下降。同时,由于DSSC中暗电流增加,DSSC的开路电压(Voc)随I₂/LiI的比值单调下降。电解质对可见光吸收的增加、暗电流的增强以及电解质离子电导率的降低,导致相应固态DSSC的性能随I₂浓度的增加而变化。