Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)
Publication date: 22nd December 2022
Lead- free vacancy ordered halide double perovskites (VOP) can be considered as an alternative to conventional lead- based halide perovskite (ABX3) due to its excellent stability, high absorption coefficient, panchromatic absorption and compositional tunability which makes it suitable for photovoltaic applications such as solar cells and photo-electrochemical studies. Halide perovskites have attracted great attention in solar energy conversion in the last decade; however, their stability remained a pitching issue which essentially restricted these materials from being employed. It requires different layers of encapsulation to protect the perovskite material from the electrolyte medium during water splitting. Since VOP is lead free and stable in water, it can be used as an unprotected photo-electrode for water splitting. This reduces major charge transfer losses at the interface of encapsulation and perovskite which is a major advantage making it suitable for solar water splitting.
Platinum- based VOP namely, Cs2PtX6 (X= Cl, Br, I) has been employed in solar cells as the absorption layer which generated a current density of 2.42mA/cm2. VOP also possess an advantage of tuning the halide site via anion exchange. Anion exchange can occur from Cs2PtCl6 to Cs2PtBr6, Cs2PtCl6 to Cs2PtI6 and Cs2PtBr6 to Cs2PtI6. Exchange is carried out by immersing the material in LiX (X= required halide) solution and it follows core-shell mechanism. The new halide replaces the existing halide from the outer surface of the perovskite and slowly progress towards the centre with time forming type II heterostructure. This can be carried out not only with LiBr but with any required halide containing solution. This was confirmed by carrying out the same with HX, NaX and KX solutions. It is also found that temperature plays an important role in the exchange. Conversion of Cs2PtCl6 to Cs2PtBr6 LiBr required heating whereas conversion of Cs2PtCl6 and Cs2PtBr6 to Cs2PtI6 using LiI required no heat. For the same set of conversion from Cs2PtCl6 to Cs2PtBr6 NaBr and KBr converted the material even without heating and with heating the time for complete conversion reduced. Understanding the mechanism of charge transfer and the role of various factors such as type of salt, concentration of solution, amount of perovskite material in it and temperature that plays a crucial role in determining the rate of exchange process has been studied.
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