Counter electrode (CE) is a key part of enhancing power conversion efficiency (PCE) and strengthening cyclic stability in quantum dot sensitized solar cells (QDSSCs). Consequently, searching for alternative and high-quality CE materials has far-reaching consequences for extending the lifetime, increasing utilization and even further achieving commercialization of QDSSCs. Herein, we put forward an idea that the Co3S4 hollow nanocages were coated with CuCo–B alloy-nanosheets, and efficient Co3S4@CuCo–B composite CE was prepared by in-situ reduction method, and applied to QDSSCs. Because of its three-dimensional hollow structure, the Co3S4@CuCo–B composite has a higher specific surface area, encourages electrolyte diffusion, and enhances QDSSC stability. Alternatively, the work function analysis shows that Co3S4 modified by CuCo–B enhances the driving force of interfacial electric field and promotes electron transfer. The photovoltaic performance of QDSSC assembled with Co3S4@CuCo–B composite CE has demonstrated competitive ability via implementing a PCE up to 8.27 %, Jsc = 26.45 mA cm−2, Voc = 0.683 V and FF = 0.46. Among them, the PCE of Co3S4@CuCo–B composite CE respectively has ∼14.4 % and 29.6 % enhancements in comparison with pure CuCo–B and Co3S4 CEs. And Co3S4@CuCo–B composite CE displays stable current density after 200 cycle tests, demonstrating excellent cyclic stability. This work suggests that Co3S4@CuCo–B composite lays the theoretical foundation for becoming a high-performance CE.
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