Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

Xu, Zhaojian; Kerner, Ross A.; Harvey, Steven P.; Zhu, Kai; Berry, Joseph J.; Rand, Barry P.

doi:10.1021/acsenergylett.2c02385

Title: Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

Journal Article · 13 December 2022 · ACS Energy Letters

DOI: https://doi.org/10.1021/acsenergylett.2c02385 · OSTI ID:1908586

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^[2]; Berry, Joseph J. ^[3];

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Princeton University, NJ (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); University of Colorado, Boulder, CO (United States)

Voltage-induced halide segregation greatly limits the optoelectronic applications of mixed-halide perovskite devices, but a mechanistic explanation behind this phenomenon remains unclear. In this work, we use electron microscopy and elemental mapping to directly measure the halide redistribution in mixed-halide perovskite solar cells with quasi-ion-impermeable contact layers under different bias polarities to find iodide and bromide accumulation at the cathode and anode, respectively. This is consistent with a mechanism based on preferential iodide oxidation at the anode, leading to unbalanced I$$^{+}_{i}$$, I$$^{-}_{X}$$, and Br$$^{-}_{X}$$ fluxes. Importantly, switching the anode from "inert" Au to "active" Ag prevents segregation because Ag oxidation precludes the oxidation of lattice iodide, which suggests employing redox-active additives as a general strategy to suppress halide segregation. Finally, these results show that halide perovskite devices operate as solid-state electrochemical cells when threshold voltages are exceeded, providing fresh insight to understand the impacts of voltage bias on halide perovskite devices.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); Office of Naval Research (ONR); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1908586

Report Number(s):: NREL/JA-5900-84175; MainId:84948; UUID:20d77097-06ee-4f53-b074-53163403f12b; MainAdminID:68392

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 1 Vol. 8; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

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