A mechanistic study of the dopant-induced breakdown in halide perovskites using solid state energy storage devices
Abstract
Doping halide perovskites (HPs) with extrinsic species, such as alkali metal ions, plays a critical, albeit often elusive role in optimising optoelectronic devices. Here, we use solid state lithium ion battery inspired devices with a polyethylene oxide-based polymer electrolyte to dope HPs controllably with lithium ions. We perform a suite of operando material analysis techniques while dynamically varying Li doping concentrations. We determine and quantify three doping regimes; a safe regime, with doping concentrations of <1020 cm–3 (2% Li : Pb mol%) in which the HP may be modified without detrimental effect to its structure; a minor decomposition regime, in which the HP is partially transformed but remains the dominant species; and a major decomposition regime in which the perovskite is superseded by new phases. We provide a mechanistic description of the processes mediating between each stage and find evidence for metallic Pb(0), LiBr and LiPbBr2 as final decomposition products. Combining results from synchrotron X-ray diffraction measurements with in situ photoluminescence and optical reflection microscopy studies, we distinguish the influences of free charge carriers and intercalated lithium independently. We find that the charge density is equally as important as the geometric considerations of the dopant species and thereby provide amore »
- Authors:
-
- Univ. of Cambridge (United Kingdom)
- Univ. Paderborn (Germany); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Univ. of Cambridge (United Kingdom); Harvard Univ., Cambridge, MA (United States)
- Univ. of Cambridge (United Kingdom); Heidelberg Univ. (Germany)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Engineering and Physical Sciences Research Council (EPSRC)
- OSTI Identifier:
- 1987327
- Grant/Contract Number:
- AC02-76SF00515; EP/L016087/1
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 15; Journal Issue: 10; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Mathieson, Angus M., Dose, Wesley M., Steinrück, Hans-Georg, Takacs, Christopher J., Feldmann, Sascha, Pandya, Raj, Merryweather, Alice J., Mackanic, David, Rao, Akshay, Deschler, Felix, and De Volder, Michael. A mechanistic study of the dopant-induced breakdown in halide perovskites using solid state energy storage devices. United States: N. p., 2022.
Web. doi:10.1039/d2ee01754g.
Mathieson, Angus M., Dose, Wesley M., Steinrück, Hans-Georg, Takacs, Christopher J., Feldmann, Sascha, Pandya, Raj, Merryweather, Alice J., Mackanic, David, Rao, Akshay, Deschler, Felix, & De Volder, Michael. A mechanistic study of the dopant-induced breakdown in halide perovskites using solid state energy storage devices. United States. https://doi.org/10.1039/d2ee01754g
Mathieson, Angus M., Dose, Wesley M., Steinrück, Hans-Georg, Takacs, Christopher J., Feldmann, Sascha, Pandya, Raj, Merryweather, Alice J., Mackanic, David, Rao, Akshay, Deschler, Felix, and De Volder, Michael. Tue .
"A mechanistic study of the dopant-induced breakdown in halide perovskites using solid state energy storage devices". United States. https://doi.org/10.1039/d2ee01754g. https://www.osti.gov/servlets/purl/1987327.
@article{osti_1987327,
title = {A mechanistic study of the dopant-induced breakdown in halide perovskites using solid state energy storage devices},
author = {Mathieson, Angus M. and Dose, Wesley M. and Steinrück, Hans-Georg and Takacs, Christopher J. and Feldmann, Sascha and Pandya, Raj and Merryweather, Alice J. and Mackanic, David and Rao, Akshay and Deschler, Felix and De Volder, Michael},
abstractNote = {Doping halide perovskites (HPs) with extrinsic species, such as alkali metal ions, plays a critical, albeit often elusive role in optimising optoelectronic devices. Here, we use solid state lithium ion battery inspired devices with a polyethylene oxide-based polymer electrolyte to dope HPs controllably with lithium ions. We perform a suite of operando material analysis techniques while dynamically varying Li doping concentrations. We determine and quantify three doping regimes; a safe regime, with doping concentrations of <1020 cm–3 (2% Li : Pb mol%) in which the HP may be modified without detrimental effect to its structure; a minor decomposition regime, in which the HP is partially transformed but remains the dominant species; and a major decomposition regime in which the perovskite is superseded by new phases. We provide a mechanistic description of the processes mediating between each stage and find evidence for metallic Pb(0), LiBr and LiPbBr2 as final decomposition products. Combining results from synchrotron X-ray diffraction measurements with in situ photoluminescence and optical reflection microscopy studies, we distinguish the influences of free charge carriers and intercalated lithium independently. We find that the charge density is equally as important as the geometric considerations of the dopant species and thereby provide a quantitative framework upon which the future design of doped-perovskite energy devices should be based.},
doi = {10.1039/d2ee01754g},
journal = {Energy & Environmental Science},
number = 10,
volume = 15,
place = {United States},
year = {Tue Sep 06 00:00:00 EDT 2022},
month = {Tue Sep 06 00:00:00 EDT 2022}
}
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