Resonant inelastic X-ray scattering and X-ray absorption spectroscopy on the cathode materials LiMnPO4 and LiMn0.9Fe0.1PO4––a comparative study

Literature Information

Publication Date 2011-10-10
DOI 10.1039/C1CP20673G
Impact Factor 3.676
Authors

H. M. Hollmark, T. Gustafsson, K. Edström, L.-C. Duda


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Abstract

We present a study of the charge-state behavior of the Li-ion battery cathode materials LixMnPO4 and LixMn0.9Fe0.1PO4 using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). A set of six identical battery cathodes for each material have been cycled and left in different charge states in the range of x = 0.2…1.0 before disassembly in an Ar glove box. Unexpectedly, we find that the Mn 3d-bands are almost inert to the delithiation process, suggesting that Mn ions participate to a very small extent in the charge compensation process. In LixMn0.9Fe0.1PO4 the Fe 3d-band shows much more response to delithiation than the Mn 3d-band. The O 2p-band hybridizes with the bands of the other ions in LixMnPO4 and LixMn0.9Fe0.1PO4 and thus, indirectly, carries useful information about the effects of delithiation at all ion sites. We conclude that the redox reactions during lithiation/delithiation of these materials are complex and involve repopulation of charges for all constituent elements.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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