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Title: Engineering the Transformation Strain in LiMn y Fe 1–y PO 4 Olivines for Ultrahigh Rate Battery Cathodes

Abstract

Alkali ion intercalation compounds used as battery electrodes often exhibit first-order phase transitions during electro-chemical cycling, accompanied by significant transformation strains. Despite 30 years of research into the behavior of such compounds, the relationship between transformation strain and electrode performance, especially the rate at which working ions (e.g., Li) can be intercalated and deintercalated, is still absent. In this work, we use the LiMnyFe1-yPO4 system for a systematic study, and measure using operando synchrotron radiation powder X-ray diffraction (SR-PXD) the dynamic strain behavior as a function of the Mn content (y) in powders of similar to 50 nm average diameter. The dynamically produced strain deviates significantly from what is expected from the equilibrium phase diagrams and demonstrates metastability but nonetheless spans a wide range from 0 to 8 vol % with y. For the first time, we show that the discharge capacity at high C-rates (20-50C rate) varies in inverse proportion to the transformation strain, implying that engineering electrode materials for reduced strain can be used to maximize the power capability of batteries.

Authors:
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Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1376721
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 16; Journal Issue: 4; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
Li-ion batteries; X-ray diffraction; cathode; lithium manganese iron phosphate; misfit strain; operando; phase transformation; rate capability

Citation Formats

Ravnsbæk, Dorthe B., Xiang, Kai, Xing, Wenting, Borkiewicz, Olaf J., Wiaderek, Kamila M., Gionet, Paul, Chapman, Karena W., Chupas, Peter J., Tang, Ming, and Chiang, Yet-Ming. Engineering the Transformation Strain in LiMn y Fe 1–y PO 4 Olivines for Ultrahigh Rate Battery Cathodes. United States: N. p., 2016. Web. doi:10.1021/acs.nanolett.5b05146.
Ravnsbæk, Dorthe B., Xiang, Kai, Xing, Wenting, Borkiewicz, Olaf J., Wiaderek, Kamila M., Gionet, Paul, Chapman, Karena W., Chupas, Peter J., Tang, Ming, & Chiang, Yet-Ming. Engineering the Transformation Strain in LiMn y Fe 1–y PO 4 Olivines for Ultrahigh Rate Battery Cathodes. United States. https://doi.org/10.1021/acs.nanolett.5b05146
Ravnsbæk, Dorthe B., Xiang, Kai, Xing, Wenting, Borkiewicz, Olaf J., Wiaderek, Kamila M., Gionet, Paul, Chapman, Karena W., Chupas, Peter J., Tang, Ming, and Chiang, Yet-Ming. 2016. "Engineering the Transformation Strain in LiMn y Fe 1–y PO 4 Olivines for Ultrahigh Rate Battery Cathodes". United States. https://doi.org/10.1021/acs.nanolett.5b05146.
@article{osti_1376721,
title = {Engineering the Transformation Strain in LiMn y Fe 1–y PO 4 Olivines for Ultrahigh Rate Battery Cathodes},
author = {Ravnsbæk, Dorthe B. and Xiang, Kai and Xing, Wenting and Borkiewicz, Olaf J. and Wiaderek, Kamila M. and Gionet, Paul and Chapman, Karena W. and Chupas, Peter J. and Tang, Ming and Chiang, Yet-Ming},
abstractNote = {Alkali ion intercalation compounds used as battery electrodes often exhibit first-order phase transitions during electro-chemical cycling, accompanied by significant transformation strains. Despite 30 years of research into the behavior of such compounds, the relationship between transformation strain and electrode performance, especially the rate at which working ions (e.g., Li) can be intercalated and deintercalated, is still absent. In this work, we use the LiMnyFe1-yPO4 system for a systematic study, and measure using operando synchrotron radiation powder X-ray diffraction (SR-PXD) the dynamic strain behavior as a function of the Mn content (y) in powders of similar to 50 nm average diameter. The dynamically produced strain deviates significantly from what is expected from the equilibrium phase diagrams and demonstrates metastability but nonetheless spans a wide range from 0 to 8 vol % with y. For the first time, we show that the discharge capacity at high C-rates (20-50C rate) varies in inverse proportion to the transformation strain, implying that engineering electrode materials for reduced strain can be used to maximize the power capability of batteries.},
doi = {10.1021/acs.nanolett.5b05146},
url = {https://www.osti.gov/biblio/1376721}, journal = {Nano Letters},
issn = {1530-6984},
number = 4,
volume = 16,
place = {United States},
year = {Wed Apr 13 00:00:00 EDT 2016},
month = {Wed Apr 13 00:00:00 EDT 2016}
}