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Title: Exploring the influence of iron substitution in lithium rich layered oxides Li 2Ru 1–xFe xO 3: triggering the anionic redox reaction

Lithium rich layered materials are an interesting class of materials which exploit both anionic and cationic redox reactions to store energy upwards of 250 mA h g –1. This paper aims to understand the nature of the redox reactions taking place in these compounds. Li 2RuO 3 was used as the base compound, which is then compared with compounds generated by partially substituting Ru with Ti and Fe respectively. Electrochemical tests indicate that Fe substitution in the sample leads to an improvement in capacity, cycle life and reduction of potential decay. To elucidate the reason for this improvement in operando diffraction experiments were carried out, highlighting the formation of a secondary de-lithiated phase. The distortion of the pristine structure eventually induces frontier orbital reorganization leading to the oxygen redox reaction resulting in extra capacity. Local changes at Fe and Ru ions are recorded using in operando X-ray absorption spectroscopy (XAS). It was noted that while Ru undergoes a reversible redox reaction, Fe undergoes a significant irreversible change in its coordination environment during cycling. In conclusion, the changes in the coordination environment of oxygen and formation of O 2 n– type species were probed in situ using soft X-rays.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [3] ; ORCiD logo [1] ;  [4] ;  [5] ; ORCiD logo [5] ;  [6]
  1. Nanyang Technological Univ. (Singapore)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. TUM CREATE (Singapore)
  4. Nanyang Technological Univ. (Singapore); Univ. College London, London (United Kingdom); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  6. Nanyang Technological Univ. (Singapore); TUM CREATE (Singapore)
Publication Date:
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 27; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1373203

Satish, Rohit, Lim, Kipil, Bucher, Nicolas, Hartung, Steffen, Aravindan, Vanchiappan, Franklin, Joseph, Lee, Jun -Sik, Toney, Michael F., and Madhavi, Srinivasan. Exploring the influence of iron substitution in lithium rich layered oxides Li2Ru1–xFexO3: triggering the anionic redox reaction. United States: N. p., Web. doi:10.1039/c7ta04194b.
Satish, Rohit, Lim, Kipil, Bucher, Nicolas, Hartung, Steffen, Aravindan, Vanchiappan, Franklin, Joseph, Lee, Jun -Sik, Toney, Michael F., & Madhavi, Srinivasan. Exploring the influence of iron substitution in lithium rich layered oxides Li2Ru1–xFexO3: triggering the anionic redox reaction. United States. doi:10.1039/c7ta04194b.
Satish, Rohit, Lim, Kipil, Bucher, Nicolas, Hartung, Steffen, Aravindan, Vanchiappan, Franklin, Joseph, Lee, Jun -Sik, Toney, Michael F., and Madhavi, Srinivasan. 2017. "Exploring the influence of iron substitution in lithium rich layered oxides Li2Ru1–xFexO3: triggering the anionic redox reaction". United States. doi:10.1039/c7ta04194b. https://www.osti.gov/servlets/purl/1373203.
@article{osti_1373203,
title = {Exploring the influence of iron substitution in lithium rich layered oxides Li2Ru1–xFexO3: triggering the anionic redox reaction},
author = {Satish, Rohit and Lim, Kipil and Bucher, Nicolas and Hartung, Steffen and Aravindan, Vanchiappan and Franklin, Joseph and Lee, Jun -Sik and Toney, Michael F. and Madhavi, Srinivasan},
abstractNote = {Lithium rich layered materials are an interesting class of materials which exploit both anionic and cationic redox reactions to store energy upwards of 250 mA h g–1. This paper aims to understand the nature of the redox reactions taking place in these compounds. Li2RuO3 was used as the base compound, which is then compared with compounds generated by partially substituting Ru with Ti and Fe respectively. Electrochemical tests indicate that Fe substitution in the sample leads to an improvement in capacity, cycle life and reduction of potential decay. To elucidate the reason for this improvement in operando diffraction experiments were carried out, highlighting the formation of a secondary de-lithiated phase. The distortion of the pristine structure eventually induces frontier orbital reorganization leading to the oxygen redox reaction resulting in extra capacity. Local changes at Fe and Ru ions are recorded using in operando X-ray absorption spectroscopy (XAS). It was noted that while Ru undergoes a reversible redox reaction, Fe undergoes a significant irreversible change in its coordination environment during cycling. In conclusion, the changes in the coordination environment of oxygen and formation of O2n– type species were probed in situ using soft X-rays.},
doi = {10.1039/c7ta04194b},
journal = {Journal of Materials Chemistry. A},
number = 27,
volume = 5,
place = {United States},
year = {2017},
month = {6}
}

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