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Title: Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials

Abstract

Layered sodium transition metal oxides of NaTMO 2 (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO 2. Here we report a novel spontaneous TM layer rippling in the sodium ion battery cathode materials, revealed by in-situ X-ray diffraction, Cs-corrected scanning transmission electron microscopy and density functional theory simulation, where the softening and distortion of FeO 6 octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [3];  [2];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466611
Report Number(s):
BNL-207944-2018-JAAM
Journal ID: ISSN 1616-301X
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 39; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
29 ENERGY PLANNING, POLICY AND ECONOMY; NaTMO2; Sodium ion battery; density functional theory

Citation Formats

Chen, Xi, Hwang, Sooyeon, Chisnell, Robin, Wang, Yichao, Wu, Fan, Kim, Sooran, Lynn, Jeffrey W., Su, Dong, and Li, Xin. Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials. United States: N. p., 2018. Web. doi:10.1002/adfm.201803896.
Chen, Xi, Hwang, Sooyeon, Chisnell, Robin, Wang, Yichao, Wu, Fan, Kim, Sooran, Lynn, Jeffrey W., Su, Dong, & Li, Xin. Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials. United States. doi:10.1002/adfm.201803896.
Chen, Xi, Hwang, Sooyeon, Chisnell, Robin, Wang, Yichao, Wu, Fan, Kim, Sooran, Lynn, Jeffrey W., Su, Dong, and Li, Xin. Tue . "Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials". United States. doi:10.1002/adfm.201803896.
@article{osti_1466611,
title = {Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials},
author = {Chen, Xi and Hwang, Sooyeon and Chisnell, Robin and Wang, Yichao and Wu, Fan and Kim, Sooran and Lynn, Jeffrey W. and Su, Dong and Li, Xin},
abstractNote = {Layered sodium transition metal oxides of NaTMO2 (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO2. Here we report a novel spontaneous TM layer rippling in the sodium ion battery cathode materials, revealed by in-situ X-ray diffraction, Cs-corrected scanning transmission electron microscopy and density functional theory simulation, where the softening and distortion of FeO6 octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.},
doi = {10.1002/adfm.201803896},
journal = {Advanced Functional Materials},
number = 39,
volume = 28,
place = {United States},
year = {Tue Jul 31 00:00:00 EDT 2018},
month = {Tue Jul 31 00:00:00 EDT 2018}
}

Journal Article:
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Works referenced in this record:

Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries
journal, February 2006

  • Kang, Kisuk; Shirley Meng, Ying; Breger, Julien
  • Science, Vol. 311, Issue 5763, p. 977-980
  • DOI: 10.1126/science.1122152

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495