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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:
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. https://www.osti.gov/servlets/purl/1466611.
@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 = {2018},
month = {7}
}

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Works referenced in this record:

Vacancy Ordering in O 3 -Type Layered Metal Oxide Sodium-Ion Battery Cathodes
journal, December 2015


Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Layered-to-Rock-Salt Transformation in Desodiated Na x CrO 2 ( x 0.4)
journal, February 2016


High Performance Na 0.5 [Ni 0.23 Fe 0.13 Mn 0.63 ]O 2 Cathode for Sodium-Ion Batteries
journal, June 2014

  • Hasa, Ivana; Buchholz, Daniel; Passerini, Stefano
  • Advanced Energy Materials, Vol. 4, Issue 15
  • DOI: 10.1002/aenm.201400083

Electrochemical investigation of the P2–NaxCoO2 phase diagram
journal, December 2010

  • Berthelot, R.; Carlier, D.; Delmas, C.
  • Nature Materials, Vol. 10, Issue 1
  • DOI: 10.1038/nmat2920

Electrochemical Na Insertion and Solid Electrolyte Interphase for Hard-Carbon Electrodes and Application to Na-Ion Batteries
journal, August 2011

  • Komaba, Shinichi; Murata, Wataru; Ishikawa, Toru
  • Advanced Functional Materials, Vol. 21, Issue 20
  • DOI: 10.1002/adfm.201100854

P2-NaxVO2 system as electrodes for batteries and electron-correlated materials
journal, November 2012

  • Guignard, Marie; Didier, Christophe; Darriet, Jacques
  • Nature Materials, Vol. 12, Issue 1
  • DOI: 10.1038/nmat3478

Electrochemical Properties of Monoclinic NaMnO2
journal, January 2011

  • Ma, Xiaohua; Chen, Hailong; Ceder, Gerbrand
  • Journal of The Electrochemical Society, Vol. 158, Issue 12
  • DOI: 10.1149/2.035112jes

Sodium deintercalation from sodium iron oxide
journal, June 1994


NaTiO 2 : a layered anode material for sodium-ion batteries
journal, January 2015

  • Wu, Di; Li, Xin; Xu, Bo
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE03045A

Suppression of thermal conductivity by rattling modes in thermoelectric sodium cobaltate
journal, August 2013

  • Voneshen, D. J.; Refson, K.; Borissenko, E.
  • Nature Materials, Vol. 12, Issue 11
  • DOI: 10.1038/nmat3739

Study on the Reversible Electrode Reaction of Na 1– x Ni 0.5 Mn 0.5 O 2 for a Rechargeable Sodium-Ion Battery
journal, May 2012

  • Komaba, Shinichi; Yabuuchi, Naoaki; Nakayama, Tetsuri
  • Inorganic Chemistry, Vol. 51, Issue 11
  • DOI: 10.1021/ic300357d

Layered Oxide Cathodes for Sodium-Ion Batteries: Phase Transition, Air Stability, and Performance
journal, November 2017


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

P2-Na0.6[Cr0.6Ti0.4]O2 cation-disordered electrode for high-rate symmetric rechargeable sodium-ion batteries
journal, April 2015

  • Wang, Yuesheng; Xiao, Ruijuan; Hu, Yong-Sheng
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7954

Crystal Structures and Electrode Performance of Alpha-NaFeO2 for Rechargeable Sodium Batteries
journal, January 2012


X-ray diffraction line broadening: modeling and applications to high-Tc superconductors
journal, May 1993

  • Balzar, D.
  • Journal of Research of the National Institute of Standards and Technology, Vol. 98, Issue 3
  • DOI: 10.6028/jres.098.026

High performance manganese-based layered oxide cathodes: overcoming the challenges of sodium ion batteries
journal, January 2017

  • Ortiz-Vitoriano, Nagore; Drewett, Nicholas E.; Gonzalo, Elena
  • Energy & Environmental Science, Vol. 10, Issue 5
  • DOI: 10.1039/C7EE00566K

Patterning of sodium ions and the control of electrons in sodium cobaltate
journal, February 2007

  • Roger, M.; Morris, D. J. P.; Tennant, D. A.
  • Nature, Vol. 445, Issue 7128
  • DOI: 10.1038/nature05531

NaFe0.5Co0.5O2 as high energy and power positive electrode for Na-ion batteries
journal, September 2013


Superconductivity in two-dimensional CoO2 layers
journal, March 2003

  • Takada, Kazunori; Sakurai, Hiroya; Takayama-Muromachi, Eiji
  • Nature, Vol. 422, Issue 6927
  • DOI: 10.1038/nature01450

Direct visualization of the Jahn–Teller effect coupled to Na ordering in Na5/8MnO2
journal, May 2014

  • Li, Xin; Ma, Xiaohua; Su, Dong
  • Nature Materials, Vol. 13, Issue 6
  • DOI: 10.1038/nmat3964

Role of Ligand-to-Metal Charge Transfer in O3-Type NaFeO 2 –NaNiO 2 Solid Solution for Enhanced Electrochemical Properties
journal, January 2014

  • Wang, Xianfen; Liu, Guandong; Iwao, Tatsumi
  • The Journal of Physical Chemistry C, Vol. 118, Issue 6
  • DOI: 10.1021/jp411382r

Cordierite-indialite relations
journal, January 1957


Synthesis and Stoichiometry of Different Layered Sodium Cobalt Oxides
journal, September 2014

  • Lei, Yuechuan; Li, Xin; Liu, Lei
  • Chemistry of Materials, Vol. 26, Issue 18
  • DOI: 10.1021/cm5021788

Origin of Structural Degradation During Cycling and Low Thermal Stability of Ni-Rich Layered Transition Metal-Based Electrode Materials
journal, October 2017

  • Dixit, Mudit; Markovsky, Boris; Schipper, Florian
  • The Journal of Physical Chemistry C, Vol. 121, Issue 41
  • DOI: 10.1021/acs.jpcc.7b06122

A comparison of destabilization mechanisms of the layered NaxMO2 and LixMO2 compounds upon alkali de-intercalation
journal, January 2012

  • Kim, Sangtae; Ma, Xiaohua; Ong, Shyue Ping
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 44
  • DOI: 10.1039/c2cp43377j

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

Layered Na[Ni1/3Fe1/3Mn1/3]O2 cathodes for Na-ion battery application
journal, January 2012


Double-Focusing Thermal Triple-Axis Spectrometer at the NCNR
journal, January 2012

  • Lynn, J. W.; Chen, Y.; Chang, S.
  • Journal of Research of the National Institute of Standards and Technology, Vol. 117
  • DOI: 10.6028/jres.117.002

P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries
journal, April 2012

  • Yabuuchi, Naoaki; Kajiyama, Masataka; Iwatate, Junichi
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3309

Assessment of van der Waals inclusive density functional theory methods for layered electroactive materials
journal, January 2017

  • Lozano, Ariel; Escribano, Bruno; Akhmatskaya, Elena
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 15
  • DOI: 10.1039/C7CP00284J

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017


Na + /vacancy disordering promises high-rate Na-ion batteries
journal, March 2018


Honeycomb-Ordered Na 3 Ni 1.5 M 0.5 BiO 6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries
journal, November 2017


Synthesis, Structure, and Electrochemical Properties of the Layered Sodium Insertion Cathode Material: NaNi 1 / 3 Mn 1 / 3 Co 1 / 3 O 2
journal, April 2012

  • Sathiya, M.; Hemalatha, K.; Ramesha, K.
  • Chemistry of Materials, Vol. 24, Issue 10
  • DOI: 10.1021/cm300466b

O3-type Na(Mn0.25Fe0.25Co0.25Ni0.25)O2: A quaternary layered cathode compound for rechargeable Na ion batteries
journal, December 2014


Electrochemical intercalation activity of layered NaCrO2 vs. LiCrO2
journal, March 2010


Electrochemical Properties of Monoclinic NaNiO 2
journal, November 2012

  • Vassilaras, Plousia; Ma, Xiaohua; Li, Xin
  • Journal of The Electrochemical Society, Vol. 160, Issue 2
  • DOI: 10.1149/2.023302jes

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Jahn–Teller Assisted Na Diffusion for High Performance Na Ion Batteries
journal, September 2016


New Insight into Structural Evolution in Layered NaCrO 2 during Electrochemical Sodium Extraction
journal, December 2014

  • Kubota, Kei; Ikeuchi, Issei; Nakayama, Tetsuri
  • The Journal of Physical Chemistry C, Vol. 119, Issue 1
  • DOI: 10.1021/jp5105888

Accuracy of density functional theory in predicting formation energies of ternary oxides from binary oxides and its implication on phase stability
journal, April 2012


Structure of the high voltage phase of layered P2-Na 2/3−z [Mn 1/2 Fe 1/2 ]O 2 and the positive effect of Ni substitution on its stability
journal, January 2015

  • Talaie, Elahe; Duffort, Victor; Smith, Hillary L.
  • Energy & Environmental Science, Vol. 8, Issue 8
  • DOI: 10.1039/C5EE01365H

Research Development on Sodium-Ion Batteries
journal, October 2014

  • Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500192f

Understanding the Structural Evolution and Redox Mechanism of a NaFeO 2 -NaCoO 2 Solid Solution for Sodium-Ion Batteries
journal, June 2016

  • Kubota, Kei; Asari, Takuya; Yoshida, Hiroaki
  • Advanced Functional Materials, Vol. 26, Issue 33
  • DOI: 10.1002/adfm.201601292