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Title: Super Charge Separation and High Voltage Phase in NaxMnO2

Abstract

NaxMnO2 shows Mn3+ and Mn4+ charge separation with the charge stripe ordering upon Na deintercalation at x = 5/8. In this paper it is shown that, surprisingly, at lower Na compositions of 5/8 > x ≥ 1/18 the phase evolution pathway of NaxMnO2 upon Na deintercalation shows a unique phenomenon of super charge separation, where the Mn3+ and Mn4+ ions fully charge-separate into charge superplanes formed by succession of charge stripes in the third dimension. Furthermore, the Mn3+ superplanes attract Na ions electronically, and dominate the antiferromagnetic interactions in NaMnO2. Na ions in Mn3+ superplanes also naturally pillar the MnO2 layers to form the unusual O1 phases with large interlayer distances at x < 1/3, which dominates the unique electrochemical behavior of NaMnO2.

Authors:
 [1];  [1];  [2];  [3];  [2];  [2];  [3];  [4];  [1]
+ Show Author Affiliations
  1. Harvard Univ., Cambridge, MA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. North Carolina State Univ., Raleigh, NC (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
Harvard University; USDOE
OSTI Identifier:
1524584
Alternate Identifier(s):
OSTI ID: 1479523
Grant/Contract Number:  
AC02-06CH11357; AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials (Online)
Additional Journal Information:
Journal Name: Advanced Functional Materials (Online); Journal Volume: 28; Journal Issue: 50; Journal ID: ISSN 1616-3028
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Na ion batteries; magnetic properties of sodium manganese oxides; novel high-voltage phases; reversible asymmetric structural evolutions; super charge-separations

Citation Formats

Chen, Xi, Wang, Yichao, Wiaderek, Kamila, Sang, Xiahan, Borkiewicz, Olaf, Chapman, Karena, LeBeau, James, Lynn, Jeffrey, and Li, Xin. Super Charge Separation and High Voltage Phase in NaxMnO2. United States: N. p., 2018. Web. doi:10.1002/adfm.201805105.
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Chen, Xi, Wang, Yichao, Wiaderek, Kamila, Sang, Xiahan, Borkiewicz, Olaf, Chapman, Karena, LeBeau, James, Lynn, Jeffrey, & Li, Xin. Super Charge Separation and High Voltage Phase in NaxMnO2. United States. https://doi.org/10.1002/adfm.201805105
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Chen, Xi, Wang, Yichao, Wiaderek, Kamila, Sang, Xiahan, Borkiewicz, Olaf, Chapman, Karena, LeBeau, James, Lynn, Jeffrey, and Li, Xin. Sun . "Super Charge Separation and High Voltage Phase in NaxMnO2". United States. https://doi.org/10.1002/adfm.201805105. https://www.osti.gov/servlets/purl/1524584.
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@article{osti_1524584,
title = {Super Charge Separation and High Voltage Phase in NaxMnO2},
author = {Chen, Xi and Wang, Yichao and Wiaderek, Kamila and Sang, Xiahan and Borkiewicz, Olaf and Chapman, Karena and LeBeau, James and Lynn, Jeffrey and Li, Xin},
abstractNote = {NaxMnO2 shows Mn3+ and Mn4+ charge separation with the charge stripe ordering upon Na deintercalation at x = 5/8. In this paper it is shown that, surprisingly, at lower Na compositions of 5/8 > x ≥ 1/18 the phase evolution pathway of NaxMnO2 upon Na deintercalation shows a unique phenomenon of super charge separation, where the Mn3+ and Mn4+ ions fully charge-separate into charge superplanes formed by succession of charge stripes in the third dimension. Furthermore, the Mn3+ superplanes attract Na ions electronically, and dominate the antiferromagnetic interactions in NaMnO2. Na ions in Mn3+ superplanes also naturally pillar the MnO2 layers to form the unusual O1 phases with large interlayer distances at x < 1/3, which dominates the unique electrochemical behavior of NaMnO2.},
doi = {10.1002/adfm.201805105},
journal = {Advanced Functional Materials (Online)},
number = 50,
volume = 28,
place = {United States},
year = {Sun Oct 21 00:00:00 EDT 2018},
month = {Sun Oct 21 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/adfm.201805105
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Cited by: 25 works
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Figures / Tables:

Figure 1 Figure 1: Electrochemical profile and phase evolution of O’3-NaMnO2. The voltage profile of NaMnO2 in the first cycle between 2.0V and 4.5V at C/50 rate as a function of Na composition measured from an in-situ synchrotron XRD battery cell (XRD is shown in Figure 2), from which the phase evolutionmore » for charge (top bar) and discharge (bottom bar) is obtained. The corresponding interlayer distance at each Na composition for charge or discharge is shown by filled or empty symbols, respectively. The symbol for interlayer distance of O’3 phase is in red circles (filled or empty) and O1 phase in gray squares (filled or empty).« less
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    Works referencing / citing this record:

    Beyond Expert‐Level Performance Prediction for Rechargeable Batteries by Unsupervised Machine Learning
    journal, October 2019

    A Study of Cu Doping Effects in P2‐Na 0.75 Mn 0.6 Fe 0.2 (Cu x Ni 0.2‐ x )O 2 Layered Cathodes for Sodium‐Ion Batteries
    journal, April 2020

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      Figures / Tables found in this record:

      Figure 1 (p. 4)figure
      Figure 2 (p. 5)figure
      Figure 3 (p. 8)figure
      Figure 4 (p. 11)figure
      Figure 5 (p. 13)figure
      Figure 6 (p. 16)figure
      Figure 7 (p. 19)figure
      Figure 8 (p. 21)figure
      Figure S1 (p. 34)figure
      Figure S2 (p. 35)figure
      Figure S3 (p. 36)figure
      Figure S4 (p. 37)figure
      Figure S5 (p. 39)figure
      Figure S6 (p. 40)figure
      Figure S7 (p. 41)figure
      Figure S8 (p. 42)figure
      Figure S9 (p. 43)figure
      Table S1 (p. 44)table
      Table S2 (p. 45)table
      Table S3 (p. 46)table
      Table S4 (p. 47)table
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