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Title: Li-Substituted Layered Spinel Cathode Material for Sodium Ion Batteries

Abstract

The O3-type layered Na(NixFeyMnz)O2 (0 < x, y, z < 1) cathode materials have attracted great interest in sodium-ion batteries due to the abundance and cost of raw materials and their high specific capacities. However, the cycling stability and rate ca-pability at high voltages (> 4.0V) of these materials remains an issue. In this work, we successfully synthesized a Li-substituted layered-tunneled (O3-spinel) intergrowth cathode (LS-NFM) to address these issues. The remarkable structural compatibility and connectivity of the two phases were confirmed by X-ray diffraction (XRD), selected area electron diffrac-tion (SAED) and high resolution transmission electron microscopy (HRTEM). LS-NFM electrode reached a discharge capaci-ty of 96 mAh g-1 with a capacity retention of 86% after 100 cycles at a current rate of 100 mA g-1 in a voltage window of 2.0 - 4.2 V. Moreover, the LS-NFM cathode exhibited an enhanced rate capability in comparison to the un-doped layered cath-ode (NFM). The enhanced rate capability of LS-NFM can be explained by the significantly increased effective Na+ diffusivity measured by galvanostatic intermittent titration technique (GITT) compared to the un-doped control NFM cathode, which can be ascribed to the improved charge transport kinetics through shortened diffusion path by direct connection between the 3Dmore » channels in the spinel phase and 2D channels in the layered phase. The results from ex situ hard/soft X-ray adsorption spectroscopy (XAS) suggest that the capacity of LS-NFM cathode is mainly associated with the Ni2+/Ni4+ redox couple, and slightly from the Fe3+/Fe4+ redox couple. The voltage profile of the LS-NFM cathode exhibited a reversible plateau above 4.0 V, indicating great stability at high voltages and structural stabilization by the spinel phase. In addition to the substitution of various transition metals, or the modification of the stoichiometry of each transition metal, this study provides a new strategy to improve electrochemical performance of layered cathode materials for sodium ion batteries.« less

Authors:
 [1];  [1];  [2];  [3]; ORCiD logo [3];  [4];  [1];  [1];  [1];  [5]; ORCiD logo [6]
  1. Boise State Univ., ID (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Boise State Univ., ID (United States); Shanghai Jiao Tong Univ., Shanghai (China)
  5. Iowa State Univ., Ames, IA (United States)
  6. Boise State Univ., ID (United States); Center for Advanced Energy Studies, Boulevard, Idaho Falls, ID (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Boise State Univ., ID (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1542342
Alternate Identifier(s):
OSTI ID: 1494597; OSTI ID: 1711437
Grant/Contract Number:  
AC02-05CH11231; SC0019121; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 22; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Intergrowth, layered oxide, spinel, cathode, sodium ion battery

Citation Formats

Deng, Changjian, Skinner, Paige, Liu, Yuzi, Sun, Meiling, Tong, Wei, Ma, Chunrong, Lau, Miu Lun, Hunt, Riley, Barnes, Pete, Xu, Jing, and Xiong, Hui. Li-Substituted Layered Spinel Cathode Material for Sodium Ion Batteries. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b02614.
Deng, Changjian, Skinner, Paige, Liu, Yuzi, Sun, Meiling, Tong, Wei, Ma, Chunrong, Lau, Miu Lun, Hunt, Riley, Barnes, Pete, Xu, Jing, & Xiong, Hui. Li-Substituted Layered Spinel Cathode Material for Sodium Ion Batteries. United States. doi:10.1021/acs.chemmater.8b02614.
Deng, Changjian, Skinner, Paige, Liu, Yuzi, Sun, Meiling, Tong, Wei, Ma, Chunrong, Lau, Miu Lun, Hunt, Riley, Barnes, Pete, Xu, Jing, and Xiong, Hui. Wed . "Li-Substituted Layered Spinel Cathode Material for Sodium Ion Batteries". United States. doi:10.1021/acs.chemmater.8b02614. https://www.osti.gov/servlets/purl/1542342.
@article{osti_1542342,
title = {Li-Substituted Layered Spinel Cathode Material for Sodium Ion Batteries},
author = {Deng, Changjian and Skinner, Paige and Liu, Yuzi and Sun, Meiling and Tong, Wei and Ma, Chunrong and Lau, Miu Lun and Hunt, Riley and Barnes, Pete and Xu, Jing and Xiong, Hui},
abstractNote = {The O3-type layered Na(NixFeyMnz)O2 (0 < x, y, z < 1) cathode materials have attracted great interest in sodium-ion batteries due to the abundance and cost of raw materials and their high specific capacities. However, the cycling stability and rate ca-pability at high voltages (> 4.0V) of these materials remains an issue. In this work, we successfully synthesized a Li-substituted layered-tunneled (O3-spinel) intergrowth cathode (LS-NFM) to address these issues. The remarkable structural compatibility and connectivity of the two phases were confirmed by X-ray diffraction (XRD), selected area electron diffrac-tion (SAED) and high resolution transmission electron microscopy (HRTEM). LS-NFM electrode reached a discharge capaci-ty of 96 mAh g-1 with a capacity retention of 86% after 100 cycles at a current rate of 100 mA g-1 in a voltage window of 2.0 - 4.2 V. Moreover, the LS-NFM cathode exhibited an enhanced rate capability in comparison to the un-doped layered cath-ode (NFM). The enhanced rate capability of LS-NFM can be explained by the significantly increased effective Na+ diffusivity measured by galvanostatic intermittent titration technique (GITT) compared to the un-doped control NFM cathode, which can be ascribed to the improved charge transport kinetics through shortened diffusion path by direct connection between the 3D channels in the spinel phase and 2D channels in the layered phase. The results from ex situ hard/soft X-ray adsorption spectroscopy (XAS) suggest that the capacity of LS-NFM cathode is mainly associated with the Ni2+/Ni4+ redox couple, and slightly from the Fe3+/Fe4+ redox couple. The voltage profile of the LS-NFM cathode exhibited a reversible plateau above 4.0 V, indicating great stability at high voltages and structural stabilization by the spinel phase. In addition to the substitution of various transition metals, or the modification of the stoichiometry of each transition metal, this study provides a new strategy to improve electrochemical performance of layered cathode materials for sodium ion batteries.},
doi = {10.1021/acs.chemmater.8b02614},
journal = {Chemistry of Materials},
number = 22,
volume = 30,
place = {United States},
year = {2018},
month = {10}
}

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Figures / Tables:

Figure 2 Figure 2: HRTEM images of a) as-prepared, b) 1st discharged and c) 50th discharged LS-NFM sample. The red and white dashed square indicates the spinel and layered components, respectively, where the corresponding FFT images are shown as insets. The red and white circle indicate the spinel (111) plane with themore » zone axis [110] and layered (003) plane with the zone axis [100], respectively. The SAED images of d) as-prepared, e) 1st discharged and f) 50th discharged LS-NFM sample where the red circles and white arrows or circle indicate the planes from spinel and layered phase, respectively.« less

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Works referencing / citing this record:

Ni-based cathode materials for Na-ion batteries
journal, June 2019


Ni-based cathode materials for Na-ion batteries
journal, June 2019


Layer‐Based Heterostructured Cathodes for Lithium‐Ion and Sodium‐Ion Batteries
journal, February 2019

  • Deng, Ya‐Ping; Wu, Zhen‐Guo; Liang, Ruilin
  • Advanced Functional Materials, Vol. 29, Issue 19
  • DOI: 10.1002/adfm.201808522

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.