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Title: Quantification of Honeycomb Number-Type Stacking Faults: Application to Na 3 Ni 2 BiO 6 Cathodes for Na-Ion Batteries

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [3];  [5];  [1]
  1. Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, United States; Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, United States
  2. Department of Chemistry, Stony Brook University, Stony Brook, New York 11794-3400, United States
  3. Condensed Matter Physics and Material Science Department, Brookhaven National Laboratory, Upton, New York 11973, United States
  4. Photon Science Division, Brookhaven National Laboratory, Upton, New York 11973, United States
  5. Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388765
DOE Contract Number:
SC0001294
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 55; Journal Issue: 17; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University
Country of Publication:
United States
Language:
English
Subject:
energy storage (including batteries and capacitors), defects, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Liu, Jue, Yin, Liang, Wu, Lijun, Bai, Jianming, Bak, Seong-Min, Yu, Xiqian, Zhu, Yimei, Yang, Xiao-Qing, and Khalifah, Peter G. Quantification of Honeycomb Number-Type Stacking Faults: Application to Na 3 Ni 2 BiO 6 Cathodes for Na-Ion Batteries. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b01078.
Liu, Jue, Yin, Liang, Wu, Lijun, Bai, Jianming, Bak, Seong-Min, Yu, Xiqian, Zhu, Yimei, Yang, Xiao-Qing, & Khalifah, Peter G. Quantification of Honeycomb Number-Type Stacking Faults: Application to Na 3 Ni 2 BiO 6 Cathodes for Na-Ion Batteries. United States. doi:10.1021/acs.inorgchem.6b01078.
Liu, Jue, Yin, Liang, Wu, Lijun, Bai, Jianming, Bak, Seong-Min, Yu, Xiqian, Zhu, Yimei, Yang, Xiao-Qing, and Khalifah, Peter G. Mon . "Quantification of Honeycomb Number-Type Stacking Faults: Application to Na 3 Ni 2 BiO 6 Cathodes for Na-Ion Batteries". United States. doi:10.1021/acs.inorgchem.6b01078.
@article{osti_1388765,
title = {Quantification of Honeycomb Number-Type Stacking Faults: Application to Na 3 Ni 2 BiO 6 Cathodes for Na-Ion Batteries},
author = {Liu, Jue and Yin, Liang and Wu, Lijun and Bai, Jianming and Bak, Seong-Min and Yu, Xiqian and Zhu, Yimei and Yang, Xiao-Qing and Khalifah, Peter G.},
abstractNote = {},
doi = {10.1021/acs.inorgchem.6b01078},
journal = {Inorganic Chemistry},
number = 17,
volume = 55,
place = {United States},
year = {Mon Aug 08 00:00:00 EDT 2016},
month = {Mon Aug 08 00:00:00 EDT 2016}
}
  • Here, ordered and disordered samples of honeycomb-lattice Na 3Ni 2BiO 6 were investigated as cathodes for Na-ion batteries, and it was determined that the ordered sample exhibits better electrochemical performance, with a specific capacity of 104 mA h/g delivered at plateaus of 3.5 and 3.2 V (vs Na +/Na) with minimal capacity fade during extended cycling. Advanced imaging and diffraction investigations showed that the primary difference between the ordered and disordered samples is the amount of number-type stacking faults associated with the three possible centering choices for each honeycomb layer. A labeling scheme for assigning the number position of honeycombmore » layers is described, and it is shown that the translational shift vectors between layers provide the simplest method for classifying different repeat patterns. We demonstrate that the number position of honeycomb layers can be directly determined in high-angle annular dark-field scanning transmission electron microscopy (STEM-HAADF) imaging studies. By the use of fault models derived from STEM studies, it is shown that both the sharp, symmetric subcell peaks and the broad, asymmetric superstructure peaks in powder diffraction patterns can be quantitatively modeled. About 20% of the layers in the ordered monoclinic sample are faulted in a nonrandom manner, while the disordered sample stacking is not fully random but instead contains about 4% monoclinic order. Furthermore, it is shown that the ordered sample has a series of higher-order superstructure peaks associated with 6-, 9-, 12-, and 15-layer periods whose existence is transiently driven by the presence of long-range strain that is an inherent consequence of the synthesis mechanism revealed through the present diffraction and imaging studies. This strain is closely associated with a monoclinic shear that can be directly calculated from cell lattice parameters and is strongly correlated with the degree of ordering in the samples. The present results are broadly applicable to other honeycomb-lattice systems, including Li 2MnO 3 and related Li-excess cathode compositions.« less
  • Developing high-voltage layered cathodes for sodium-ion batteries (SIBs) has always been a severe challenge. Herein, a new family of honeycomb-layered Na 3Ni 1.5M 0.5BiO 6 (M = Ni, Cu, Mg, Zn) with a monoclinic superstructure has been shown to combine good Na + (de)intercalation activity with a competitive 3.3 V high voltage. By coupling the electrochemical process with ex situ X-ray absorption spectroscopy as well as in situ X-ray diffraction, the charge compensation mechanism and structural evolution of these new cathodes are clearly investigated. Interestingly, both Ni 2+/Ni 3+ and Cu 2+/Cu 3+ participate in the redox reaction upon cycling,more » and the succession of single-phase, two-phase, or three-phase regions upon Na+ extraction/insertion were identified with rather good accuracy. Furthermore, this research strategy could provide insights into the structure–function–property relationships on a new series of honeycomb-ordered materials with the general formula Na 3Ni 1.5M 0.5BiO 6 and also serve as a bridge to guide future design of high-performance cathodes for SIBs.« less