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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:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1322360
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 55; Journal Issue: 17
Country of Publication:
United States
Language:
ENGLISH

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. 2016. "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_1322360,
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 = 2016,
month = 9
}
  • 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
  • Na-ion batteries are appealing alternatives to Li-ion battery systems for large-scale energy storage applications in which elemental cost and abundance are important. Although it is difficult to find Na-ion batteries which achieve substantial specific capacities at voltages above 3 V (vs Na⁺/Na), the honeycomb-layered compound Na(Ni 2/3Sb 1/3)O₂ can deliver up to 130 mAh/g of capacity at voltages above 3 V with this capacity concentrated in plateaus at 3.27 and 3.64 V. Comprehensive crystallographic studies have been carried out in order to understand the role of disorder in this system which can be prepared in both “disordered” and “ordered” forms,more » depending on the synthesis conditions. The average structure of Na(Ni 2/3Sb 1/3)O₂ is always found to adopt an O3-type stacking sequence, though different structures for the disordered (R3¯ m, #166, a = b = 3.06253(3) Å and c = 16.05192(7) Å) and ordered variants ( C2/m, #12, a = 5.30458(1) Å, b = 9.18432(1) Å, c = 5.62742(1) Å and β = 108.2797(2)°) are demonstrated through the combined Rietveld refinement of synchrotron X-ray and time-of-flight neutron powder diffraction data. However, pair distribution function studies find that the local structure of disordered Na(Ni 2/3Sb 1/3)O₂ is more correctly described using the honeycomb-ordered structural model, and solid state NMR studies confirm that the well-developed honeycomb ordering of Ni and Sb cations within the transition metal layers is indistinguishable from that of the ordered phase. The disorder is instead found to mainly occur perpendicular to the honeycomb layers with an observed coherence length of not much more than 1 nm seen in electron diffraction studies. When the Na environment is probed through ²³Na solid state NMR, no evidence is found for prismatic Na environments, and a bulk diffraction analysis finds no evidence of conventional stacking faults. The lack of long range coherence is instead attributed to disorder among the three possible choices for distributing Ni and Sb cations into a honeycomb lattice in each transition metal layer. It is observed that the full theoretical discharge capacity expected for a Ni³⁺/²⁺ redox couple (133 mAh/g) can be achieved for the ordered variant but not for the disordered variant (~110 mAh/g). The first 3.27 V plateau during charging is found to be associated with a two-phase O3 ↔ P3 structural transition, with the P3 stacking sequence persisting throughout all further stages of desodiation.« less