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

Abstract

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, 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.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [2];  [2];  [3];  [3];  [4]; ORCiD logo [5]; ORCiD logo [1]
  1. Chinese Academy of Sciences (CAS), Beijing (China); Univ. of Chinese Academy of Sciences, Beijing (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Qingdao Univ., Qingdao (China)
  4. Chinese Academy of Sciences (CAS), Beijing (China); Univ. of Chinese Academy of Science, Beijing (China)
  5. Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1409508
Report Number(s):
BNL-114520-2017-JA
Journal ID: ISSN 2380-8195; R&D Project: MA453MAEA; VT1201000
Grant/Contract Number:
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 2; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; National Synchrotron Light Source

Citation Formats

Wang, Peng -Fei, Guo, Yu -Jie, Duan, Hui, Zuo, Tong -Tong, Hu, Enyuan, Attenkofer, Klaus, Li, Hongliang, Zhao, Xiu Song, Yin, Ya -Xia, Yu, Xiqian, and Guo, Yu -Guo. Honeycomb-Ordered Na3Ni1.5M0.5BiO6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries. United States: N. p., 2017. Web. doi:10.1021/acsenergylett.7b00930.
Wang, Peng -Fei, Guo, Yu -Jie, Duan, Hui, Zuo, Tong -Tong, Hu, Enyuan, Attenkofer, Klaus, Li, Hongliang, Zhao, Xiu Song, Yin, Ya -Xia, Yu, Xiqian, & Guo, Yu -Guo. Honeycomb-Ordered Na3Ni1.5M0.5BiO6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries. United States. doi:10.1021/acsenergylett.7b00930.
Wang, Peng -Fei, Guo, Yu -Jie, Duan, Hui, Zuo, Tong -Tong, Hu, Enyuan, Attenkofer, Klaus, Li, Hongliang, Zhao, Xiu Song, Yin, Ya -Xia, Yu, Xiqian, and Guo, Yu -Guo. 2017. "Honeycomb-Ordered Na3Ni1.5M0.5BiO6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries". United States. doi:10.1021/acsenergylett.7b00930.
@article{osti_1409508,
title = {Honeycomb-Ordered Na3Ni1.5M0.5BiO6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries},
author = {Wang, Peng -Fei and Guo, Yu -Jie and Duan, Hui and Zuo, Tong -Tong and Hu, Enyuan and Attenkofer, Klaus and Li, Hongliang and Zhao, Xiu Song and Yin, Ya -Xia and Yu, Xiqian and Guo, Yu -Guo},
abstractNote = {Developing high-voltage layered cathodes for sodium-ion batteries (SIBs) has always been a severe challenge. Herein, a new family of honeycomb-layered Na3Ni1.5M0.5BiO6 (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 Ni2+/Ni3+ and Cu2+/Cu3+ participate in the redox reaction upon cycling, 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 Na3Ni1.5M0.5BiO6 and also serve as a bridge to guide future design of high-performance cathodes for SIBs.},
doi = {10.1021/acsenergylett.7b00930},
journal = {ACS Energy Letters},
number = ,
volume = 2,
place = {United States},
year = 2017,
month =
}

Journal Article:
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  • 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