Insights into the Effects of Zinc Doping on Structural Phase Transition of P2-Type Sodium Nickel Manganese Oxide Cathodes for High-Energy Sodium Ion Batteries

Journal Article · Wed Aug 31 00:00:00 EDT 2016 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.6b06701· OSTI ID:1338410

Wu, Xuehang; Xu, Gui-Liang; Zhong, Guiming; Gong, Zhengliang; McDonald, Matthew J.; Zheng, Shiyao; Fu, Riqiang; Chen, Zonghai; Amine, Khalil; Yang, Yong

P2-type sodium nickel manganese oxide-based cathode materials with higher energy densities are prime candidates for applications in rechargeable sodium ion batteries. A systematic study combining in situ high energy X-ray diffraction (HEXRD), ex situ Xray absorption fine spectroscopy (XAFS), transmission electron microscopy (TEM), and solid-state nuclear magnetic resonance (SSNMR) techniques was carried out to gain a deep insight into the structural evolution of P2-Na_0.66Ni_0.33-xZn_xMn_0.67O₂ (x = 0, 0.07) during cycling. In situ HEXRD and ex situ TEM measurements indicate that an irreversible phase transition occurs upon sodium insertion-extraction of Na_0.66Ni_0.33Mn_0.67O₂. Zinc doping of this system results in a high structural reversibility. XAFS measurements indicate that both materials are almost completely dependent on the Ni⁴⁺/Ni³⁺/ Ni²⁺ redox couple to provide charge/discharge capacity. SS-NMR measurements indicate that both reversible and irreversible migration of transition metal ions into the sodium layer occurs in the material at the fully charged state. The irreversible migration of transition metal ions triggers a structural distortion, leading to the observed capacity and voltage fading. Our results allow a new understanding of the importance of improving the stability of transition metal layers.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States)
• Sponsoring Organization: National Natural Science Foundation of China (NNSFC); National Basic Research Program of China; USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technology
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1338410
• Journal Information: ACS Applied Materials and Interfaces, Vol. 8, Issue 34; ISSN 1944-8244
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
Zn doping
cathode material
sodium ion battery
sodium nickel manganese oxide
structural transition