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Title: Tuning P2-Structured Cathode Material by Na-Site Mg Substitution for Na-Ion Batteries

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b08638· OSTI ID:1488528
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [2];  [1]
  1. Fudan Univ., Shanghai (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

Most of P2-type layered oxides suffer from multiple voltage plateaus, due to Na+/vacancy-order superstructures caused by strong interplay between Na-Na electrostatic interactions and charge ordering in the transition-metal layers. In this paper, Mg-ions are successfully introduced into Na sites in addition to the conventional transition metal sites in P2-type Na0.7[Mn0.6Ni0.4]O2 as new cathode materials for sodium-ion batteries. Mg-ions in Na layer serve as “pillar” to stabilize the layered structure, especially for high voltage charging meanwhile Mg-ions in transition metal layer can destroy charge ordering. More importantly, Mg ion occupation in both sodium and transition metal layers will be able to create “Na-O-Mg” and “Mg-O-Mg” configurations in layered structure, resulting in ionic O 2p character, which allocates these O 2p states on top of those interact with transition metals in O-valence band, thus promoting reversible oxygen redox. This innovative design contributes smooth voltage profile and high structural stability. Na0.7Mg0.05[Mn0.6Ni0.2Mg0.15]O2 exhibits superior electrochemical performance, especially good capacity retention at high current rate under a high cut-off voltage (4.2 V). A new P2 phase is formed after charge, rather than O2 phase for the unsubstituted material. Besides, multiple intermediate phases are observed during high-rate charging. Na-ion transport kinetics are mainly affected by elemental-related redox couple and structural reorganization. In conclusion, these findings will open new opportunities for designing and optimizing layer-structured cathodes for sodium-ion batteries.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; AC02-05CH11231; AC02-06CH11357
OSTI ID:
1488528
Report Number(s):
BNL-209807-2018-JAAM
Journal Information:
Journal of the American Chemical Society, Vol. 141, Issue 2; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 166 works
Citation information provided by
Web of Science

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Cited By (9)

Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode journal December 2019
O3‐Type Layered Ni‐Rich Oxide: A High‐Capacity and Superior‐Rate Cathode for Sodium‐Ion Batteries journal December 2019
Hierarchical Engineering of Porous P2‐Na 2/3 Ni 1/3 Mn 2/3 O 2 Nanofibers Assembled by Nanoparticles Enables Superior Sodium‐Ion Storage Cathodes journal November 2019
Dopant Segregation Boosting High‐Voltage Cyclability of Layered Cathode for Sodium Ion Batteries journal September 2019
A Stable Layered Oxide Cathode Material for High‐Performance Sodium‐Ion Battery journal March 2019
Layered P2‐Type K 0.44 Ni 0.22 Mn 0.78 O 2 as a High‐Performance Cathode for Potassium‐Ion Batteries journal October 2019
Facile self-templated synthesis of P2-type Na 0.7 CoO 2 microsheets as a long-term cathode for high-energy sodium-ion batteries journal January 2019
A novel composite strategy to build a sub-zero temperature stable anode for sodium-ion batteries journal January 2019
Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode journal January 2020

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Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
Na-ion Battery
Mg Substitution
Cathode materials
P2-structure
X-ray absorption spectroscopy