Both cationic and anionic redox chemistry in a P2-type sodium layered oxide

被引:137
作者
Wang, Peng-Fei [1 ]
Xiao, Yao [2 ]
Piao, Nan [1 ]
Wang, Qin-Chao [3 ]
Ji, Xiao [1 ]
Jin, Ting [1 ]
Guo, Yu-Jie [2 ]
Liu, Sufu [1 ]
Deng, Tao [1 ]
Cui, Chunyu [1 ]
Chen, Long [1 ]
Guo, Yu-Guo [2 ]
Yang, Xiao-Qing [3 ]
Wang, Chunsheng [1 ]
机构
[1] Univ Maryland, Dept Chem & Biomol Engn, College Pk, MD 20742 USA
[2] Chinese Acad Sci, CAS Res Educ Ctr Excellence Mol Sci, CAS Key Lab Mol Nanostruct & Nanotechnol, BNLMS,Inst Chem, Beijing 100190, Peoples R China
[3] Brookhaven Natl Lab, Upton, NY 11973 USA
关键词
Sodium-ion batteries; Cathode; Anionic redox; P2-type; Electrochemistry; HIGH-CAPACITY; CATHODE; PHASE; COMPOSITE;
D O I
10.1016/j.nanoen.2020.104474
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The demand for high energy Na-ion batteries has promoted intensive research on high energy oxygen redox chemistry in layered transition metal oxide cathodes. However, most layered cathodes with oxygen redox might suffer from irreversible electrochemical reaction, fast capacity decay and underlying O-2 release. Herein, we report that copper element with a strong electronegativaty can stablize Na-deficient P-2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase to achieve both cationic and anionic redox chemistry. Hard and soft X-ray absorption spectra demonstrate that all Mn3+/Mn4+, Cu2+/Cu3+ and O2-/(O-2)(n-) participate in the redox reaction upon Na+ ions extraction and insertion. Density functional theory (DFT) calculations confirm that the strong covalency between copper and oxygen ensures the cationic and anionic redox activity in P-2-Na2/3Mn0.72Cu0.22Mg0.06O2 phase. The P-2-Na2/3Mn0.72Cu0.22Mg0.06O2 cathode could deliver stable cycling life with 87.9% capacity retention at 1C during 100 cycles, as well as high rate performance (70.3 mA h g(-1) cycled at 10C). Our findings not only provide a promising guidelines to enhance the electrochemical performance of layered oxides based on anionic redox activity, but also explore the potential science behind oxygen redox process.
引用
收藏
页数:8
相关论文
共 45 条
[11]   What Triggers Oxygen Loss in Oxygen Redox Cathode Materials? [J].
House, Robert A. ;
Maitra, Urmimala ;
Jin, Liyu ;
Lozano, Juan G. ;
Somerville, James W. ;
Rees, Nicholas H. ;
Naylor, Andrew J. ;
Duda, Laurent C. ;
Massel, Felix ;
Chadwick, Alan V. ;
Ramos, Silvia ;
Pickup, David M. ;
McNally, Daniel E. ;
Lu, Xingye ;
Schmitt, Thorsten ;
Roberts, Matthew R. ;
Bruce, Peter G. .
CHEMISTRY OF MATERIALS, 2019, 31 (09) :3293-3300
[12]   Sodium-ion batteries: present and future [J].
Hwang, Jang-Yeon ;
Myung, Seung-Taek ;
Sun, Yang-Kook .
CHEMICAL SOCIETY REVIEWS, 2017, 46 (12) :3529-3614
[13]   A phase-transition-free cathode for sodium-ion batteries with ultralong cycle life [J].
Jiang, Kezhu ;
Xu, Sheng ;
Guo, Shaohua ;
Zhang, Xiaoyu ;
Zhang, Xueping ;
Qiao, Yu ;
Fang, Tiancheng ;
Wang, Peng ;
He, Ping ;
Zhou, Haoshen .
NANO ENERGY, 2018, 52 :88-94
[14]   Copper substituted P2-type Na0.67CuxMn1-xO2: a stable high-power sodium-ion battery cathode [J].
Kang, Wenpei ;
Zhang, Zhenyu ;
Lee, Pui-Kit ;
Ng, Tsz-Wai ;
Li, Wenyue ;
Tang, Yongbing ;
Zhang, Wenjun ;
Lee, Chun-Sing ;
Yu, Denis Yau Wai .
JOURNAL OF MATERIALS CHEMISTRY A, 2015, 3 (45) :22846-22852
[15]   Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J].
Kresse, G ;
Furthmuller, J .
PHYSICAL REVIEW B, 1996, 54 (16) :11169-11186
[16]   Electrochemistry and Solid-State Chemistry of NaMeO2 (Me=3d Transition Metals) [J].
Kubota, Kei ;
Kumakura, Shinichi ;
Yoda, Yusuke ;
Kuroki, Kazutoshi ;
Komaba, Shinichi .
ADVANCED ENERGY MATERIALS, 2018, 8 (17)
[17]   P′2-Na2/3Mn0.9Me0.1O2 (Me = Mg, Ti, Co, Ni, Cu, and Zn): Correlation between Orthorhombic Distortion and Electrochemical Property [J].
Kumakura, Shinichi ;
Tahara, Yoshiyuki ;
Sato, Syuhei ;
Kubota, Kei ;
Komaba, Shinichi .
CHEMISTRY OF MATERIALS, 2017, 29 (21) :8958-8962
[18]   Sodium and Manganese Stoichiometry of P2-Type Na2/3MnO2 [J].
Kumakura, Shinichi ;
Tahara, Yoshiyuki ;
Kubota, Kei ;
Chihara, Kuniko ;
Komaba, Shinichi .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (41) :12760-12763
[19]   A New Type of Li-Rich Rock-Salt Oxide Li2Ni1/3Ru2/3O3 with Reversible Anionic Redox Chemistry [J].
Li, Xiang ;
Qiao, Yu ;
Guo, Shaohua ;
Jiang, Kezhu ;
Ishida, Masayoshi ;
Zhou, Haoshen .
ADVANCED MATERIALS, 2019, 31 (11)
[20]   Insights into the Na+ Storage Mechanism of Phosphorus-Functionalized Hard Carbon as Ultrahigh Capacity Anodes [J].
Li, Yu ;
Yuan, Yifei ;
Bai, Ying ;
Liu, Yuanchang ;
Wang, Zhaohua ;
Li, Limin ;
Wu, Feng ;
Amine, Khalil ;
Wu, Chuan ;
Lu, Jun .
ADVANCED ENERGY MATERIALS, 2018, 8 (18)