Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES

被引:75
作者
Doubaji, Siham [2 ]
Philippe, Bertrand [3 ]
Saadoune, Ismael [2 ,4 ]
Gorgoi, Mihaela [5 ]
Gustafsson, Torbjorn [1 ]
Solhy, Abderrahim [4 ]
Valvo, Mario [1 ]
Rensmo, Hakan [3 ]
Edstrom, Kristina [1 ]
机构
[1] Uppsala Univ, Dept Chem, Angstrom Lab, S-72121 Uppsala, Sweden
[2] Univ Cadi Ayyad, FST Marrakesh, LCME, Marrakech 40000, Morocco
[3] Uppsala Univ, Dept Phys & Astron, S-75120 Uppsala, Sweden
[4] Univ Mohammed VI Polytech, Ctr Adv Mat, Ben Guerir, Morocco
[5] Helmholtz Zentrum Berlin Mat & Energie, D-12489 Berlin, Germany
基金
瑞典研究理事会;
关键词
electrochemistry; interfaces; photoelectron spectroscopy; reaction mechanisms; sodium; X-RAY PHOTOELECTRON; SOLID-ELECTROLYTE INTERPHASE; POSITIVE ELECTRODE; ELECTROCHEMICAL PROPERTIES; TRANSITION-METALS; HIGH-VOLTAGE; LIMO2; M; SPECTROSCOPY; LITHIUM; SURFACE;
D O I
10.1002/cssc.201501282
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The cathode material P2-NaxCo2/3Mn2/9Ni1/9O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0V; all are in the 4+ state at the end of charging. Reduction to Co3+, Ni3+, and Mn3+ occurs upon discharging and, at low potential, there is partial reversible reduction to Co2+ and Ni2+. A thin layer of Na2CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5V), whereas fluorophosphates are produced at the end of discharging (2.0V).
引用
收藏
页码:97 / 108
页数:12
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