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Published on: November 11, 2013
Composition-structure relationships in the Li-ion battery electrode material LiNi(0.5)Mn(1.5)O(4)
Jordi Cabana1, Montserrat Casas-Cabanas, Fredrick O Omenya
1Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720.
Chemistry of Materials : a Publication of the American Chemical Society
|September 25, 2012
Summary
This study reveals that manganese excess in LiNi(0.5)Mn(1.5)O(4) forms secondary phases, not oxygen vacancies. Deviations in transition metal ordering impact magnetic and electrochemical properties.
Area of Science:
- Materials Science
- Solid-State Chemistry
- Electrochemistry
Background:
- Lithium transition metal oxides are crucial for energy storage applications.
- Controlling stoichiometry and cation ordering in LiNi(0.5)Mn(1.5)O(4) is key to optimizing performance.
- Understanding secondary phase formation and its impact is essential.
Purpose of the Study:
- To investigate the relationship between stoichiometry, secondary phases, and transition metal ordering in LiNi(0.5)Mn(1.5)O(4).
- To correlate crystal-chemical properties with magnetic and electrochemical behavior.
- To provide in-depth knowledge for material design.
Main Methods:
- Synthesis of LiNi(0.5)Mn(1.5)O(4) at varying temperatures.
- Characterization using electron microscopy, neutron diffraction, and X-ray absorption spectroscopy.
- Cationic ordering analysis via neutron diffraction and Li MAS NMR spectroscopy.
Main Results:
- All synthesized samples exhibited manganese excess, leading to secondary rock salt phase formation instead of oxygen vacancies.
- Local deviations from the ideal 3:1 Mn:Ni ordering were observed, even in samples showing superlattice ordering.
- Different disordered cation arrangements were identified, influencing magnetic behavior.
Conclusions:
- Manganese excess in LiNi(0.5)Mn(1.5)O(4) primarily results in secondary phase formation.
- Transition metal ordering deviations significantly affect the material's properties.
- Crystal-chemical insights are vital for tailoring electrochemical performance.
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