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Design of Nickel-Based Cation-Disordered Rock-Salt Oxides: The Effect of Transition Metal (M = V, Ti, Zr) Substitution in LiNi0.5M0.5O2 Binary Systems

Musa Ali Cambaz , Bhaghavathi P. Vinayan , Holger Euchner, Rune E. Johnsen, Alexander A. Guda∥, Andrey Mazilkin, Yury V. Rusalev∥, Alexander L. Trigub, Axel Gross , and Maximilian Fichtner

Abstract: Cation-disordered oxides have been ignored as positive electrode material for a long time due to structurally limited lithium insertion/extraction capabilities. In this work, a case study is carried out on nickel-based cation-disordered Fm3̅m LiNi0.5M0.5O2 positive electrode materials. The present investigation targets tailoring the electrochemical properties for nickel-based cation-disordered rock-salt by electronic considerations. The compositional space for binary LiM+3O2 with metals active for +3/+4 redox couples is extended to ternary oxides with LiA0.5B0.5O2 with A = Ni2+ and B = Ti4+, Zr4+, and V+4 to assess the impact of the different transition metals in the isostructural oxides. The direct synthesis of various new unknown ternary nickel-based Fm3m̅ cation- disordered rock-salt positive electrode materials is presented with a particular focus on the LiNi0.5V0.5O2 system. This positive electrode material for Li-ion batteries displays an average voltage of ∼2.55 V and a high discharge capacity of 264 mAhg−1 corresponding to 0.94 Li. For appropriate cutoff voltages, a long cycle life is achieved. The charge compensation mechanism is probed by XANES, confirming the reversible oxidation and reduction of V4+/V5+. The enhancement in the electrochemical performances within the presented compounds stresses the importance of mixed cation-disordered transition metal oxides with different electronic configuration. 

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Reversible Delithiation of Disordered Rock Salt LiVO2

Christian Baur, Dr. Johann Chable, Dr. Franziska Kleinm, Dr. Venkata Sai Kiran Chakravadhanula, Prof. Maximilian Fichtner

Abstract: A rigid crystal lattice, in which cations occupy specific positions, is generally regarded as a critical requirement to enable Li+ diffusion in the bulk of conventional cathode materials, whereas disorder is generally considered as detrimental. Herein, we demonstrate that facile and reversible insertion and extraction of Li+ is possible with LiVO2, a new cation‐disordered rock salt compound (space group: Fm3 m), which is, to the best of our knowledge, described for the first time. This new polymorph of LiVO2 is synthesized by mechanical alloying. Rietveld refinements of the X‐ray diffractions patterns and SAED (selected‐area electron diffraction) patterns attested the formation of the disordered LiVO2 rock salt phase. Galvanostatic cycling experiments were employed to characterize the electrochemical performance of the material, demonstrating that reversible cycling over 100 cycles with a discharge capacity around 100 mAh g−1 is possible.

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