New insights into the electrochemical performance of Li2MnSiO4: effect of cationic substitutions
作者： A. Saracibar , Z. Wang , K. J. Carroll , Y. S. Meng , M. E. Arroyo-de Dompablo
DOI: 10.1039/C4TA03367A
关键词:
摘要: The performance of the Li2MnSiO4 cathode material is hindered by voltage decay and capacity fading caused structural instability. To rationalize origin such instability, we have investigated a total 142 Li2yMnSiO4 configurations at y = 0.125, 0.25, 0.333, 0.375, 0.417, 0.5, 0.625, 0.666, 0.75 0.875 density functional theory methods. It found that most stable with ≤ 0.5 consist Mn4+ Mn3+ in octahedral or five-fold coordination. This induces crystal deformation, loss orthogonal symmetry, notorious volume decrease (7% for LiMnSiO4 14% Li0.5MnSiO4). effect Mn substitution on structure delithiated silicates Li0.5Mn0.75M0.25SiO4 computationally M Mg, Fe, Co Ni. Fe substitutes possess coordination, sharing edges adjacent Si polyhedra. DFT results suggest among studied substituents, only Ni could help to maintain integrity samples. Experimentally, Li2Mn1−xNixSiO4 samples x 0, 0.1 0.2 were synthesized electrochemically tested.
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