Modifying Jahn-Teller distortion by epitaxial stress in LaMnO3 films for tunning electron localization

The effect of epitaxial stress on Jahn-Teller distortion in epitaxial LaMnO3 (LMO) films has been investigated. Both 2θ-ω scans and reciprocal space maps indicate that LMO samples are subjected to compressive stress. Obvious Laue oscillations can be detected in 2θ-ω scans, indicating the high quality of samples. Reciprocal space maps of symmetry peak (001) and asymmetry peak (-103) imply different epitaxial stress for LMO films deposited on different substrates. Raman spectra measurements reveal that the degree of Jahn-Teller distortion can be well tuned via the epitaxial stress which may further influence on the electron localization in the films. This study might benefit to understanding the correlation between crystalline structure and electrical transport properties of LMO films and related LMO-based superlattices.

Synthesis of O3-Na0.8Fe0.6Mn0.3O2 Positive Electrode and Its Application to Sodium Ion Batteries

Herein, we report precise variation of Fe and Mn constituent in the sodium magnate layered cathodes with the compositions of Na0.8Fe0.4Mn0.5O2, Na0.8Fe0.5Mn0.4O2, Na0.8Fe0.6Mn0.3O2, Na0.8Fe0.6Mn0.4O2, Na0.8Fe0.7Mn0.4O2, Na0.9Fe0.6Mn0.3O2 in order to attain a high performing cathode. Based on this transition metal stoichiometry, an interesting sodium magnate combination of Na0.8Fe0.6Mn0.3O2, with O3-type crystal phase, possess R3m space group along with the superior electrochemical behavior is obtained. On charge-discharge capacities in the range of 2.0-3.8 V at 0.1 C, it shows the comparatively higher performance of the first and the second charge capacity of 115 and 180 mAhg-1 and discharge capacity of 184 and 181 mAhg-1, respectively. The best sample was then compared with the closely related Na0.8Fe0.6Mn0.4O2, Na0.9Fe0.6Mn0.3O2 combination in terms of valence ratio and influence of excess sodium for the structure robustness, stability along with purity. The best sample with the composition Na0.8Fe0.6Mn0.3O2 does not show detectable impure phase while Na0.8Fe0.6Mn0.4O2 and Na0.9Fe0.6Mn0.3O2 shows a tendency of P-type (Cmca space group) behavior with 30.8% and 32.8%, respectively. The enhancement of iron constituent increases not only the performances but also the stabilization of sodium vacancy ordering and substitution of Mn with a substantial reduction of Jahn-Teller distortion, mounting biphasic characteristics and high peak intensity of 41.5 °.

The Superexchange mechanism in crystalline compounds. The case of KMF3(M=Mn, Fe, Co, Ni) perovskites.

The ferromagnetic and antiferromagnetic wavefunctions of four KMF3 (M= Mn, Fe, Co and Ni) perovskites have been obtained quantum-mechanically with the CRYSTAL code, by using the Hartree-Fock (HF) Hamiltonian and three flavours of DFT (PBE, B3LYP and PBE0) and an all-electron Gaussian type basis set. In the Fe and Co cases, with d6and d7occupation, the Jahn-Teller distortion of the cubic cell is as large as 0.12 Å. Various features of the superexchange interaction energies (SIE), namely additivity, dependence on the M-M distance, on the MFM̂ angle, and on the adopted functional, are explored. The contribution to SIE by the Coulomb, exchange and kinetic energy terms is analyzed. It is shown that, when using density functionals, SIE clearly correlates with the amount of exact (Hartree-Fock) exchange in the functional. The effect of SIE on the equilibrium geometry and volume of the unit cell is discussed, and it is shown that the key quantity is the spin polarization of the (closed shell) F ions along the M-F-M path. The effect of this magnetic pressure is evaluated quantitatively for the first time.

Chemical Modulation of Local Transition Metal Environment Enables Reversible Oxygen Redox in Mn-Based Layered Cathodes

<p>Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to the complicated concurrent structural and chemical transformations. Herein, we show that local Mn‒O symmetry induced structural and chemical evolutions majorly dictate the reversibility of oxygen redox of Na_xLi_yMn_1-yO₂ in Na cells. We find that Na_xLi­_yMn_1-yO₂ with Jahn-Teller distorted MnO₆ octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn-Teller distortion of MnO₆ octahedra can be suppressed by modulating the local charge of Mn and Mn‒O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution resulting in more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped Na_xLi_yMn_1-yO₂. Through this work, we show that promoting reversible oxygen redox can benefit from structural stabilization at local length scale, and that modifying the chemical environment through doping chemistry is an efficient strategy to promote local structural stability and thus, oxygen redox.</p>