Tuning the electronic, ion transport, and stability properties of Li-rich Manganese-based oxide materials with oxide perovskite coatings: a first-principles computational study

Lithium-rich manganese-based oxides (LRMO) are regarded as promising cathode materials for powering electric applications due to their high capacity (250 mAh g–1) and energy density (~900 Wh kg–1). However, poor cycle stability and capacity fading have impeded the commercialization of this family of materials as battery components. Surface modification based on coating has proven successful in mitigating some of these problems, but a microscopic understanding of how such improvements are attained is still lacking, thus impeding systematic and rational design of LRMO-based cathodes. In this work, first-principles density functional theory (DFT) calculations are carried out to fill out such a knowledge gap and to propose a promising LRMO-coating material. It is found that SrTiO3 (STO), an archetypal and highly stable oxide perovskite, represents an excellent coating material for Li1.2Ni0.2Mn0.6O2 (LNMO), a prototypical member of the LRMO family. An accomplished atomistic model is constructed to theoretically estimate the structural, electronic, oxygen vacancy formation energy, and lithium-transport properties of the LNMO/STO interface system, thus providing insightful comparisons with the two integrating bulk materials. It is found that (i) electronic transport in the LNMO cathode is enhanced due to partial closure of the LNMO band gap (~0.4 eV) and (ii) the lithium ions can easily diffuse near the LNMO/STO interface and within STO due to the small size of the involved ion-hopping energy barriers. Furthermore, the formation energy of oxygen vacancies notably increases close to the LNMO/STO interface, thus indicating a reduction in oxygen loss at the cathode surface and a potential inhibition of undesirable structural phase transitions. This theoretical work therefore opens up new routes for the practical improvement of cost-affordable lithium-rich cathode materials based on highly stable oxide perovskite coatings.Peer ReviewedPostprint (published version

Enhanced Oxygen Reduction Activities of Pt Supported on Nitrogen-Doped Carbon Nanocapsules

The nitrogen-doped carbon nanocapsules (NCNCs) were explored as catalyst support for oxygen reduction reaction (ORR) in acid electrolyte. The deposition of Pt particles on NCNCs support was characterized using various physico-chemical techniques, such as scanning electron microscope, transmission electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy. The high resolution transmission electron microscopy reveals that Pt particles are uniformly dispersed onto the NCNCs and particles size of about 2.2 nm was observed. The electrochemical ORR activities of the Pt supported on NCNCs catalysts were studied and compared with a commercial catalyst. Pt/NCNC showed enhanced ORR activity and better stability than a commercial Pt/C catalyst. The enhanced performance of Pt supported NCNCs can be attributed to the better dispersion and utilization of Pt nanoparticles. © 2014 Elsevier Ltd.

Prevention of redox shuttle using electropolymerized polypyrrole film in a lithium–oxygen battery

Among the recent advancements in lithium–oxygen (Li–O2) chemistries, redox mediators (RMs) have been revealed to play a significant role in decreasing overpotential on charging and in improving cycling performance. However, an intrinsic problem is redox shuttle of RMs, which leads to degraded RM utilization and induces the accumulation of discharge products on the cathode surface; this remains a significant issue in the current battery cell configuration (Li anode/separator/cathode). To address this detrimental problem, herein we propose a novel Li–O2 cell incorporating a freestanding electropolymerized polypyrrole (PPy) film for the restriction of the redox-shuttle phenomenon of lithium iodide (Li anode/separator/PPy film/cathode). In this study, a PPy film, which is prepared through oxidative electropolymerization using an ionic liquid of 1-methyl-1-butylpyrrolidinium mixed with pyrrole and lithium bis(trifluoromethanesulfonyl)imide, is introduced between the cathode and the separator. From the charge–discharge voltage profile, it is confirmed that the PPy film suppresses the diffusion of the oxidized I3− to the Li anode, while allowing Li ion transport. Secondary scanning electron microscope measurements confirm that the chemical reactions between I3− and Li2O2 are facilitated by the presence of the PPy film because I3− remains near the cathode surface during the charging process. As a result, the cycling performance in the Li–O2 cells with PPy film exhibits a cycling life four times as long as that of the Li–O2 cells without PPy film