Guaiacol as an Organic Superoxide Dismutase Mimics for Anti-ageing a Ru-based Li-rich Layered Oxide Cathode.

High-capacity Li-rich layered oxides using oxygen redox as well as transition metal redox suffer from its structural instability due to lattice oxygen escaped from its structure during oxygen redox and the following electrolyte decomposition by the reactive oxygen species. Herein, we rescued a Li-rich layered oxide based on 4d transition metal by employing an organic superoxide dismutase mimics as a homogeneous electrolyte additive. Guaiacol scavenged superoxide radicals via dismutation or disproportionation to convert two superoxide molecules to peroxide and dioxygen after absorbing lithium superoxide on its partially negative oxygen of methoxy and hydroxyl groups. Additionally, guaiacol was decomposed to form a thin and stable cathode-electrolyte interphase (CEI) layer, endowing the cathode with the interfacial stability.

Reversible Deposition and Stripping of the Cathode Electrolyte Interphase on Li2RuO3.

Performance decline in Li-excess cathodes is generally attributed to structural degradation at the electrode-electrolyte interphase, including transition metal migration into the lithium layer and oxygen evolution into the electrolyte. Reactions between these new surface structures and/or reactive oxygen species in the electrolyte can lead to the formation of a cathode electrolyte interphase (CEI) on the surface of the electrode, though the link between CEI composition and the performance of Li-excess materials is not well understood. To bridge this gap in understanding, we use solid-state nuclear magnetic resonance (SSNMR) spectroscopy, dynamic nuclear polarization (DNP) NMR, and electrochemical impedance spectroscopy (EIS) to assess the chemical composition and impedance of the CEI on Li2RuO3 as a function of state of charge and cycle number. We show that the CEI that forms on Li2RuO3 when cycled in carbonate-containing electrolytes is similar to the solid electrolyte interphase (SEI) that has been observed on anode materials, containing components such as PEO, Li acetate, carbonates, and LiF. The CEI composition deposited on the cathode surface on charge is chemically distinct from that observed upon discharge, supporting the notion of crosstalk between the SEI and the CEI, with Li+-coordinating species leaving the CEI during delithiation. Migration of the outer CEI combined with the accumulation of poor ionic conducting components on the static inner CEI may contribute to the loss of performance over time in Li-excess cathode materials.

A New Class of Ternary Compound for Lithium-Ion Battery: from Composite to Solid Solution.

Searching for high-performance cathode materials is a crucial task to develop advanced lithium-ion batteries (LIBs) with high-energy densities for electrical vehicles (EVs). As a promising lithium-rich material, Li2MnO3 delivers high capacity over 200 mAh g-1 but suffers from poor structural stability and electronic conductivity. Replacing Mn4+ ions by relatively larger Sn4+ ions is regarded as a possible strategy to improve structural stability and thus cycling performance of Li2MnO3 material. However, large difference in ionic radii of Mn4+ and Sn4+ ions leads to phase separation of Li2MnO3 and Li2SnO3 during high-temperature synthesis. To prepare solid-solution phase of Li2MnO3-Li2SnO3, a buffer agent of Ru4+, whose ionic radius is in between that of Mn4+ and Sn4+ ions, is introduced to assist the formation of a single solid-solution phase. The results show that the Li2RuO3-Li2MnO3-Li2SnO3 ternary system evolves from mixed composite phases into a single solid-solution phase with increasing Ru content. Meanwhile, discharge capacity of this ternary system shows significantly increase at the transformation point which is ascribed to the improvement of Li+/e- transportation kinetics and anionic redox chemistry for solid-solution phase. The role of Mn/Sn molar ratio of Li2RuO3-Li2MnO3-Li2SnO3 ternary system has also been studied. It is revealed that higher Sn content benefits cycling stability of the system because Sn4+ ions with larger sizes could partially block the migration of Mn4+ and Ru4+ from transition metal layer to Li layer, thus suppressing structural transformation of the system from layered-to-spinel phase. These findings may enable a new route for exploring ternary or even quaternary lithium-rich cathode materials for LIBs.

Influence of Ti(4+) on the electrochemical performance of Li-rich layered oxides - high power and long cycle life of Li2Ru1-xTixO3 cathodes.

Li-rich layered oxides are the most attractive cathodes for lithium-ion batteries due to their high capacity (>250 mAh g(-1)). However, their application in electric vehicles is hampered by low power density and poor cycle life. To address these, layered Li2Ru0.75Ti0.25O3 (LRTO) was synthesized and the influence of electroinactive Ti(4+) on the electrochemical performance of Li2RuO3 was investigated. LRTO exhibited a reversible capacity of 240 mAh g(-1) under 14.3 mA g(-1) with 0.11 mol of Li loss after 100 cycles compared to 0.22 mol of Li for Li2Ru0.75Sn0.25O3. More Li(+) can be extracted from LRTO (0.96 mol of Li) even after 250 cycles at 143 mA g(-1) than Li2RuO3 (0.79 mol of Li). High reversible Li extraction and long cycle life were attributed to structural stability of the LiM2 layer in the presence of Ti(4+), facilitating the lithium diffusion kinetics. The versatility of the Li2MO3 structure may initiate exploration of Ti-based Li-rich layered oxides for vehicular applications.