Hexagonal and cubic phases of manganese oxide mesoporous structures (MOMS) have been prepared by means of the oxidation of Mn(OH) 2 . The hexagonal MOMS materials form a hexagonal array of pores with an open porous structure, thick walls (1.7 nanometers), and exceptional thermal stability (1000°C). The walls of the mesopores are composed of microcrystallites of dense phases of Mn 2 O 3 and Mn 3 O 4 , with MnO 6 octahedra as the primary building blocks. The calcined hexagonal MOMS have an electrical conductivity of 8.13 × 10 −6 per ohm·centimeter, an average manganese oxidation state of 3.55, and a band gap of 2.46 electron volts. Catalytic oxidations of cyclohexane and n -hexane in aqueous solutions in a batch reactor show conversions of ∼10 and ∼8 percent, respectively. Characterization and catalytic data suggest that MOMS systems show significant enhancement in thermal stability with respect to octahedral molecular sieve materials.

Large-scale electric energy storage is fundamental to the use of renewable energy. Recently, research and development efforts on room-temperature sodium-ion batteries (NIBs) have been revitalized, as NIBs are considered promising, low-cost alternatives to the current Li-ion battery technology for large-scale applications. Herein, we introduce a novel layered oxide cathode material, NaNiMnO. This new compound provides a high reversible capacity of 138 mAh g and an average potential of 3.25 V vs Na/Na with a single smooth voltage profile. Its remarkable rate and cycling performances are attributed to the elimination of the P2-O2 phase transition upon cycling to 4.5 V. The first charge process yields an abnormally excess capacity, which has yet to be observed in other P2 layered oxides. Metal K-edge XANES results show that the major charge compensation at the metal site during Na-ion deintercalation is achieved via the oxidation of nickel (Ni) ions, whereas, to a large extent, manganese (Mn) ions remain in their Mn state. Interestingly, electron energy loss spectroscopy (EELS) and soft X-ray absorption spectroscopy (sXAS) results reveal differences in electronic structures in the bulk and at the surface of electrochemically cycled particles. At the surface, transition metal ions (TM ions) are in a lower valence state than in the bulk, and the O K-edge prepeak disappears. On the basis of previous reports on related Li-excess LIB cathodes, it is proposed that part of the charge compensation mechanism during the first cycle takes place at the lattice oxygen site, resulting in a surface to bulk transition metal gradient. We believe that by optimizing and controlling oxygen activity, Na layered oxide materials with higher capacities can be designed.

This article reviews Ni-based layered oxide cathodes for Li-ion batteries, primarily from a materials design perspective.

Recent research has explored combining conventional transition-metal redox with anionic lattice oxygen redox as a new and exciting direction to search for high-capacity lithium-ion cathodes. Here, we probe the poorly understood electrochemical activity of anionic oxygen from a material perspective by elucidating the effect of the transition metal on oxygen redox activity. We study two lithium-rich layered oxides, specifically lithium nickel metal oxides where metal is either manganese or ruthenium, which possess a similar structure and discharge characteristics, but exhibit distinctly different charge profiles. By combining X-ray spectroscopy with operando differential electrochemical mass spectrometry, we reveal completely different oxygen redox activity in each material, likely resulting from the different interaction between the lattice oxygen and transition metals. This work provides additional insights into the complex mechanism of oxygen redox and development of advanced high-capacity lithium-ion cathodes.

The increasing interest in high energy and high capacity batteries triggers the demand of clarifying the reaction mechanism in battery cathodes during high potential operations. This is critical for further improving the performance of commercially viable Ni rich compounds, however, the mechanism often involves both transition metal and oxygen activities that remain elusive. Here we report a comprehensive study of the both the

The phase transition, charge compensation, and local chemical environment of Ni in LiNiO were investigated to understand the degradation mechanism. The electrode was subjected to a variety of bulk and surface-sensitive characterization techniques under different charge-discharge cycling conditions. We observed the phase transition from the original hexagonal H1 phase to another two hexagonal phases (H2 and H3) upon Li deintercalation. Moreover, the gradual loss of H3-phase features was revealed during the repeated charges. The reduction in Ni redox activity occurred at both the charge and the discharge states, and it appeared both in the bulk and at the surface over the extended cycles. The degradation of crystal structure significantly contributes to the reduction of Ni redox activity, which in turn causes the cycling performance decay of LiNiO.

A comprehensive study of different local bonding environments in boron nitride-bulk and thin filmshas been performed by core level photoabsorption. Several new features not present in crystalline reference samples are found in the absorption spectra of the thin films. These are identified as nitrogen vacancies in the hexagonal bonding of BN, nitrogen interstitials, boron clustering, sp 3-like metastable phases and sp 3 phases. Quantitative information on the concentration and distribution of point defects is easily extracted from the photoabsorption data and is discussed with regard to formation of riew phases, the B :N ratio in the films, and compared with a random model of defect formation. Information on the stability of the new bonding environments is gained by annealing the thin films. Modification of the orientation of the sp 2 hexagonal planes is attained by ion bombardment and annealing, and is monitored by angle resolved photoabsorption.

By scrutinizing the energy storage process in Li-ion batteries, tuning Li-ion migration behavior by atomic level tailoring will unlock great potential for pursuing higher electrochemical performance. Vacancy, which can effectively modulate the electrical ordering on the nanoscale, even in tiny concentrations, will provide tempting opportunities for manipulating Li-ion migratory behavior. Herein, taking CuGeO as a model, oxygen vacancies obtained by reducing the thickness dimension down to the atomic scale are introduced in this work. As the Li-ion storage progresses, the imbalanced charge distribution emerging around the oxygen vacancies could induce a local built-in electric field, which will accelerate the ions' migration rate by Coulomb forces and thus have benefits for high-rate performance. Furthermore, the thus-obtained CuGeO ultrathin nanosheets (CGOUNs)/graphene van der Waals heterojunctions are used as anodes in Li-ion batteries, which deliver a reversible specific capacity of 1295 mAh g at 100 mA g, with improved rate capability and cycling performance compared to their bulk counterpart. Our findings build a clear connection between the atomic/defect/electronic structure and intrinsic properties for designing high-efficiency electrode materials.