RESUMEN
Li-rich Mn-based layered oxides (LLO) hold great promise as cathode materials for lithium-ion batteries (LIBs) due to their unique oxygen redox (OR) chemistry, which enables additional capacity. However, the LLOs face challenges related to the instability of their OR process due to the weak transition metal (TM)-oxygen bond, leading to oxygen loss and irreversible phase transition that results in severe capacity and voltage decay. Herein, a synergistic electronic regulation strategy of surface and interior structures to enhance oxygen stability is proposed. In the interior of the materials, the local electrons around TM and O atoms may be delocalized by surrounding Mo atoms, facilitating the formation of stronger TMâO bonds at high voltages. Besides, on the surface, the highly reactive O atoms with lone pairs of electrons are passivated by additional TM atoms, which provides a more stable TMâO framework. Hence, this strategy stabilizes the oxygen and hinders TM migration, which enhances the reversibility in structural evolution, leading to increased capacity and voltage retention. This work presents an efficient approach to enhance the performance of LLOs through surface-to-interior electronic structure modulation, while also contributing to a deeper understanding of their redox reaction.
RESUMEN
The lifespan of lithium-ion batteries varies enormously from fundamental study to practical applications. This big difference has been typically ascribed to the high degree of uncertainty in unpredictable and complicated operation conditions in real-life applications. Here, we report that the pause of the charging-discharging process, which is frequently operated in practice but rarely studied in academics, is an important reason for the performance degradation of the NCM111 cathode. It is found that the pause during cycling could trigger a remarkable drop in capacity, giving rise to â¼30% more capacity decay compared with the continuously cycled sample. In situ synchrotron X-ray diffraction analysis reveals that the harmful H1-H2 phase transition, which typically appears in the initial cycle but disappears in subsequent cycles, is reactivated by the pausing process. The anisotropic lattice strains that occur during the H1-H2 transition result in mechanical fractures that terminate with an inert NiO-type rock-salt phase on the surface of particles. The present study indicates that the discontinuous usage of rechargeable batteries is also a key factor for cycle life, which might provide a distinct perspective on the performance decay in practical applications.
RESUMEN
The capacity degredation in layered Ni-rich LiNixCoyMnzO2 (x ≥ 0.8) cathode largely originated from drastic surface reactions and intergranular cracks in polycrystalline particles. Herein, we report a highly stable single-crystal LiNi0.83Co0.12Mn0.05O2 cathode material, which can deliver a high specific capacity (â¼209 mAh g-1 at 0.1 C, 2.8-4.3 V) and meanwhile display excellent cycling stability (>96% retention for 100 cycles and >93% for 200 cycles). By a combination of in situ X-ray diffraction and in situ pair distribution function analysis, an intermediate monoclinic distortion and irregular H3 stack are revealed in the single crystals upon charging-discharging processes. These structural changes might be driven by unique Li-intercalation kinetics in single crystals, which enables an additional strain buffer to reduce the cracks and thereby ensure the high cycling stability.
RESUMEN
The correlation between structure and function lies at the heart of materials science and engineering. Especially, modern functional materials usually contain inhomogeneities at an atomic level, endowing them with interesting properties regarding electrons, phonons, and magnetic moments. Over the past few decades, many of the key developments in functional materials have been driven by the rapid advances in short-range crystallographic techniques. Among them, pair distribution function (PDF) technique, capable of utilizing the entire Bragg and diffuse scattering signals, stands out as a powerful tool for detecting local structure away from average. With the advent of synchrotron X-rays, spallation neutrons, and advanced computing power, the PDF can quantitatively encode a local structure and in turn guide atomic-scale engineering in the functional materials. Here, the PDF investigations in a range of functional materials are reviewed, including ferroelectrics/thermoelectrics, colossal magnetoresistance (CMR) magnets, high-temperature superconductors (HTSC), quantum dots (QDs), nano-catalysts, and energy storage materials, where the links between functions and structural inhomogeneities are prominent. For each application, a brief description of the structure-function coupling will be given, followed by selected cases of PDF investigations. Before that, an overview of the theory, methodology, and unique power of the PDF method will be also presented.
RESUMEN
Platinum is the most active and commonly used electrocatalyst for hydrogen evolution reaction (HER). However, its expensive price and scarce supply limit its world-wide use for mass production of H2 by water electrolysis. Promising candidates for high-performance hydrogen evolution reaction with exceptionally low Pt loading are urgently required to obtain clean and sustainable chemical fuels. Herein, yolk-shell Pt-CoP polyhedra were prepared to realize low Pt loading on low-cost CoP polyhedral substrates via low-temperature calcination and phosphorization of ZIF-67 combined with a subsequent microwave-assisted platinum reduction process. Owing to the unique yolk-shell structure, large surface area, numerous active sites, trace Pt modification and improved conductivity, the resultant catalyst exhibits highly efficient electrocatalytic activities for the HER with the low overpotentials of only 48 mV and 88 mV at 10 mA cm-2 and excellent stability in the 1 M KOH and 1 M PBS solution, superior to most of the newly reported noble metal-based or transition metal-based catalysts, even the state-of-art Pt/C catalysts.
