RESUMEN
Porous strategies based on nanoengineering successfully mitigate several problems related to volume expansion of alloying anodes. However, practical application of porous alloying anodes is challenging because of limitations such as calendering incompatibility, low mass loading, and excessive usage of nonactive materials, all of which cause a lower volumetric energy density in comparison with conventional graphite anodes. In particular, during calendering, porous structures in alloying-based composites easily collapse under high pressure, attenuating the porous characteristics. Herein, this work proposes a calendering-compatible macroporous architecture for a Si-graphite anode to maximize the volumetric energy density. The anode is composed of an elastic outermost carbon covering, a nonfilling porous structure, and a graphite core. Owing to the lubricative properties of the elastic carbon covering, the macroporous structure coated by the brittle Si nanolayer can withstand high pressure and maintain its porous architecture during electrode calendering. Scalable methods using mechanical agitation and chemical vapor deposition are adopted. The as-prepared composite exhibits excellent electrochemical stability of >3.6 mAh cm-2 , with mitigated electrode expansion. Furthermore, full-cell evaluation shows that the composite achieves higher energy density (932 Wh L-1 ) and higher specific energy (333 Wh kg-1 ) with stable cycling than has been reported in previous studies.
RESUMEN
Aluminum-air batteries are promising candidates for next-generation high-energy-density storage, but the inherent limitations hinder their practical use. Here, we show that silver nanoparticle-mediated silver manganate nanoplates are a highly active and chemically stable catalyst for oxygen reduction in alkaline media. By means of atomic-resolved transmission electron microscopy, we find that the formation of stripe patterns on the surface of a silver manganate nanoplate originates from the zigzag atomic arrangement of silver and manganese, creating a high concentration of dislocations in the crystal lattice. This structure can provide high electrical conductivity with low electrode resistance and abundant active sites for ion adsorption. The catalyst exhibits outstanding performance in a flow-based aluminum-air battery, demonstrating high gravimetric and volumetric energy densities of ~2552 Wh kgAl-1 and ~6890 Wh lAl-1 at 100 mA cm-2, as well as high stability during a mechanical recharging process.
RESUMEN
Replacing noble-metal-based oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts is the key to developing efficient Zn-air batteries (ZABs). Here, a homogeneous ternary Ni46 Co40 Fe14 nanoalloy with a size distribution of 30-60 nm dispersed in a carbon matrix (denoted as C@NCF-900) as a highly efficient bifunctional electrocatalyst produced via supercritical reaction and subsequent heat treatment at 900 °C is reported. Among all the transition-metal-based electrocatalysts, the C@NCF-900 exhibits the highest ORR performance in terms of half-wave potential (0.93 V) in 0.1 m KOH. Moreover, C@NCF-900 exhibits negligible activity decay after 10 000 voltage cycles with minor reduction (0.006 V). In ZABs, C@NCF-900 outperforms the mixture of Pt/C 20 wt% and IrO2 , cycled over 100 h under 58% depth of discharge condition. Furthermore, density functional theory (DFT) calculations and in situ X-ray absorption spectroscopy strongly support the active sites and site-selective reaction as a plausible ORR/OER mechanism of C@NCF-900.
RESUMEN
Lithium-excess 3d-transition-metal layered oxides (Li1+xNiyCozMn1-x-y-zO2, >250 mAh g-1) suffer from severe voltage decay upon cycling, which decreases energy density and hinders further research and development. Nevertheless, the lack of understanding on chemical and structural uniqueness of the material prevents the interpretation of internal degradation chemistry. Here, we discover a fundamental reason of the voltage decay phenomenon by comparing ordered and cation-disordered materials with a combination of X-ray absorption spectroscopy and transmission electron microscopy studies. The cation arrangement determines the transition metal-oxygen covalency and structural reversibility related to voltage decay. The identification of structural arrangement with de-lithiated oxygen-centred octahedron and interactions between octahedrons affecting the oxygen stability and transition metal mobility of layered oxide provides the insight into the degradation chemistry of cathode materials and a way to develop high-energy density electrodes.
RESUMEN
The layered nickel-rich materials have attracted extensive attention as a promising cathode candidate for high-energy density lithium-ion batteries (LIBs). However, they have been suffering from inherent structural and electrochemical degradation including severe capacity loss at high electrode loading density (>3.0 g cm-3 ) and high temperature cycling (>60 °C). In this study, an effective and viable way of creating an artificial solid-electrolyte interphase (SEI) layer on the cathode surface by a simple, one-step approach is reported. It is found that the initial artificial SEI compounds on the cathode surface can electrochemically grow along grain boundaries by reacting with the by-products during battery cycling. The developed nickel-rich cathode demonstrates exceptional capacity retention and structural integrity under industrial electrode fabricating conditions with the electrode loading level of ≈12 mg cm-2 and density of ≈3.3 g cm-3 . This finding could be a breakthrough for the LIB technology, providing a rational approach for the development of advanced cathode materials.
