Developing
high-efficiency dual-functional catalysts to promote
oxygen electrode reactions is critical for achieving high-performance
aprotic lithium–oxygen (Li–O2) batteries.
Herein, Sr and Fe cation-codoped LaCoO3 perovskite (La0.8Sr0.2Co0.8Fe0.2O3−σ, LSCFO) porous nanoparticles are fabricated as promising electrocatalysts
for Li–O2 cells. The results demonstrate that the
LSCFO-based Li–O2 batteries exhibit an extremely
low overpotential of 0.32 V, ultrahigh specific capacity of 26 833
mA h g–1, and superior long-term cycling stability
(200 cycles at 300 mA g–1). These prominent performances
can be partially attributed to the existence of abundant coordination
unsaturated sites caused by oxygen vacancies in LSCFO. Most importantly,
density functional theory (DFT) calculations reveal that codoping
of Sr and Fe cations in LaCoO3 results in the increased
covalency of Co 3d–O 2p bonds and the transition of Co3+ from an ordinary low-spin state to an intermediate-spin
state, eventually resulting in the transformation from nonconductor
LCO to metallic LSCFO. In addition, based on the theoretical calculations,
it is found that the inherent adsorption capability of LSCFO toward
the LiO2 intermediate is reduced due to the increased covalency
of Co 3d–O 2p bonds, leading to the formation of large granule-like
Li2O2, which can be effectively decomposed on
the LSCFO surface during the charging process. Notably, this work
demonstrates a unique insight into the design of advanced perovskite
oxide catalysts via adjusting the covalency of transition-metal–oxygen
bonds for high-performance metal–air batteries.
Effect of plant protein mixtures on the microstructure and rheological properties of myofibrillar protein gel derived from red sea bream (Pagrosomus major), Food Hydrocolloids (2019), doi:
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