Unlike
the more established lithium-ion based energy storage chemistries,
the complex intercalation chemistry of multivalent cations in a host
lattice is not well understood, especially the relationship between
the intercalating species solution chemistry and the prevalence and
type of side reactions. Among multivalent metals, a promising model
system can be based on nonaqueous Zn2+ ion chemistry. Several
examples of these systems support the use of a Zn metal anode, and
reversible intercalation cathodes have been reported. This study utilizes
a combination of analytical tools to probe the chemistry of a nanostructured
δ-MnO2 cathode in association with a nonaqueous acetonitrile–Zn(TFSI)2 electrolyte and a Zn metal anode. As many of the issues related
to understanding a multivalent battery relate to the electrolyte–electrode
interface, the high surface area of a nanostructured cathode provides
a significant interface between the electrolyte and cathode host that
maximizes the spectroscopic signal of any side reactions or minor
mechanistic pathways. Numerous factors affecting capacity fade and
issues associated with the second phase formation including Mn dissolution
in heavily cycled Zn/δ-MnO2 cells are presented including
dramatic mechanistic differences in the storage mechanism of this
couple when compared to similar aqueous electrolytes are noted.
Sponge-like composites assembled by cobalt sulfides quantum dots (Co 9 S 8 QD), mesoporous hollow carbon polyhedral (HCP) matrix, and a reduced graphene oxide (rGO) wrapping sheets are synthesized by a simultaneous thermal reduction, carbonization, and sulfidation of zeolitic imidazolate frameworks@GO precursors. Specifically, Co 9 S 8 QD with size less than 4 nm are homogenously embedded within HCP matrix, which is encapsulated in macroporous rGO, thereby leading to the double carbon-confined hierarchical composites with strong coupling effect. Experimental data combined with density functional theory calculations reveal that the presence of coupled rGO not only prevents the aggregation and excessive growth of particles, but also expands the lattice parameters of Co 9 S 8 crystals, enhancing the reactivity for sodium storage. Benefiting from the hierarchical porosity, conductive network, structural integrity, and a synergistic effect of the components, the sponge-like composites used as binder-free anodes manifest outstanding sodium-storage performance in terms of excellent stable capacity (628 mAh g −1 after 500 cycles at 300 mA g −1 ) and exceptional rate capability (529, 448, and 330 mAh g −1 at 1600, 3200, and 6400 mA g −1 ). More importantly, the synthetic method is very versatile and can be easily extended to fabricate other transition-metal-sulfides-based sponge-like composites with excellent electrochemical performances.
Fischer–Tropsch
synthesis to lower olefins (FTO) opens up
a compact and economical way to the production of lower olefin directly
from syngas (CO and H2) derived from natural gas, coal,
or renewable biomass. The present work is dedicated to a systematic
study on the effect of K in the reduced graphene oxide (rGO) supported
iron catalysts on the catalytic performance in FTO. It is revealed
that the activity, expressed as moles of CO converted to hydrocarbons
per gram Fe per second (iron time yield to hydrocarbons, termed as
FTY), increased first with the content of K, passed through a maximum
at 646 μmolCO gFe
–1 s–1 over the FeK1/rGO catalyst, and then decreased at
higher K contents. Unlike the evolution of the activity, the selectivity
to lower olefins increased steadily with K, giving the highest selectivity
to lower olefins of 68% and an olefin/paraffin (O/P) ratio of 11 in
the C2–C4 hydrocarbons over the FeK2/rGO
catalyst. The volcanic evolution of the activity is attributed to
the interplay among the positive effect of K on the formation of Hägg
carbide, the active phase for FTO, and the negative roles of K in
increasing the size of Hägg carbide at high content and blocking
the active phase by K-induced carbon deposition. The monotonic increase
in the selectivity to lower olefins is ascribed to the improved chain-growth
ability and surface CO/H2 ratio in the presence of K, which
favorably suppressed the unwanted CH4 production and secondary
hydrogenation of lower olefins.
Lithium-ion batteries (LIBs) have been demonstrated as one of the most promising energy storage devices for applications in electric vehicles, smart grids, large-scale energy storage systems, and portable electronics.
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