The sluggish redox
kinetics of polysulfides and difficult oxidation
process of Li2S severely hinder practical application of
Li–S batteries under high sulfur loading and a low electrolyte
dosage. To address these issues, we develop a bifunctional catalyst
by manipulation of anion N doping in CoSe2 (N-CoSe2). Theoretical simulation results uncover that an introduced
N element into CoSe2 could form a shorter Co–N bond,
create a higher charge number of the Co central atom, bring new defect
levels, and induce the Co 3d band closer to Fermi level. Further atomic
level analysis revealed that N-CoSe2 could form shorter
Co–S bonds with sulfur species and simultaneously weaken the
S–S bridged bond of Li2S4 and Li–S
bond of Li2S, which eventually facilitate the polysulfide
conversion reaction in the discharge process and the Li2S oxidation in the charge process. With N-CoSe2 as a bifunctional
catalyst, the battery exhibited a high areal capacity of 9.26 mAh
g–1 under the low E/S (electrolyte/sulfur) ratio
of 4.4 μL mg–1. Understanding the design concept
of a bifunctional catalyst with anion doping would provide a new vision
for realizing a high-performance Li–S battery.
Precisely tuning the coordination
environment of the metal center
and further maximizing the activity of transition metal–nitrogen
carbon (M-NC) catalysts for high-performance lithium–sulfur
batteries are greatly desired. Herein, we construct an Fe-NC material
with uniform and stable Fe-N2 coordination structure. The
theoretical and experimental results indicate that the unsaturated
Fe-N2 center can act as a multifunctional site for anchoring
lithium polysulfides (LiPSs), accelerating the redox conversion of
LiPSs and reducing the reaction energy barrier of Li2S
decomposition. Consequently, the batteries based on a porous carbon
nitride supported Fe-N2 site (Fe-N2/CN) host
exhibit excellent cycling performance with a capacity decay of 0.011%
per cycle at 2 C after 2000 cycles. This work deepens the understanding
of the relationship between electronic structure of M-NC sites and
the catalysis effect for the conversion of LiPSs. This strategy also
provides a potent guidance for the further application of M-NC materials
in advanced lithium–sulfur batteries.
Template-directed synthesized Fe0.1-Ni-MOF nanoarray (Fe0.1-Ni-MOF/NF) behaves efficiently as an electrocatalyst for alkaline water oxidation with a strong electrochemical durability.
The slow redox kinetics of polysulfides and the difficulties in decomposition of Li2S during the charge and discharge processes are two serious obstacles to the practical application of lithium-sulfur batteries. Herein, we construct the Fe-Co diatomic catalytic materials supported by hollow carbon spheres to achieve high-efficiency catalysis for the conversion of polysulfides and the decomposition of Li2S simultaneously. The Fe atom center is beneficial to accelerate the discharge reaction process, and the Co atom center is favorable for charging process. Theoretical calculations combined with experiments reveal that this excellent bifunctional catalytic activity originates from the diatomic synergy between Fe and Co atom. As a result, the assembled cells exhibit the high rate performance (the discharge specific capacity achieves 688 mAh g−1 at 5 C) and the excellent cycle stability (the capacity decay rate is 0.018% for 1000 cycles at 1 C).
Controlling exposed crystal facets through crystal facet engineering is an efficient strategy for enhancing the catalytic activity of nanocrystalline catalysts. Herein, the active tin dioxide nano–octahedra enclosed by {332} crystal facets (SnO2 {332}) are synthesized on reduced graphene oxide and demonstrate powerful chemisorption and catalytic ability, accelerating the redox kinetics of sulfur species in lithium–sulfur chemistry. Attributed to abundant unsaturated–coordinated Sn sites on {332} crystal planes, SnO2 {332} has outstanding adsorption and catalytic properties. The material not only adsorbs and converts polysulfides efficiently, but also prominently lowers the decomposition energy barrier of Li2S. The batteries with these high active electrocatalysts exhibit excellent cycling stability with a low capacity attenuation of 0.021% every cycle during 2000 cycles at 2 C. Even with a sulfur loading of 8.12 mg cm−2, the batteries can still cycle stably and maintain a prominent areal capacity of 6.93 mAh cm−2 over 100 cycles. This research confirms that crystal facet engineering is a promising strategy to optimize the performance of catalysts, deepens the understanding of surface structure‐oriented electrocatalysis in Li–S chemistry, while aiding the rational design of advanced sulfur electrodes.
Polyvinyl alcohol (PVA) as a “glue” to cement the metal organic framework (Zn-MOF) sheet as a reasonable artificial SEI film. The artificial SEI film can efficiently adapt to the changes of the volume during the cycle, significantly improve the stability of the Li metal anode.
Lithium−sulfur (Li−S) batteries are one of the most promising candidates for next-generation energy storage systems because of their high theoretical energy density. However, the shuttling behavior and sluggish conversion kinetics of lithium polysulfides (LiPSs) limit their practical application. Herein, Bdoped MoS 2 nanosheets are synthesized on carbon nanotubes (denoted as CNT@MoS 2 -B) to function as catalysts to boost the performance of Li−S batteries. The poor catalytic performance of the pristine MoS 2 is revealed to be the result of unsuitable orbital orientation of the basal plane, which hinders the orbital overlap with sulfur species. B in CNT@MoS 2 -B is sp 3 hybridized, and it has a vacant σ orbital perpendicular to the basal plane, which can maximize the head-on orbital overlap with S. The incorporation of B significantly increases the reactivity of MoS 2 basal plane, which can facilitate the kinetics of Li 2 S formation and dissolution. With these merits, the S/CNT@MoS 2 -B cathodes deliver high rate capability and outstanding cycling stability, holding great promise for both scientific research and practical application. This work affords fresh insights for developing effective catalysts to accelerate LiPS conversion.
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