Flat–Zigzag Interface Design of Chalcogenide Heterostructure toward Ultralow Volume Expansion for High‐Performance Potassium Storage

Abstract

Heterostructure construction of layered metal chalcogenides can boost their alkali‐metal storage performance, where the charge transfer kinetics can be promoted by the built‐in electric fields. However, these heterostructures usually undergo interface separation due to severe layer expansion, especially for large‐size potassium accommodation, resulting in the deconstruction of heterostructures and battery performance fading. Herein, first a stable interface design strategy where two metal chalcogenides with totally different layer‐morphologies are stacked to form large K+ transport channels, rendering ultralow interlayer expansion, is presented. As a proof of concept, the flat–zigzag MoS2/Bi2S3 heterostructures stacked with zigzag‐morphology Bi2S3 and flat‐morphology MoS2 present an ultralow expansion ratio (1.98%) versus MoS2 (9.66%) and Bi2S3 (9.61%), which deliver an ultrahigh potassium storage capacity of above 600 mAh g−1 and capacity retention of 76% after 500 cycles, together with the built‐in electric field of heterostructures. Once the heterostructures are used as an anode for potassium‐based dual‐ion batteries (K‐DIBs), it achieves a superior full‐cell capacity of ≈166 mAh g−1 with a capacity retention of 71% after 400 cycles, which is an outstanding performance among the reported K‐DIBs. This proposed interface stacking strategy may offer a new way toward stable heterostructure design for metal ions storage and transport applications.

High-Performance Alkali Metal Ion Storage in Bi2Se3 Enabled by Suppression of Polyselenide Shuttling Through Intrinsic Sb-Substitution Engineering

“…In addition, serious electrode pulverization related to the large volume change during the repeated sodiation/desodiation process gives rise to inferior rate capability and poor long-term cycling stability . Moreover, the notorious shuttling effect of the soluble polyselenides formed during a charge/discharge process could induce gradual loss of electroactive materials, consequently leading to the irreversible fast capacity deterioration and short lifespan. , To mitigate the above challenges, some effective approaches have been employed to enhance the alkali metal ion storage performances of Bi 2 Se 3 , including elemental doping, spatial confinement engineering, construction of heterostructures, regulation of morphology, nano engineering, and the integration of conductive substrate material . Element doping could effectively tune the electronic structure, accelerate the transfer of electrons, and enhance the electrochemical activity, consequently accelerating the reaction kinetics .…”

Ultrafine ZnSe/CoSe nanodots encapsulated in core–shell MOF-derived hierarchically porous N-doped carbon nanotubes for superior lithium/sodium storage

“…In addition to the graphitic carbon nanosheets or organic molecules derived carbon [15][16][17], zeolitic imidazolate frameworks (ZIFs), a subclass of MOFs, derived composites have a unique porous structure with high speci c surface area and uniform N doping, hence ZIFs derived metallic compounds/N doped porous carbon composites have been intensively investigated for LIBs and SIBs [18][19][20][21]. In particular, compared to mono metal compounds, the heterostructured electrodes with two metal compounds have a strong synergistic effect between the different components at the interface, achieving higher electrical/ionic conductivities and lower activation energy, accelerating the reaction kinetics, and thus conducting the electrochemical performance [22][23][24][25][26][27]. For example, In 2 Se 3 /CoSe 2 hollow nanorods derived from the in situ gaseous selenization of ZIF-67 that grown on the surface of In-based MOF (MIL-68) [22], and CoSe@N-doped carbon anchored onto graphene with modi ed MoSe 2 nanosheets were prepared by a self-template and subsequent selenization strategy [23].…”

“…18–21 In particular, compared to mono metal compounds, heterostructured electrodes with two metal compounds have a strong synergistic effect between the different components at the interface, achieving higher electrical/ionic conductivities and lower activation energy, accelerating the reaction kinetics, and thus improving the electrochemical performance. 22–28 For example, In 2 Se 3 /CoSe 2 hollow nanorods derived from the in situ gaseous selenization of ZIF-67 that grew on the surface of an In-based MOF (MIL-68) were prepared by a self-template and subsequent selenization strategy. 22 In particular, the core–shell ZIF-8@ZIF-67 particles are effective precursors because their derived hybrids have closely packed double shells, in which the ZIF-8-derived inner shell acts as the nanostructured hollow framework to facilitate the diffusion kinetics while the ZIF-67-derived outer shell has a stable structure and good conductivity, and a phase boundary of heterogeneous ZnSe/CoSe x can be constructed.…”

Carbon layer-confined MoS2/Ni3S2 heterostructure with enhanced sodium and potassium storage performance

“…26–28 For instance, Wu et al 29 synthesized a uniform MnS/MoS 2 with a superior rate capability of 78.3 mA h g −1 at 10 A g −1 when used as an anode for SIBs. Tang et al 30 prepared a flat-zigzag MoS 2 /Bi 2 S 3 heterostructure with an excellent rate performance of 311 mA h g −1 at 1 A g −1 . Although heterostructure construction can bring a lot of advantages to MoS 2 -based heterostructure electrodes, the cycling stability and rate capability at ultrahigh rates are still unsatisfactory due to the large volume expansion of the commonly used sulfides during cycling.…”

“…[26][27][28] For instance, Wu et al 29 synthesized a uniform MnS/MoS 2 with a superior rate capability of 78.3 mA h g −1 at 10 A g −1 when used as an anode for SIBs. Tang et al 30 prepared a at-zigzag MoS 2 /Bi 2 S 3 heterostructure with an excellent rate performance of 311 mA h g −1 at 1 A g −1 .…”