Modulating Bond Interactions and Interface Microenvironments between Polysulfide and Catalysts toward Advanced Metal–Sulfur Batteries

Abstract

Advanced metal-sulfur batteries (MSBs) are regarded as promising next-generation energy storage devices. Recently, engineering polysulfide redox catalysts (PSRCs) to stabilize and catalytically convert polysulfide intermediates is proposed as an effective strategy to address the grand challenge of "shuttle effects" in the cathode. Therefore, modulating the bond interactions and interface microenvironments and disclosing the structure-performance correlations between polysulfide and catalysts are essential to guide the future cathode design in MSBs. Herein, from a multidisciplinary view, the most recent process in the reaction principles, in situ characterizations, bond interaction modulation, and interface microenvironment optimization of polysulfide redox catalysts, is comprehensively summarized. Especially, unique insights are provided into the strategies for tailoring the bond interactions of PSRCs, such as heteroatom doping, vacancy engineering, heterostructure, coordination structure arrangements, and crystal phase modulation. Furthermore, the importance of interface microenvironments and substrate effects in different PSRCs are exposed, and a detailed comparison is given to unveil the critical parameters for their future developments. Finally, the critical design principles on electrode microenvironments for advanced MSBs are also proposed to stimulate the practically widespread utilization of PSRCs-equipped cathodes in MSBs. Overall, this review provides cutting-edge guidance for future developments in high-energy-density and long-life MSBs.

Reactive oxygen nanobiocatalysts: activity-mechanism disclosures, catalytic center evolutions, and changing states

“…biocatalysis fields. 188 Accompanied by the fast development of biocatalytic processes, more attention is needed to be paid to these advanced methods to clearly detect the complex catalytic conversion chemistry and thus reveal the catalytic mechanisms of RONBCs.…”

“…In addition to these ex situ normal characterisations, novel target-oriented characterisation techniques, especially in situ methods, such as in situ XAS, in situ Raman, and in situ XRD, have emerged as advanced techniques to perform real-time monitoring for better understanding the catalytic mechanisms, facilitating the DFT calculation, and directing the fabrication of catalysts in electrocatalysis, 181–184 photocatalysis, 185–187 and biocatalysis fields. 188 Accompanied by the fast development of biocatalytic processes, more attention is needed to be paid to these advanced methods to clearly detect the complex catalytic conversion chemistry and thus reveal the catalytic mechanisms of RONBCs.…”

Metal Alloys‐Structured Electrocatalysts: Metal–Metal Interactions, Coordination Microenvironments, and Structural Property–Reactivity Relationships

“…Microenvironment tailoring: The metal-support interactions can tailor the microenvironments via the electron transferring and coordination structure design, which may directly enhance the intrinsic catalytic activities of active sites. [52] Besides, the strong metal-support interactions can prevent the metallic alloy from leaching during electrocatalysis, thus effectively promoting catalytic stability. [53,54] Synergizing several promotional effects is highly valid for modulating the metal-metal interactions and coordination microenvironments of MAECs that are efficient for uncovering the structure-activity relationships in various electrocatalytic reac-tions.…”

Electrocatalytic Porphyrin/Phthalocyanine‐Based Organic Frameworks: Building Blocks, Coordination Microenvironments, Structure‐Performance Relationships

“…Table 4 presents a comprehensive summary of the advantages, disadvantages, and key issues of the above standard in situ techniques. [165][166][167][168][169][170] In conclusion, as a novel research direction in electrocatalysis (CO 2 RR, ORR, and water splitting), POFs-based materials have attracted much attention. A series of synthetic methods and modification strategies are used to construct POFs-based materials with high tunability and catalytic activities for electrocatalytic applications.…”