Ultrathin core–shell V3S4@C nanosheets assembled into hierarchical nanotubes (V3S4@C NS‐HNTs) are synthesized by a self‐template strategy and evaluated as general anodes for alkali‐ion batteries. Structural/physicochemical characterizations and DFT calculations bring insights into the intrinsic relationship between crystal structures and electrochemical mechanisms of the V3S4@C NS‐HNTs electrode. The V3S4@C NS‐HNTs are endowed with strong structural rigidness owing to the layered VS2 subunits and interlayer occupied V atoms, and efficient alkali‐ion adsorption/diffusion thanks to the electroactive V3S4‐C interfaces. The resulting V3S4@C NS‐HNTs anode exhibit distinct alkali‐ion‐dependent charge storage mechanisms and exceptional long‐durability cyclic performance in storage of K+, benefiting from synergistic contributions of pseudocapacitive and reversible intercalation/de‐intercalation behaviors superior to those of the conversion‐reaction‐based Li+‐/Na+‐storage counterparts.
Highly conductive metal selenides are gaining prominence as promising electrode materials in electrochemical energy‐storage fields. However, phase‐pure bimetallic selenides are scarcely retrieved, and their underlying charge‐storage mechanisms are still far from clear. Here, first a solvothermal strategy is devised to purposefully fabricate monodisperse hollow NiCoSe2 (H‐NiCoSe2) sub‐microspheres. Inherent formation of metallic H‐NiCoSe2 is tentatively put forward with comparative structure‐evolution investigations. Interestingly, the fresh H‐NiCoSe2 does not demonstrate striking supercapacitive behaviors when evaluated for electrochemical supercapacitors (ESs). But it exhibits competitive pseudocapacitance of ≈750 F g−1 at a rate of 3 A g−1 with a high loading of 7 mg cm−2 after ≈100 cyclic voltammetry (CV) cycles. With systematic physicochemical/electrochemical analyses, intrinsic energy‐storage mechanism of the H‐NiCoSe2 is convincingly revealed that the electrooxidation‐generated biactive CoOOH/NiOOH phases in aqueous KOH over CV scanning, rather than the H‐NiCoSe2 itself, account for the remarkable pesudocapacitance observed after cycling. An assembled H‐NiCoSe2‐based asymmetric device has delivered an energy density of ≈25.5 Wh kg−1 with a power rate of ≈3.75 kW kg−1, and long‐span cycle life. More significantly, the electrode design and new perspectives here hold profound promise in enriching material synthesis methodologies and in‐depth understanding of the complex charge‐storage process of newly emerging pseudocapacitive materials for next‐generation ESs.
A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic [(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV-vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59-3.68) have been quantified according to their L(III)-edge X-ray absorption near-edge structure (XANES) profiles.
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