Na 2 S was prepared from stoichiometric Na (Acros Organics, rod, 99.8%, mechanically cleaned prior to use) and S (see main text) in separate alumina crucibles (Almath) in an evacuated silica ampoule. The reactants were heated at 1°C min −1 to 300°C for 48 h and cooled ambiently to room temperature. The ground product was a fine powder of a slightly tan-color. The product was determined to be phase pure by XRD.
PNb 9 O 25 , a Wadsley-Roth compound whose structure is obtained by appropriate crystallographic shear of the ReO 3 structure, is a high-power electrode material that can reach 85 % of the equilibrium capacity in 30 minutes and 67% in 6 minutes. Here we show that multielectron redox, as observed through X-ray absorption spectroscopy and X-ray photoelectron spectroscopy, and an insulator-to-metal transition upon lithium insertion, as suggested by a number of complementary techniques, contribute to the impressive performance. Chemically tuning the tetrahedral site between phosphorus and vanadium leads to significant changes in the electrochemistry and kinetics of lithium insertion in the structure, pointing to larger implications for the use of crystallographic shear phases as fast-charging electrode materials.
Understanding the structural transformations that materials undergo during (de)insertion of Li ions is crucial for designing high-performance intercalation hosts as these deformations can lead to significant capacity fade. Herein, we present a study of the metallic defect perovskite ReO3 to determine whether these distortions are driven by polaronic charge transport (i.e., the electrons and ions moving through the lattice in a coupled way) due to the semiconducting nature of most oxide hosts. Employing numerous techniques, including electrochemical probes, operando X-ray diffraction, X-ray photoelectron spectroscopy, and density functional theory calculations, we find that the cubic structure of ReO3 experiences multiple phase changes involving the correlated twisting of rigid octahedral subunits upon lithiation. This results in exceptionally poor long-term cyclability due to large strains upon lithiation, even though metallic character is maintained throughout. This suggests that phase transformations during alkali ion intercalation are the result of local strains in the lattice and not exclusively due to polaron migration.
The effects of shear planes in perovskitic materials have been studied in order to identify their role in the electrochemical behavior and structural evolution of Li+ intercalation hosts.
Development of next-generation battery technologies is imperative in the pursuit of a clean energy future. Toward that end, battery chemistries capable of multielectron redox processes are at the forefront of studies on Li-based systems to increase the gravimetric capacity of the cathode. Multielectron processes rely either on the iterative redox of transition metal cations or redox involving both the transition metal cations and the anionic framework. Targeting coupled cation and anion redox to achieve multielectron charge storage is difficult, however, because the structure−property relationships that govern reversibility are poorly understood. In an effort to develop fundamental understanding of anion redox, we have developed a materials family that displays tunable anion redox over a range of potentials that are dependent on a systematic modification of the stoichiometry. We report anion redox in the chalcogenide solid solution Li 2 FeS 2−y Se y , wherein the mixing of the sulfide and selenide anions yields a controllable shift in the high voltage oxidation plateau. Electrochemical measurements indicate that reversible multielectron redox occurs across the solid solution. X-ray absorption spectroscopy supports the oxidation of both iron and selenium at high states of charge, while Raman spectroscopy indicates the formation of Se−Se dimers in Li 2 FeSe 2 upon Li deintercalation, providing insight into the charge mechanism of the Li-rich iron chalcogenides. Anion substitution presents direct control over the functional properties of multielectron redox materials for next generation battery technologies.
We report the successful electrochemical intercalation of F-ions into a densely packed perovskite oxide from a liquid electrolyte at room temperature. Using galvanostatic oxidation and electrochemical impedance spectroscopy coupled with operando X-ray diffraction, we show that roughly 0.5 equivalents of F-ions can be inserted onto the vacant A-site of the perovskite ReO3. Density functional theory calculations indicate that the intercalated phase is thermodynamically unfavorable compared to other less densely packed polymorphs of ReO3F. Pairing X-ray spectroscopy, neutron total scattering measurements, and magic-angle spinning 19F NMR confirms a rapid decomposition of the product on removal from the cell but nevertheless, these results clearly demonstrate that small anions like fluoride can be intercalated into solids as readily as alkali cations at room temperature, which opens new opportunities to electrochemically fluorinate many new materials. File list (2)download file view on ChemRxiv FxReO3.pdf (12.07 MiB) download file view on ChemRxiv supporting_information.pdf (5.70 MiB)
The growing demand for bioelectronics has generated widespread interest in implantable energy storage. These implantable bioelectronic devices, powered by a complementary battery/capacitor system, have faced difficulty in miniaturization without compromising their functionality. This paper reports on the development of a promising high‐rate cathode material for implantable power sources based on Li‐exchanged Na1.5VOPO4F0.5 anchored on reduced graphene oxide (LNVOPF‐rGO). LNVOPF is unique in that it offers dual charge storage mechanisms, which enable it to exhibit mixed battery/capacitor electrochemical behavior. In this work, electrochemical Li‐ion exchange of the LNVOPF structure is characterized by operando X‐ray diffraction. Through designed nanostructuring, the charge storage kinetics of LNVOPF are improved, as reflected in the stored capacity of 107 mAh g−1 at 20C. A practical full cell device composed of LNVOPF and T‐Nb2O5, which serves as a pseudocapacitive anode, is fabricated to demonstrate not only high energy/power density storage (100 Wh kg−1 at 4000 W kg−1) but also reliable pulse capability and biocompatibility, a desirable combination for applications in biostimulating devices. This work underscores the potential of miniaturizing biomedical devices by replacing a conventional battery/capacitor couple with a single power source.
The importance of metal migration during multi-electron redox activity has been characterized, revealing a competing demand to satisfy bonding requirements and local strains in structures upon alkali intercalation.The local structural evolution required to accommodate alkali intercalation in Y2(MoO4)3 and Al2(MoO4)3 during Li (de)insertion has been contrasted by operando characterization methods, including X-ray absorption spectroscopy and diffraction, along with nuclear magnetic resonance measurements. Computational modeling further rationalized behavioral differences. The local structure of Y2(MoO4)3 was maintained upon lithiation while the structure of Al2(MoO4)3 underwent substantial local atomic rearrangements as the stronger ionic character of the bonds in Al2(MoO4)3 allowed Al to mix off its starting octahedral position to accomodate strain during cycling. However, this mixing was prevented in the more covalent Y2(MoO4)3 which could only accommodate this strain through rotational motion of the polyhedral subunits. Knowing that an increased ionic character can facilitate the diffusion of redox-inactive metals when cycling multi-electron electrodes offers a powerful design principle, to improve kinetics for example, when identifying next-generation intercalation hosts that can store more than one electron per transition metal.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.