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The aging mechanism of 10% and 30% nickel-substituted manganese hexacyanoferrate cathode material in aqueous zinc-ion batteries has been explored through the advanced synchrotron-based two-dimensional X-ray fluorescence technique. Thanks to the two-dimension modality, not only were the metal concentration dynamics throughout the entire electrodes followed during the aging process, but their spatial distribution was also revealed, suggesting the route of the material transformation. The dissolution of Mn and Ni, as well as the penetration of Zn inside the framework were detected, while the Mn aggregations were found outside the hexacyanoferrate framework. Additionally, the possibility of conducting X-ray absorption spectroscopy measurements on the regions of interest made it possible to explore the chemical state of each metal, and furthermore, synchrotron-based powder X-ray diffraction demonstrated the gradual structural modification in 30% Ni-containing sample series in terms of the different phase formation. [ABSTRACT FROM AUTHOR]

Symmetric batteries, in which the same active material is used for the positive and the negative electrode, simplifying the manufacture process and reducing the fabrication cost, have attracted extensive interest for large-scale stationary energy storage. In this paper, we propose a symmetric battery based on titanium hexacyanoferrate (TiHCF) with two well-separated redox peaks of Fe3+/Fe2+ and Ti4+/Ti3+ and tested it in aqueous Na-ion/ K-ion/Mg-ion electrolytes. The result shows that all the symmetric batteries exhibit a voltage plateau centered at around 0.6 V, with discharge capacity around 30 mAhg−1 at C/5. Compared to a Mg-ion electrolyte, the TiHCF symmetric batteries in Na-ion and K-ion electrolytes have better stability. The calculated diffusion coefficient of Na+, K+, and Mg2+ are in the same order of magnitude, which indicates that the three-dimensional ionic channels and interstices in the lattice of TiHCF are large enough for an efficient Na+, K+ and Mg2+ insertion and extraction. [ABSTRACT FROM AUTHOR]

Among different Prussian Blue Analogues (PBAs), manganese hexacyanoferrate (MnHCF), with open framework and two abundant electroactive metal sites, exhibits high potential for the grid-scale aqueous rechargeable zinc-ion batteries (ARZIBs) application. Until now, the intercalation mechanism of Zn 2+ into MnHCF has not been clearly illustrated. In this work, combining different synchrotron X-ray techniques, the structural and microscopic evolution of MnHCF in 3 m ZnSO 4 electrolyte is comprehensively studied, and a thorough understanding of the intercalation/release dynamic, in terms of local and long-range domain, is provided. The elemental distribution and structural information of Fe, Mn, Zn inside MnHCF electrodes is obtained from the X-ray fluorescence (XRF) elemental maps and X-ray absorption spectroscopy (XAS). The in-depth analysis of extended X-ray absorption fine structure (EXAFS) signals confirm that the rearrangement of Mn site, evidencing the cleavage of the Mn─N bond with the formation of a Mn─O bond, in an octahedral environment. The phase transformation of MnHCF takes place exclusively during the 1st cycle, and a mixture of rhombohedral and cubic zinc hexacynoferrate (ZnHCF) phases are formed during the first charge process. Thereafter, the newly formed cubic ZnHCF phase becomes the only stable one, existing in the subsequent cycles and exhibiting excellent electrochemical stability., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

High-entropy oxides (HEOs) have emerged as promising anode materials for next-generation lithium-ion batteries (LIBs). Among them, spinel HEOs with vacant lattice sites allowing for lithium insertion and diffusion seem particularly attractive. In this work, electrospun oxygen-deficient (Mn,Fe,Co,Ni,Zn) HEO nanofibers are produced under environmentally friendly calcination conditions and evaluated as anode active material in LIBs. A thorough investigation of the material properties and Li + storage mechanism is carried out by several analytical techniques, including ex situ synchrotron X-ray absorption spectroscopy. The lithiation process is elucidated in terms of lithium insertion, cation migration, and metal-forming conversion reaction. The process is not fully reversible and the reduction of cations to the metallic form is not complete. In particular, iron, cobalt, and nickel, initially present mainly as Fe 3+ , Co 3+ /Co 2+ , and Ni 2+ , undergo reduction to Fe 0 , Co 0 , and Ni 0 to different extent (Fe < Co < Ni). Manganese undergoes partial reduction to Mn 3+ /Mn 2+ and, upon re-oxidation, does not revert to the pristine oxidation state (+4). Zn 2+ cations do not electrochemically participate in the conversion reaction, but migrating from tetrahedral to octahedral positions, they facilitate Li-ion transport within lattice channels opened by their migration. Partially reversible crystal phase transitions are observed., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)