Oxygen-Storage Materials to Stabilize the Oxygen Redox Activity of Three-Layered Sodium Transition Metal Oxides

Author(s):  
Mariya L. Kalapsazova ◽  
Krassimir L. Kostov ◽  
Rositsa R. Kukeva ◽  
Ekaterina N. Zhecheva ◽  
Radostina K. Stoyanova
Author(s):  
Qiannan Liu ◽  
Zhe Hu ◽  
Weijie Li ◽  
Chao Zou ◽  
Huile Jin ◽  
...  

This work provides guidance on controlling anionic redox activity and finding novel high-capacity transition metal oxide cathodes for sodium-ion batteries.


2021 ◽  
Author(s):  
Donggun Eum ◽  
Byunghoon Kim ◽  
Jun-Hyuk Song ◽  
Hyeokjun Park ◽  
Sung Joo Kim ◽  
...  

Abstract Lattice oxygen redox activity offers an unexplored way to access the latent superior electrochemical property of transition metal oxides for rechargeable batteries. However, the redox reaction of the lattice oxygen is often accompanied by unfavorable structural transformations and the corresponding degradation of electrochemical performances, precluding its practical application. Herein, we explore the close interplay between the local structural change during the dynamic intercalation process and the solid-state oxygen electrochemistry in the short- or long-term battery operation for layered transition metal oxides. By employing two model systems of the layered Na0.6(Li0.2TixMn0.8−x)O2 with the oxygen redox capability, it is demonstrated that the substantially distinct evolutions in the oxygen redox activity and reversibility are caused by different cation migration mechanisms available in the system during the de/intercalation (i.e. out-of-plane and in-plane migrations of transition metals (TMs)). We show that the π stabilization upon the oxygen oxidation initially aids in the reversibility of the oxygen redox and is predominant in the absence of TM migrations, however, the π-interacting oxygens are gradually replaced by the σ-interacting oxygens that trigger the formation of O–O dimers and the structural destabilization over cycles. More importantly, it is revealed that the distinct TM migration paths available in the respective layered materials govern the conversion from π to σ interactions and its kinetics. It infers that regulating the dynamics of TMs in the layered materials can play a key role in delaying or inhibiting the deterioration of the oxygen redox reversibility. These findings constitute a step forward in unraveling the correlation between the local structural evolution and the reversibility of solid-state oxygen electrochemistry, and provide a guidance for developing oxygen-redox layered electrode materials.


Author(s):  
R. Ai ◽  
H.-J. Fan ◽  
L. D. Marks

It has been known for a long time that electron irradiation induces damage in maximal valence transition metal oxides such as TiO2, V2O5, and WO3, of which transition metal ions have an empty d-shell. This type of damage is excited by electronic transition and can be explained by the Knoteck-Feibelman mechanism (K-F mechanism). Although the K-F mechanism predicts that no damage should occur in transition metal oxides of which the transition metal ions have a partially filled d-shell, namely submaximal valence transition metal oxides, our recent study on ReO3 shows that submaximal valence transition metal oxides undergo damage during electron irradiation.ReO3 has a nearly cubic structure and contains a single unit in its cell: a = 3.73 Å, and α = 89°34'. TEM specimens were prepared by depositing dry powders onto a holey carbon film supported on a copper grid. Specimens were examined in Hitachi H-9000 and UHV H-9000 electron microscopes both operated at 300 keV accelerating voltage. The electron beam flux was maintained at about 10 A/cm2 during the observation.


Author(s):  
Michel Fialin ◽  
Guy Rémond

Oxygen-bearing minerals are generally strong insulators (e.g. silicates), or if not (e.g. transition metal oxides), they are included within a rock matrix which electrically isolates them from the sample holder contacts. In this respect, a thin carbon layer (150 Å in our laboratory) is evaporated on the sections in order to restore the conductivity. For silicates, overestimated oxygen concentrations are usually noted when transition metal oxides are used as standards. These trends corroborate the results of Bastin and Heijligers on MgO, Al2O3 and SiO2. According to our experiments, these errors are independent of the accelerating voltage used (fig.l).Owing to the low density of preexisting defects within the Al2O3 single-crystal, no significant charge buildup occurs under irradiation at low accelerating voltage (< 10keV). As a consequence, neither beam instabilities, due to electrical discharges within the excited volume, nor losses of energy for beam electrons before striking the sample, due to the presence of the electrostatic charge-induced potential, are noted : measurements from both coated and uncoated samples give comparable results which demonstrates that the carbon coating is not the cause of the observed errors.


Crystals ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 256
Author(s):  
Christian Rodenbücher ◽  
Kristof Szot

Transition metal oxides with ABO3 or BO2 structures have become one of the major research fields in solid state science, as they exhibit an impressive variety of unusual and exotic phenomena with potential for their exploitation in real-world applications [...]


2021 ◽  
Vol 36 ◽  
pp. 514-550
Author(s):  
Zhihao Lei ◽  
Jang Mee Lee ◽  
Gurwinder Singh ◽  
C.I. Sathish ◽  
Xueze Chu ◽  
...  

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