The interfacial reactions in sodium‐ion batteries (SIBs) are not well understood yet. The formation of a stable solid electrolyte interphase (SEI) in SIBs is still challenging due to the higher solubility of the SEI components compared to lithium analogues. This study therefore aims to shed light on the dissolution of SEI influenced by the electrolyte chemistry. By conducting electrochemical tests with extended open circuit pauses, and using surface spectroscopy, we determine the extent of self‐discharge due to SEI dissolution. Instead of using a conventional separator, β‐alumina was used as sodium‐conductive membrane to avoid crosstalk between the working and sodium‐metal counter electrode. The relative capacity loss after a pause of 50 hours in the tested electrolyte systems ranges up to 30 %. The solubility of typical inorganic SEI species like NaF and Na2CO3 was determined. The electrolytes were then saturated by those SEI species in order to oppose ageing due to the dissolution of the SEI.
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Rechargeable sodium-ion batteries have recently attracted renewed interest as an alternative to Li-ion batteries for electric energy storage applications, because of the low cost and wide availability of sodium resources. Thus, the electrochemical energy storage community has been devoting increased attention to designing new cathode materials for sodium-ion batteries. Here we investigate P2-Na 0.78 Co 1/2 Mn 1/3 Ni 1/6 O 2 as a cathode material for sodium ion batteries. The main focus is to understand the mechanism of the electrochemical performance of this material, especially differences observed in redox reactions at high potentials. Between 4.2 V and 4.5 V, the material delivers a reversible capacity which is studied in detail using advanced analytical techniques. In situ X-ray diffraction reveals the reversibility of the P2-type structure of the material. Combined soft X-ray absorption spectroscopy and resonant inelastic X-ray scattering demonstrates that Na deintercalation at high voltages is charge compensated by formation of localized electron holes on oxygen atoms.
mixtures thereof) [1,2] represent a major family of positive electrode materials for sodium-ion batteries (SIBs). They adopt one of the polymorphs O3, P3, and P2, depending on the coordination environment of the Na ions and the number of MnO 2 slabs in the unit cell. [3] The compositional and structural phase spaces available to these materials are vast, which enables properties such as capacity, rate capability, operating voltage, and cyclability to be carefully tuned. [4,5] In general, substitution of spectator elements, such as Li, [6] Mg, [7,8] and Zn [9] for Mn provides a rigid crystal structure during cycling and suppresses Jahn-Teller distortions, at the expense of Mn-derived capacity. Additionally, these electrochemically inactive dopants enable the activation of oxygen redox by creating nonbonding O 2p states at the top of the valence band upon desodiation, which represents an effective way to raise the energy density of positive electrode materials. [10][11][12][13][14][15][16] However, the oxidation of oxygen at high voltages often leads to large voltage hysteresis due to cationic migration from the transition metal layers to the alkali metal layers with concomitant structural Activation of oxygen redox represents a promising strategy to enhance the energy density of positive electrode materials in both lithium and sodium-ion batteries. However, the large voltage hysteresis associated with oxidation of oxygen anions during the first charge represents a significant challenge. Here, P3-type Na 0.67 Li 0.2 Mn 0.8 O 2 is reinvestigated and a ribbon superlattice is identified for the first time in P3-type materials. The ribbon superstructure is maintained over cycling with very minor unit cell volume changes in the bulk while Li ions migrate reversibly between the transition metal and Na layers at the atomic scale. In addition, a range of spectroscopic techniques reveal that a strongly hybridized Mn 3d-O 2p favors ligand-to-metal charge transfer, also described as a reductive coupling mechanism, to stabilize reversible oxygen redox. By preparing materials under three different synthetic conditions, the degree of ordering between Li and Mn is varied. The sample with the maximum cation ordering delivers the largest capacity regardless of the voltage windows applied. These findings highlight the importance of cationic ordering in the transition metal layers, which can be tuned by synthetic control to enhance anionic redox and hence energy density in rechargeable batteries.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/aenm.202102325.
Lithium-rich layered oxides and sodium layered oxides represent attractive positive electrode materials exhibiting excess capacity delivered by additional oxygen redox activity. However, structural degradation in the bulk and detrimental reactions with the electrolyte on the surface often occur, leading to limited reversibility of oxygen redox processes. Here we present the properties of P3-type Na0.67Mg0.2Mn0.8O2 synthesized under both air and oxygen. Both materials exhibit stable cycling performance in the voltage range 1.8-3.8 V where the Mn 3+ /Mn 4+ redox couple entirely dominates the electrochemical reaction. Oxygen redox activity is triggered for both compounds in the wider voltage window 1.8-4.3 V with typical large voltage hysteresis from non-bonding O 2p states generated by substituted Mg. Interestingly, for the compound prepared under oxygen, an additional novel reversible oxygen redox activity is shown with exceptionally small voltage hysteresis (20 mV). The presence of vacancies in the transition metal layers is shown to play a critical role not only in forming unpaired O 2p states independent of substituted elements but also in stabilising the P3 structure during charge with reduced structural transformation to the O'3 phase at the end of discharge. This study reveals the important role of vacancies in P3-type sodium layered oxides to increase energy density using both cationic and anionic redox processes.
The interfacial reactions in sodium‐ion batteries (SIBs) are not well understood yet. The formation of a stable solid electrolyte interphase (SEI) in SIBs is still challenging due to the higher solubility of the SEI components compared to lithium analogues. This study therefore aims to shed light on the dissolution of SEI influenced by the electrolyte chemistry. By conducting electrochemical tests with extended open circuit pauses, and using surface spectroscopy, we determine the extent of self‐discharge due to SEI dissolution. Instead of using a conventional separator, β‐alumina was used as sodium‐conductive membrane to avoid crosstalk between the working and sodium‐metal counter electrode. The relative capacity loss after a pause of 50 hours in the tested electrolyte systems ranges up to 30 %. The solubility of typical inorganic SEI species like NaF and Na2CO3 was determined. The electrolytes were then saturated by those SEI species in order to oppose ageing due to the dissolution of the SEI.
Sodium-ion batteries have become a potential alternative to Li-ion batteries due to the abundance of sodium resources. Sodium-ion cathode materials have been widely studied with particular focus on layered oxide lithium analogues. Generally, the capacity is limited by the redox processes of transition metals. Recently, however, the redox participation of oxygen gained a lot of research interest. Here the Mg-doped cathode material P2-Na 0.56 Mg 0.04 Ni 0.19 Mn 0.70 O 2 is studied, which is shown to exhibit a good capacity (ca. 120 mAh/g) and high average operating voltage (ca. 3.5 V vs. Na + /Na). Due to the Mg-doping, the material exhibits a reversible phase transition above 4.3 V, which is attractive in terms of lifetime stability. In this study, we combine X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and resonant inelastic X-ray scattering spectroscopy techniques to shed light on both, cationic and anionic contributions towards charge compensation.
There is experimental evidence that the astaxanthin, betanin, and epigallocatechin-3-gallate (EGCG) compounds slow down the aggregation kinetics and the toxicity of the amyloid-β (Aβ) peptide. How these inhibitors affect the self-assembly at the atomic level remains elusive. To address this issue, we have performed for each ligand atomistic replica exchange molecular dynamic (REMD) simulations in an explicit solvent of the Aβ 11−40 trimer from the U-shape conformation and MD simulations starting from Aβ 1−40 dimer and tetramer structures characterized by different intra-and interpeptide conformations. We find that the three ligands have similar binding free energies on small Aβ 40 oligomers but very distinct transient binding sites that will affect the aggregation of larger assemblies and fibril elongation of the Aβ 40 peptide.
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