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- Naylor, Andrew J., et al.
(författare)
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Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes
- 2019
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488. ; 7:44, s. 25355-25368
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Tidskriftsartikel (refereegranskat)abstract
- Lithium-rich materials, such as Li1.2Ni0.2Mn0.6O2, exhibit capacities not limited by transition metal redox, through the reversible oxidation of oxide anions. Here we offer detailed insight into the degree of oxygen redox as a function of depth within the material as it is charged and cycled. Energy-tuned photoelectron spectroscopy is used as a powerful, yet highly sensitive technique to probe electronic states of oxygen and transition metals from the top few nanometers at the near-surface through to the bulk of the particles. Two discrete oxygen species are identified, On− and O2−, where n < 2, confirming our previous model that oxidation generates localised hole states on O upon charging. This is in contrast to the oxygen redox inactive high voltage spinel LiNi0.5Mn1.5O4, for which no On− species is detected. The depth profile results demonstrate a concentration gradient exists for On− from the surface through to the bulk, indicating a preferential surface oxidation of the layered oxide particles. This is highly consistent with the already well-established core–shell model for such materials. Ab initio calculations reaffirm the electronic structure differences observed experimentally between the surface and bulk, while modelling of delithiated structures shows good agreement between experimental and calculated binding energies for On−.
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| 2. |
- Ojwang, Dickson O., et al.
(författare)
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Moisture-Driven Degradation Pathways in Prussian White Cathode Material for Sodium-Ion Batteries
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:8, s. 10054-10063
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Tidskriftsartikel (refereegranskat)abstract
- The high-theoretical-capacity (∼170 mAh/g) Prussian white (PW), NaxFe[Fe(CN)6]y·nH2O, is one of the most promising candidates for Na-ion batteries on the cusp of commercialization. However, it has limitations such as high variability of reported stable practical capacity and cycling stability. A key factor that has been identified to affect the performance of PW is water content in the structure. However, the impact of airborne moisture exposure on the electrochemical performance of PW and the chemical mechanisms leading to performance decay have not yet been explored. Herein, we for the first time systematically studied the influence of humidity on the structural and electrochemical properties of monoclinic hydrated (M-PW) and rhombohedral dehydrated (R-PW) Prussian white. It is identified that moisture-driven capacity fading proceeds via two steps, first by sodium from the bulk material reacting with moisture at the surface to form sodium hydroxide and partial oxidation of Fe2+ to Fe3+. The sodium hydroxide creates a basic environment at the surface of the PW particles, leading to decomposition to Na4[Fe(CN)6] and iron oxides. Although the first process leads to loss of capacity, which can be reversed, the second stage of degradation is irreversible. Over time, both processes lead to the formation of a passivating surface layer, which prevents both reversible and irreversible capacity losses. This study thus presents a significant step toward understanding the large performance variations presented in the literature for PW. From this study, strategies aimed at limiting moisture-driven degradation can be designed and their efficacy assessed.
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