2020
DOI: 10.1016/j.nanoen.2020.104474
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Both cationic and anionic redox chemistry in a P2-type sodium layered oxide

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Cited by 109 publications
(94 citation statements)
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“…However, the substitution of Li is not necessary to create such O 2p nonbonding orbitals. 29 In fact, similar oxygen redox behavior has also been reported in Mg-substituted samples such as Na I. It is notable that most of the compounds containing Ni do not have reversible oxygen redox.…”
supporting
confidence: 59%
“…However, the substitution of Li is not necessary to create such O 2p nonbonding orbitals. 29 In fact, similar oxygen redox behavior has also been reported in Mg-substituted samples such as Na I. It is notable that most of the compounds containing Ni do not have reversible oxygen redox.…”
supporting
confidence: 59%
“…[22] For SIBs, the anionic redox reaction is available for not only Na-rich materials but also Na-deficient P2/P3-type compounds. [23][24][25][26][27][28][29][30][31][32][33][34][35] For example, manganese-based P2-type sodiumdeficient materials with low-valence substituents, such as Li, [26,30,31] Zn, [23,29] and Mg, [27,28] have demonstrated oxygenredox activity with good structural stability. It is generally accepted that a NaOA (A = Li, Na, Mg, Zn, or vacancy) local coordination environment is the essential requirement for oxygen redox activation in P2/O3 type layered Na x [ATM] O 2 (TM: transition metals).…”
Section: Introductionmentioning
confidence: 99%
“…Migration of those Li and Na in the transition metal layers toward Na layers induces formation of lone pair electrons in O 2p orbital, such that the high density of state energy for oxygen allows oxidation of oxygen although the reaction occurs kinetically sluggish. Recent progress has enabled the sluggish kinetics of oxygen-redox and low energy density caused by the low voltage of the Mn 4+ / Mn 3+ redox couple to be circumvented; specifically, covalence between O 2p and Cu 3d, [32,33] Ni 3d, [24] or Co 3d [25,35] substantially promotes facile electron transfer and increases in operation voltage and provides reversibility of the oxygen-redox reaction, proved in sodium-deficient P2-type Na 2/3 [Ni 1/3 Mn 2/3 ] O 2 [36] and Na 2/3 [Cu 0.28 Mn 0.72 ]O 2 [37] without such NaOA local configuration. Density functional theory (DFT) calculation and mapping of resonant inelastic X-ray scattering (mRIXS) demonstrated that the reversible oxygen redox could take place due to a higher covalence of NiO and CuO bonds at highest desodiated states, which leads to the energy of O 2p in e g * (NiO/ CuO) becomes higher than that of Ni 3d/Cu 3d, which, therefore, facilitates the oxygen redox reaction.…”
Section: Introductionmentioning
confidence: 99%
“…The good full‐cell electrochemistry performance further demonstrates the practicability of the HC anode material. [ 67,68 ]…”
Section: Resultsmentioning
confidence: 99%