2020
DOI: 10.1016/j.ensm.2020.03.016
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Oxygen redox activity with small voltage hysteresis in Na0.67Cu0.28Mn0.72O2 for sodium-ion batteries

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Cited by 130 publications
(104 citation statements)
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“…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%
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“…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%
“…We approach that increasing covalency in the structure could endorse to realize the activation of oxygen redox couple. Considering Pauling electronegativity of Ru (2.2), which is higher than Ni (1.91), Zn (1.65), or Mg (1.33), might induce RuO bonds more covalent so that electrons are inclined to delocalize on the ruthenium cations and oxygen anions; [36,37] namely, overlapping of Ru 4d with the O 2p orbitals may generate not only the cumulative transition metal redox but also the reversible charge compensation progressed by oxygen redox. In this work, we introduce the unique behavior of layered O3 type Na[Ni 2/3 Ru 1/3 ]O 2 , exhibits a reversible capacity of 154 mAh (g-oxide) −1 that is associated with both cationic Ni 3+ /Ni 2+ and anionic O 2− /O 1− redox pairs, for which the anionic behavior is related to an additional phase transition to the O1 phase, as observed by operando X-ray diffraction (o-XRD).…”
Section: Introductionmentioning
confidence: 99%
“…It is worth noticing that the rate capability of P2-Na 0.76 Ca 0.05 [Ni 0.23 □ 0.08 Mn 0.69 ]O 2 outperforms those of the previously reported P2-type sodium oxides cathodes featuring anionic redox activity, as highlighted in the inset of Figure 2e. [15,16,[28][29][30][31]39,40] This can be attributed to the large Na-layer distance (d ONaO ) of P2-Na 0.76 Ca 0.05 [Ni 0.23 □ 0.08 Mn 0.69 ]O 2 (Table S3, Supporting Information), which is beneficial for fast Na + diffusion. To assess the long-term cycling durability of the P2-Na 0.76 Ca 0.05 [Ni 0.23 □ 0.08 Mn 0.69 ]O 2 cathode, galvanostatic charge/discharge measurements at 1 C, 2 C, and 5 C after the preactivation at 0.1 C for 3 cycles were conducted.…”
Section: Resultsmentioning
confidence: 99%
“…Herein, we review the current status of research and remaining challenges for the anionic reaction and associated mechanisms for different structures and elements of cathode materials for SIBs. 2 Energy Material Advances [67][68][69][70], 0:4 ≤ x ≤ 0:8, y ≤ 1/3), known as P2 and P3 types, typically deliver high discharge capacities of 160-220 mAh g −1 . The prismatic environment for sodium ions enables maintenance of the large interlayer distances during de/sodiation, which is beneficial for facile diffusion of sodium ions and smooth phase transitions.…”
Section: Introductionmentioning
confidence: 99%
“…The desodiation leads to the formation of the O2 phase accompanied by a large vol-ume change of approximately 23% that induces cracking of particles; hence, the material suffers from severe capacity fade during cycling. Recently, this material was revisited to relate the high-voltage reaction occurring over 4.1 V to the oxygen-redox reaction[61][62][63][64][65][66][67][68][69][70][71][72]. Ma et al[61] investigated Na 0.78 [Ni 0.23 Mn 0.69 ]O 2 with 7% vacancies in the TM layers.…”
mentioning
confidence: 99%