Anionic redox chemistry in Na-rich Na 2 Ru 1−y Sn y O 3 positive electrode material for Na-ion batteries

Rozier, Patrick; Mariyappan, Sathiya; Paulraj, Alagar Raj; Foix, Dominique; Désaunay, Thomas; Taberna, Pierre‐Louis; Simon, Patrice; Tarascon, Jean‐Marie

doi:10.1016/j.elecom.2015.02.001

Cited by 111 publications

(102 citation statements)

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“…64 Substitution of Sn for Ru is also beneficial to activate and stabilize the anion redox, and approximately 1.2 mol of sodium ions are reversibly extracted/inserted from/into Na 2 Ru 0.75 Sn 0.25 -O 3 . 65 The observed reversible capacity is clearly larger than the theoretical capacity based on Ru 4+ /Ru 5+ redox. However, the additional capacity originating from the anion redox is deteriorated on further cycles, and this deterioration is faster than that of the lithium counterpart, Li 2 Ru 0.75 Sn 0.25 O 3 .…”

Section: Redox Reaction Of Oxide Ions For Sodium Batteriesmentioning

confidence: 80%

“…64,65 Similar to Li 2 RuO 3 , Na 2 RuO 3 crystallizes into the α-NaFeO 2 -type layered structure. Two layered polymorphs, in-plane Na/Ru ordered and disordered phases, exist and the anionic redox is activated only for the ordered phase as shown in Figure 12.…”

Section: Redox Reaction Of Oxide Ions For Sodium Batteriesmentioning

confidence: 99%

“…Indeed, the significant shrinkage of interlayer distance associated with phase transition has been observed, coupled with the anion redox for Na 2 Ru 0.75 Sn 0.25 O 3 . 65 Further systematic and comparative studies between Li and Na compounds are needed to understand the factors affecting the cyclability of the anion redox for rechargeable batteries.…”

Section: Redox Reaction Of Oxide Ions For Sodium Batteriesmentioning

confidence: 99%

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Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Yabuuchi¹

2017

Chem. Lett.

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Research interest for a solid-state redox reaction of oxide ions (oxygen) is rapidly increasing for rechargeable battery applications. This article reviews the history and development of charge compensation mechanisms with oxide ions for electrode materials of batteries. Reversible and irreversible processes are observed after the oxidation of oxide ions, and it highly depends on the natures of chemical bonds between transition metals and oxide ions. Future possibility of high-energy lithium/sodium batteries with the oxide ion redox is also discussed.

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Section: Redox Reaction Of Oxide Ions For Sodium Batteriesmentioning

confidence: 80%

Section: Redox Reaction Of Oxide Ions For Sodium Batteriesmentioning

confidence: 99%

Section: Redox Reaction Of Oxide Ions For Sodium Batteriesmentioning

confidence: 99%

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Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Yabuuchi¹

2017

Chem. Lett.

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“…They range from extending these studies to other Li-rich layered oxide phases showing anionic redox activity, either without (O-O) pairs or with it but avoiding TM migration, to the elaboration of electrochemical and phenomenological models that can fully rationalize our experimental findings. Our results should warn researchers to also keep in mind practical applications in the pursuit of anionic redox which is gaining fast importance in electrochemical systems, 65 including Na-based cathodes [66][67][68] and cation-disordered cathodes. 69 Solving these issues is not insurmountable and we hope that our timely identification of these fundamental bottlenecks toward real-world applications will encourage direct targeting of anionic redox with fundamental studies and mitigation strategies for neutralizing the problems with LR-NMC materials in general and facilitating its utilization in practical high energy density Li-ion batteries.…”

Section: Discussionmentioning

confidence: 99%

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries

Assat

Delacourt

Corte

et al. 2016

J. Electrochem. Soc.

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151

200

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Li-rich layered oxides, e.g. Li [Li 0.20 Ni 0.13 Mn 0.54 Co 0.13 ]O 2 (LR-NMC), lead high energy density Li-ion battery cathodes, thanks to the reversible redox of oxygen anions that boost charge storage capacity. Unfortunately, their commercialization has been stalled by practical issues (i.e. voltage hysteresis, poor rate capability, and voltage fade) and hence it is necessary to investigate whether these problems are intrinsically inherent to anionic redox and its structural consequences. To this end, the 'model' Li-rich layered oxide Li 2 Ru 0.75 Sn 0.25 O 3 (LRSO) is here used as a fertile test-bed for scrutinizing the effects of cationic and anionic redox independently since they are neatly isolated at low and high potentials, respectively. Through an arsenal of electrochemical techniques, we demonstrate that voltage hysteresis is triggered by anionic redox and grows progressively with deeper oxidation of oxygen in conjunction with the deterioration of both interfacial charge-transfer kinetics and bulk diffusion coefficient. We equally show that this anionic-driven poor kinetics keeps deteriorating further with cycling and we also find that voltage fades faster if oxygen is kept oxidized for longer. Our findings, which are in fact harsher for LR-NMC, convey caution that anionic redox risks practical problems; hence, when chasing larger capacities with this class of materials, we encourage considering real-world applications.

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“…However, despite the presence of [Na 1/3 Ru 2/3 ]O 2 slabs, Na 2 RuO 3 delivered a modest capacity of 135 mAh g −1 , limited to the Ru 5+ /Ru 4+ one-electron reaction. In contrast, Rozier et al 20 very recently reported that Na 2 RuO 3 can deliver a capacity greatly exceeding that of the Ru 5+ /Ru 4+ one-electron reaction. At present, the discrepancy between the reported electrochemical properties is an open question.…”

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confidence: 90%

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

et al. 2016

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Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g−1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g−1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

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Anionic redox chemistry in Na-rich Na 2 Ru 1−y Sn y O 3 positive electrode material for Na-ion batteries

Cited by 111 publications

References 12 publications

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

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