O3–NaxMn1/3Fe2/3O2as a positive electrode material for Na-ion batteries: structural evolutions and redox mechanisms upon Na+(de)intercalation

Boisse, Benoit Mortemard de; Cheng, Ju‐Hsiang; Carlier, Dany; Guignard, Marie; Pan, Chun‐Jern; Bordère, S.; Филимонов, Д. С.; Drathen, Christina; Suard, Emmanuelle; Hwang, Bing‐Joe; Wattiaux, Alain; Delmas, Claude

doi:10.1039/c4ta06688j

Cited by 123 publications

(100 citation statements)

References 61 publications

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“…2), D-Na x RuO 3 undergoes a structural change from O3 to P3 (with Na in prismatic sites owing to the ABBCCA oxide-ion stacking) on charging23. This O3→P3 transition is commonly observed in O3-NaMO 2 materials through gliding of the [Na 1/3 Ru 2/3 ]O 2 slabs from ABCABC (O3) to ABBCCA (P3) stacking925. The synchrotron XRD pattern of the charged state (D-Na 1 RuO 3 ; Supplementary Fig.…”

Section: Resultsmentioning

confidence: 98%

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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Section: Resultsmentioning

confidence: 98%

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

et al. 2016

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“…Transitions from one stacking to another are possible through slab gliding requiring only small atomic displacement and no breaking of M-O bonds. They can therefore occur at room temperature during the cycling of the battery 29,30,39,40 , as it was more recently shown in the O3-NaxMn1/3Fe2/3O2 system 41 . This difference in stacking arrangements leads to a significant change in intensity ratio between the reflections 104h and 105h in the Xray diffraction patterns indexed with an undistorted hexagonal cell.…”

Section: Evolution Of the Cell Parameters And Stackingmentioning

confidence: 94%

The Na_xMoO₂ Phase Diagram (¹/₂ ≤ x < 1): An Electrochemical Devil’s Staircase

Vitoux¹,

Guignard²,

Suchomel³

et al. 2017

Chem. Mater.

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Layered sodium transition metal oxides represent a complex class of materials that exhibit a variety of properties, e.g. superconductivity, and can feature in a range of applications, e.g. batteries. Understanding the structure-function relationship is key to developing better materials. In this context, the phase diagram of the NaxMoO2 system has been studied using electrochemistry combined with in situ synchrotron X-ray diffraction experiments. The many steps observed in the electrochemical curve of Na2/3MoO2 during cycling in a sodium battery suggests numerous reversible structural transitions during sodium (de)intercalation between Na0.5MoO2 and Na~1MoO2. In situ X-ray diffraction confirmed the complexity of the phase diagram within this domain, thirteen single phase domains with minute changes in sodium contents. Almost all display superstructure or modulation peaks in their X-ray diffraction patterns suggesting the existence of many NaxMoO2 specific phases that are believed to be characterized by sodium/vacancy ordering as well as Mo-Mo bonds and subsequent Mo-O distances patterning in the structures. Moreover, a room temperature triclinic distortion was evidenced in the composition range 0.58 ≤ x < 0.75, for the first time in a sodium layered oxide system. Monoclinic and triclinic subcell parameters were refined for every NaxMoO2 phase identified. Reversible [MoO2] slab glidings occur during the sodium (de)intercalation. This level of structural detail provides unprecedented insight on the phases present and their evolution which may allow each phase to be isolated and examined in more detail.

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“…Specially, a small amount of the O3 type could not completely transform to P3 but always involve in the electrochemical process. [171,172] Sharma et al reported that O3-Na 2/3 [Fe 2/3 Mn 1/3 ]O 2 undergoes a series of twophase and solid-solution reactions leading to a disordered phase at the charged state before undergoing solid solution and two behavior on discharge, but the structural motif and the space group are preserved. [173,174] The physical origin of bistability and differences in Na ion diffusion between P2 and O3 phases may result from the electrostatic interactions within oxide layers which control the bistable nature of these two phases.…”

Section: Fe/mn-based Oxidesmentioning

confidence: 99%

Layered Oxide Cathodes for Sodium‐Ion Batteries: Phase Transition, Air Stability, and Performance

Wang

You

Yin

et al. 2017

Advanced Energy Materials

660

464

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sources into large-scale grids, inexpensive, efficient, and fast-responding electrical energy storage (EES) systems are essential to store the off-peak energy and releasing the stored energy during the onpeak period. Among various EES systems, rechargeable batteries represent one of the most competitive technologies because of their high conversion efficiency and environmental friendliness. [1][2][3][4] For stationary EES systems, batteries with low cost, high safety, high rate capability, and long cycle stability are highly desired.Lithium (Li)-ion batteries (LIBs) have achieved great success in the market of portable electronics and electric vehicles since their commercialization by Sony Company in 1991. However, the shortage of Li resources in nature gives rise to a concern about its sustainable development in grid scale. Compared with Li, sodium resource has rich natural abundance in the earth crust and a worldwide distribution, consequently leading to a low price of sodium-based raw materials (e.g., the cost of Na 2 CO 3 is about 25-30 times lower than that of Li 2 CO 3 ). Besides, sodium has a suitable redox potential (E 0 (Na + /Na) = −2.71 V versus standard hydrogen electrode (SHE), 0.3 V above that of Li + /Li) and similar physical and chemical properties with lithium. [5,6] Therefore, rechargeable sodium-ion batteries (SIBs), which have a similar "rockingchair" working principle of LIBs, are emerging as an appealing choice as alternatives for LIBs. Note that it is difficult for SIBs to bypass LIBs in terms of energy densities because of the much higher weight of Na and lower standard electrochemical potential. [7][8][9][10] Nevertheless, the use of low-cost materials, including inexpensive Na-based raw materials and Al current collectors for both cathodes and anodes in SIBs, could significantly reduce the cost. In this case, SIBs could be applied where cost-effectiveness rather than energy density is the most critical issue, e.g., in the field of large-scale EES. As a result, sodiumbased electroactive materials are enjoying renewed interest especially for very low cost systems for grid storage. [11,12] Given that cathode materials are the key component that determines energy density and cost, tremendous efforts have been devoted to exploring suitable positive electrode materials with high reversible capacity, rapid Na ions insertion/extraction, and good cycling stability in the past few years. [13,14] A broad range of compounds, including layered oxides, polyanionic frameworks, hexacyanoferrates, and organics, haveThe increasing demand for replacing conventional fossil fuels with clean energy or economical and sustainable energy storage drives better battery research today. Sodium-ion batteries (SIBs) are considered as a promising alternative for grid-scale storage applications due to their similar "rockingchair" sodium storage mechanism to lithium-ion batteries, the natural abundance, and the low cost of Na resources. Searching for appropriate electrode materials with acceptable electrochemical perfor...

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O3–Na_xMn_1/3Fe_2/3O₂as a positive electrode material for Na-ion batteries: structural evolutions and redox mechanisms upon Na⁺(de)intercalation

Cited by 123 publications

References 61 publications

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

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

The Na_xMoO₂ Phase Diagram (¹/₂ ≤ x < 1): An Electrochemical Devil’s Staircase

Layered Oxide Cathodes for Sodium‐Ion Batteries: Phase Transition, Air Stability, and Performance

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O3–NaxMn1/3Fe2/3O2as a positive electrode material for Na-ion batteries: structural evolutions and redox mechanisms upon Na+(de)intercalation

Cited by 123 publications

References 61 publications

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

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

The NaxMoO2 Phase Diagram (1/2 ≤ x < 1): An Electrochemical Devil’s Staircase

Layered Oxide Cathodes for Sodium‐Ion Batteries: Phase Transition, Air Stability, and Performance

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Product

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O3–Na_xMn_1/3Fe_2/3O₂as a positive electrode material for Na-ion batteries: structural evolutions and redox mechanisms upon Na⁺(de)intercalation

The Na_xMoO₂ Phase Diagram (¹/₂ ≤ x < 1): An Electrochemical Devil’s Staircase