Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li<sub>3</sub>MO<sub>4</sub> Compounds (M = Ru, Nb, Sb and Ta)

Jacquet, Quentin; Rousse, Gwenaëlle; Iadecola, Antonella; Saubanère, Matthieu; Doublet, Marie-Liesse; Tarascon, Jean‐Marie

doi:10.1021/acs.chemmater.7b04117

Cited by 18 publications

(23 citation statements)

References 37 publications

(57 reference statements)

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“…The refinements did not improve with the introduction of Li vacancies or the partial occupancy of Ru in Li sites described previously . Ru adopts a slightly distorted environment with pairs of Ru–O distances at 1.91, 1.98, and 2.05 Å (Figure S3 and Table S2), thus with Ru displaced from the octahedron center . The coordination environment could not be evaluated for D-Li 3 RuO 4 because of the Li and Ru disorder (Figure S3).…”

Section: Resultsmentioning

confidence: 90%

“…However, the charge compensation mechanism was not completely elucidated, so it is unclear whether ligand-centered reactivity was realized. Furthermore, the role of structural ordering was not evaluated, yet both layered and disordered rock-salt forms of Li 3 RuO 4 are known. , …”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the role of structural ordering was not evaluated, yet both layered and disordered rock-salt forms of Li 3 RuO 4 are known. 29,30 In this study, the origin of the electrochemical properties of the two rock-salt polymorphs of Li 3 RuO 4 , disordered and layered, was ascertained. The structures are composed of arrangements of LiO 6 and RuO 6 edge-sharing octahedra with different distributions.…”

Section: Introductionmentioning

confidence: 99%

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Definition of Redox Centers in Reactions of Lithium Intercalation in Li₃RuO₄ Polymorphs

Ramakrishnan

Freeland

et al. 2020

J. Am. Chem. Soc.

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Cathodes based on layered LiMO 2 are the limiting components in the path toward Li-ion batteries with energy densities suitable for electric vehicles. Introducing an overstoichiometry of Li increases storage capacity beyond a conventional mechanism of formal transition metal redox. However, the role and fate of the oxide ligands in such intriguing additional capacity remain unclear. This reactivity was predicted in Li 3 RuO 4 , making it a valuable model system. A comprehensive analysis of the redox activity of both Ru and O under different electrochemical conditions was carried out, and the effect of Li/Ru ordering was evaluated. Li 3 RuO 4 displays highly reversible Li intercalation to Li 4 RuO 4 below 2.5 V vs Li + /Li 0 , with conventional reactivity through the formal Ru 5+ −Ru 4+ couple. In turn, it can also undergo anodic Li extraction at 3.9 V, which involves O states to a much greater extent than Ru. This reaction competes with side processes such as electrolyte decomposition and, to a much lesser extent, oxygen loss. Although the associated capacity is reversible, reintercalation unlocks a different, conventional pathway also involving the formal Ru 5+ −Ru 4+ couple despite operating above 2.5 V, leading to chemical hysteresis. This new pathway is both chemically and electrochemically reversible in subsequent cycles. This work exemplifies both the challenge of stabilizing highly depleted O states, even with 4d metals, and the ability of solids to access the same redox couple at two very different potential windows depending on the underlying structural changes. It highlights the importance of properly defining the covalency of oxides when defining charge compensation in view of the design of materials with high capacity for Li storage.

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Section: Resultsmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Definition of Redox Centers in Reactions of Lithium Intercalation in Li₃RuO₄ Polymorphs

Ramakrishnan

Freeland

et al. 2020

J. Am. Chem. Soc.

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“…Thus, the importance of further carrying comparative studies between Li and Na based materials showing anionic redox reactivity. Along that line, our group has recently studied Li 3 MO 4 (M being Ir [11] and Ru [12][13][14] ) and we have shown a sole activity of the anionic redox upon oxidation that ultimately leads to the decomposition of the material after the removal of 1 and 2 Li in Li 3 RuO 4 and Li 3 IrO 4 , respectively. As a continuation, we report herein the study of Na 3 RuO 4 in order to i) further get insights on the differences triggered by the use of Na rather than Li on the charge compensation mechanism, and ii) assess the limit of stability of Na-rich materials during oxidation.…”

Section: Introductionmentioning

confidence: 96%

Synthesis and Electrochemical Activity of Some Na(Li)‐Rich Ruthenium Oxides with the Feasibility to Stabilize Ru⁶⁺

Otoyama

Jacquet

Iadecola

et al. 2019

Advanced Energy Materials

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The capacity of Li-ion cathode materials has recently been greatly improved by the feasibility to trigger both cationic and anionic redox reactions within the same material. This concept has rapidly been implemented to Na-ion batteries to boost their energy density. The electrochemical properties of Na 3 RuO 4 with Li 3 RuO 4 are reported and compared herein. Strikingly, it is found that 3 Na can be extracted from Na 3 RuO 4 with the charge compensation mechanism enlisting first the oxidation of Ru 5+ to Ru 6+ , leading to Na 2 RuO 4 , and then the oxidation of oxygen during the rest of the charge. This drastically contrasts with the behavior of the Li counterpart since Ru never reaches that high oxidation state during lithium removal. By comparing the phase diagrams of A x RuO 4 (A being Li, Na, or K) together with density functional theory calculations, this finding is rationalized and it is demonstrated that this difference is mainly rooted in the size of the alkali cation. The bigger the alkali, the lower the coordination of Ru will be, stabilized by the same higher oxidation states. This work highlights the difference between Li and Na materials toward anionic redox and suggests the unusual coexistence of Ru 6+ and (O 2 ) n− , hence setting new challenges to theoreticians and opening opportunities for materials design.

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“…lower in energy than the I 4̅3 m structure, which has been reported as the lowest-energy phase in previous studies (Figure c,d and Table S1). − In the C 2/ m phase, both cations and anions are in a penta-coordinated structure with a distorted trigonal bipyramid geometry, which is rare in oxides. , In the configuration of [NbO 5 ], three oxygen atoms are distributed in the x – y plane, forming a quasi-equilateral triangular structure, and the other two oxygen atoms are located at the two vertices in the z direction. Therefore, the valence configuration of [NbO 5 ] is expected to be dsp 3 , which is similar to those of [CuCl 5 ], Mn(CO) 4 (NO), Fe(CO) 5 , and a predicted MgO. − As shown in Figure S2, the transition from the I 4̅3 m phase to the C 2/ m phase is achieved by the collective translation of adjacent atomic layers in the [2 2 –1] plane of I 4̅3 m phase by one-third of a layer spacing along the [2 0 –1] direction.…”

mentioning

confidence: 99%

Predicting Li-Rich Layered Oxide Compounds as High-Conductivity and Stable Solid Electrolytes

Qiu

Wang

et al. 2021

ACS Energy Lett.

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The search for new solid-state electrolytes (SSEs) with fast ionic conductivity and high electrochemical stability is one of most challenging issues for developing all-solid-state batteries. Most SSEs have specific ionic transport channels with the crystal structures of perovskite, NASICON, LISICON, and garnet. In this work, we predicted Li-rich layered Li3NbO4-type compounds as high-rate and stable SSEs. First-principles calculations show that the predicted Li3NbO4 compound has peculiar stacked structures of edge-shared [LiO5] and [NbO5] hexahedrons and exhibits higher thermodynamic stability than the experimentally synthesized compound with an octahedral stacked structure at <495 K. Its intralayer Li+ conductivity along the hexahedron–octahedron–hexahedron (h-o-h) path has a low energy barrier and low ionic conductivity. We further predicted Li2Mg0.5NbO4 as an SSE with a low ionic migration barrier of 0.33 eV, which is comparable with those of most other oxide SSEs. Therefore, the present study opens a new avenue to design high-performance SSEs in crystal space of layered rocksalt.

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Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li₃MO₄ Compounds (M = Ru, Nb, Sb and Ta)

Cited by 18 publications

References 37 publications

Definition of Redox Centers in Reactions of Lithium Intercalation in Li₃RuO₄ Polymorphs

Definition of Redox Centers in Reactions of Lithium Intercalation in Li₃RuO₄ Polymorphs

Synthesis and Electrochemical Activity of Some Na(Li)‐Rich Ruthenium Oxides with the Feasibility to Stabilize Ru⁶⁺

Predicting Li-Rich Layered Oxide Compounds as High-Conductivity and Stable Solid Electrolytes

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Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li3MO4 Compounds (M = Ru, Nb, Sb and Ta)

Cited by 18 publications

References 37 publications

Definition of Redox Centers in Reactions of Lithium Intercalation in Li3RuO4 Polymorphs

Definition of Redox Centers in Reactions of Lithium Intercalation in Li3RuO4 Polymorphs

Synthesis and Electrochemical Activity of Some Na(Li)‐Rich Ruthenium Oxides with the Feasibility to Stabilize Ru6+

Predicting Li-Rich Layered Oxide Compounds as High-Conductivity and Stable Solid Electrolytes

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Electrostatic Interactions versus Second Order Jahn–Teller Distortion as the Source of Structural Diversity in Li₃MO₄ Compounds (M = Ru, Nb, Sb and Ta)

Definition of Redox Centers in Reactions of Lithium Intercalation in Li₃RuO₄ Polymorphs

Definition of Redox Centers in Reactions of Lithium Intercalation in Li₃RuO₄ Polymorphs

Synthesis and Electrochemical Activity of Some Na(Li)‐Rich Ruthenium Oxides with the Feasibility to Stabilize Ru⁶⁺