Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox

Li, Biao; Sougrati, Moulay Tahar; Rousse, Gwenaëlle; Morozov, Anatolii V.; Dedryvère, Rémi; Iadecola, Antonella; Senyshyn, Anatoliy; Zhang, Leiting; Abakumov, Artem M.; Doublet, Marie Liesse; Tarascon, J. M.

doi:10.1038/s41557-021-00775-2

Cited by 93 publications

(112 citation statements)

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“…This wide variation in size and charge for substituted cations is not generally characteristic of oxide systems (such as MgO or CaO), and thus, may open up new prospects for fundamental and applied science. Some ZnO-based solid solutions with a rock-salt structure synthesized under HP and HT may be of interest as promising Li-containing materials [13,14,[63][64][65][66][67][68][69] or materials with high dielectric characteristics [66][67][68][69]. The described approach to stabilize rock-salt ZnO can also be used in other systems that include high-pressure phases that are difficult to quench.…”

Section: Stabilization Of Rs-zno In the Form Of Solid Solutionsmentioning

confidence: 99%

ZnO under Pressure: From Nanoparticles to Single Crystals

2022

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In the present review, new approaches for the stabilization of metastable phases of zinc oxide and the growth of ZnO single crystals under high pressures and high temperatures are considered. The problems of the stabilization of the cubic modification of ZnO as well as solid solutions on its basis are discussed. A thermodynamic approach to the description of zinc oxide melting at high pressures is described which opens up new possibilities for the growth of both undoped and doped (for example, with elements of group V) single crystals of zinc oxide. The possibilities of using high pressure to vary phase and elemental composition in order to create ZnO-based materials are demonstrated.

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Section: Stabilization Of Rs-zno In the Form Of Solid Solutionsmentioning

confidence: 99%

ZnO under Pressure: From Nanoparticles to Single Crystals

2022

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“…Intercalation or insertion solids are atomic structures capable of reversibly hosting ions/electrons without major structural disruption. 5 Intercalation processes involve vacant sites that are either originally present 6 or formed during a de-insertion reaction of alkali-ions 7 and/or transition metal (TM) migration 8 as is typically encountered in layered transition metal oxides. Cationic (TM or alkali-ions) vacancies are thus prominent species involved in redox intercalation mechanism eventually yielding long-range ordering 9 or local clustering 10 .…”

Section: Introductionmentioning

confidence: 99%

Cationic Vacancies in Anatase (TiO₂): Synthesis, Defect Characterization, and Ion-Intercalation Properties

Dambournet

2022

Acc. Chem. Res.

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CONSPECTUS. As one of the most studied materials, researches on titanium dioxide (TiO2) have flourished over the years owing to technological interests ranging from energy conversion and storage to medical implants and sensors, to name a few. In this scope, the development of synthesis routes enabling the stabilization of reactive surface structure has been largely investigated. Among these routes, solution-based synthesis has been utilized to tailor the material's properties spanning its atomic structural arrangement, or morphological aspects. One of the most investigated methods to stabilize crystals with tailored facets relies on the use of fluoride-based precursors. Fluoride ions not only provide a driving force for the stabilization of metastable/reactive surface structures but also alter the reactivity of titanium molecular precursors and in turn the structural features of the stabilized crystals. Here, we review recent progresses in the synthesis of solution-based synthesis

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“…These structural changes are closely related to the oxygen redox processes, with the partial irreversibility of the cation migration causing voltage fade [7]. Voltage hysteresis, for its part, appears to originate from kinetic limitations in the electron transfer, as recently published by Li et al [8].…”

Section: Introductionmentioning

confidence: 68%

The Influence of Synthesis Method on the Local Structure and Electrochemical Properties of Li-Rich/Mn-Rich NMC Cathode Materials for Li-Ion Batteries

et al. 2022

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Electrochemical energy storage plays a vital role in combating global climate change. Nowadays lithium-ion battery technology remains the most prominent technology for rechargeable batteries. A key performance-limiting factor of lithium-ion batteries is the active material of the positive electrode (cathode). Lithium- and manganese-rich nickel manganese cobalt oxide (LMR-NMC) cathode materials for Li-ion batteries are extensively investigated due to their high specific discharge capacities (>280 mAh/g). However, these materials are prone to severe capacity and voltage fade, which deteriorates the electrochemical performance. Capacity and voltage fade are strongly correlated with the particle morphology and nano- and microstructure of LMR-NMCs. By selecting an adequate synthesis strategy, the particle morphology and structure can be controlled, as such steering the electrochemical properties. In this manuscript we comparatively assessed the morphology and nanostructure of LMR-NMC (Li1.2Ni0.13Mn0.54Co0.13O2) prepared via an environmentally friendly aqueous solution-gel and co-precipitation route, respectively. The solution-gel (SG) synthesized material shows a Ni-enriched spinel-type surface layer at the {200} facets, which, based on our post-mortem high-angle annual dark-field scanning transmission electron microscopy and selected-area electron diffraction analysis, could partly explain the retarded voltage fade compared to the co-precipitation (CP) synthesized material. In addition, deviations in voltage fade and capacity fade (the latter being larger for the SG material) could also be correlated with the different particle morphology obtained for both materials.

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Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox

Cited by 93 publications

References 58 publications

ZnO under Pressure: From Nanoparticles to Single Crystals

ZnO under Pressure: From Nanoparticles to Single Crystals

Cationic Vacancies in Anatase (TiO₂): Synthesis, Defect Characterization, and Ion-Intercalation Properties

The Influence of Synthesis Method on the Local Structure and Electrochemical Properties of Li-Rich/Mn-Rich NMC Cathode Materials for Li-Ion Batteries

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Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox

Cited by 93 publications

References 58 publications

ZnO under Pressure: From Nanoparticles to Single Crystals

ZnO under Pressure: From Nanoparticles to Single Crystals

Cationic Vacancies in Anatase (TiO2): Synthesis, Defect Characterization, and Ion-Intercalation Properties

The Influence of Synthesis Method on the Local Structure and Electrochemical Properties of Li-Rich/Mn-Rich NMC Cathode Materials for Li-Ion Batteries

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Product

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Cationic Vacancies in Anatase (TiO₂): Synthesis, Defect Characterization, and Ion-Intercalation Properties