Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO<sub>2</sub> upon Li Extraction and Insertion

Mikhailova, Daria; Karakulina, Olesia M.; Batuk, Dmitry; Hadermann, Joke; Abakumov, Artem M.; Herklotz, Markus; Tsirlin, Alexander A.; Oswald, Steffen; Giebeler, Lars; Schmidt, Marcus; Eckert, J.; Knapp, Michael; Ehrenberg, Helmut

doi:10.1021/acs.inorgchem.6b01008

Cited by 22 publications

(37 citation statements)

References 39 publications

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“…The detailed scan spectrum of O 1s is presented in Figure 10b and composed of three components. As shown in Table 3, peak 3 was assigned to the O 2− state in rutile bulk (529.72 eV) [21,29], and peak 2 was assigned to the O 2− state in hydroxyl species on the rutile surface [30], including Ti-OH and Bi-OH (532.34 eV). It indicated that the hydroxylation process was present on rutile surface.…”

Section: Xps Analysismentioning

confidence: 99%

The Activation Mechanism of Bi3+ Ions to Rutile Flotation in a Strong Acidic Environment

et al. 2017

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Lead hydroxyl compounds are known as rutile flotation of the traditional activated component, but the optimum pH range for flotation is 2-3 using styryl phosphoric acid (SPA) as collector, without lead hydroxyl compounds in slurry solution. In this study, Bi 3+ ions as a novel activator was investigated. The results revealed that the presence of Bi 3+ ions increased the surface potential, due to the specific adsorption of hydroxyl compounds, which greatly increases the adsorption capacity of SPA on the rutile surface. Bi 3+ ions increased the activation sites through the form of hydroxyl species adsorbing on the rutile surface and occupying the steric position of the original Ca 2+ ions. The proton substitution reaction occurred between the hydroxyl species of Bi 3+ ions (Bi(OH) n +(3−n)) and the hydroxylated rutile surface, producing the compounds of Ti-O-Bi 2+. The micro-flotation tests results suggested that Bi 3+ ions could improve the flotation recovery of rutile from 61% to 90%, and from 61% to 64% for Pb 2+ ions.

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Section: Xps Analysismentioning

confidence: 99%

The Activation Mechanism of Bi3+ Ions to Rutile Flotation in a Strong Acidic Environment

et al. 2017

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“…Although O redox is anticipated, the established of TM‐O covalence bond is weak when only a 3d transition metal is involved, which could lead to O 2 release in the high voltage regions. Experimental and theoretical studies revealed that 4d and 5d transition metals effectively reduced the possibility of O 2 release via the formation of the strong covalent TM‐O bond 2d,10a,11. All of these factors should be seriously considered in material design for the practical use.…”

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confidence: 99%

Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries

et al. 2019

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of the most attractive inventions because they have dramatically improved our daily lives by enabling portable electronics, the onset of electronic mobility and electrical vehicles. [1] With the development of materials science, anionic redox chemistry, typically O redox, has enabled more energy storage than the traditional electrochemical reactions, in which the energy and power density are solely determined by the cation redox reaction of transition metals. [2] On the other hand, the rapid growth of lithium consumption leads to continuously increasing demand for lithium. Considering the uneven distribution of lithium resources, the inherent drawbacks of lithium supply and demand are difficult to overcome. [3] Therefore, an alternative to lithium must be considered, especially for large-scale energy storage applications in the foreseeable future.The Na-ion battery, which has a reaction pattern comparable with that of the Li-ion battery, is one of the promising alternatives because of its low cost and the abundance of sodium resources. [4] Currently, the study of Na-ion batteries is focused on improving their energy density. Considering the successful study of Lirich materials, one of the possible solutions to improve the capacity of Na-ion batteries is to develop Na-rich materials. It is very important to involve reversible O redox and expand the material series from the material design point of view.Recent research disclosed, the increasing of the Li(Na) content within layered structure materials can effectively influence the local atom coordination around oxygen atoms which could improve O redox upon cycling and lead to a higher capacity. [5] As demonstrated by Tarascon and Ceder et al., increasing the Li(Na) ratio can shift the O 2p nonbonding band gradually up near the Fermi level. This labile nonbonding O offers an extra way for electrons to move away, hence increasing the capacity by triggering an extra redox process. [2e,5c,6] This explanation has been successfully applied to Li 2 MnO 3 Li-rich materials [7] and is widely agreed upon. Benefitting from the established Li 2 MnO 3 Li-rich prototype, Li-rich material development has highly improved during the past decades, achieving additional capacity. [8] For the counterpart Na-ion battery design, although anionic redox was recently realized in the Mn-based To improve the energy and power density of Na-ion batteries, an increasing number of researchers have focused their attention on activation of the anionic redox process. Although several materials have been proposed, few studies have focused on the Na-rich materials compared with Li-rich materials. A key aspect is sufficient utilization of anionic species. Herein, a comprehensive study of Mn-based Na 1.2 Mn 0.4 Ir 0.4 O 2 (NMI) O3-type Na-rich materials is presented, which involves both cationic and anionic contributions during the redox process. The single-cation redox step relies on the Mn 3+ /Mn 4+ , whereas Ir atoms build a strong covalent bond with O and effectively suppress the O 2 release....

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“…(O 2 ) nperoxo-like species with O-O distances as short as 2.26 Å were also observed at high voltage and their strong covalent bonding to Rh was claimed to prevent O 2 release 11. When switching to Na-ion compounds, open questions remain.…”

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Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na₂IrO₃

et al. 2016

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The recent revival of the Na-ion battery concept has prompted intense activities in the search for new Na-based layered oxide positive electrodes. The largest capacity to date was obtained for a Na-deficient layered oxide that relies on cationic redox processes only. To go beyond this limit, we decided to chemically manipulate these Na-based layered compounds in a way to trigger the participation of the anionic network. We herein report the electrochemical properties of a Na-rich phase Na 2 IrO 3 , which can reversibly cycle 1.5 Na + per formula unit while not suffering from oxygen release nor cationic migrations. Such large capacities, as deduced by complementary XPS, X-ray/neutron diffraction and transmission electron microscopy measurements, arise from cumulative cationic and anionic redox processes occurring simultaneously at potentials as low as 3.0 V. The inability to remove more than 1.5 Na + is rooted in the formation of an O1-type phase having highly stabilized Na sites as confirmed by DFT calculations, which could rationalize as well the competing metal/oxygen redox processes in Na 2 IrO 3. This work will help to define the most fertile directions in the search for novel high energy Na-rich materials based on more sustainable elements than Ir.

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Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO₂ upon Li Extraction and Insertion

Cited by 22 publications

References 39 publications

The Activation Mechanism of Bi3+ Ions to Rutile Flotation in a Strong Acidic Environment

The Activation Mechanism of Bi3+ Ions to Rutile Flotation in a Strong Acidic Environment

Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries

Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na₂IrO₃

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Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO2 upon Li Extraction and Insertion

Cited by 22 publications

References 39 publications

The Activation Mechanism of Bi3+ Ions to Rutile Flotation in a Strong Acidic Environment

The Activation Mechanism of Bi3+ Ions to Rutile Flotation in a Strong Acidic Environment

Manganese‐Based Na‐Rich Materials Boost Anionic Redox in High‐Performance Layered Cathodes for Sodium‐Ion Batteries

Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na2IrO3

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Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO₂ upon Li Extraction and Insertion

Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na₂IrO₃