Na2.4Al0.4Mn2.6O7 anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism

Soares, Cindy; Silván, Begoña; Choi, Yong Seok; Celorrio, Verónica; Seymour, Valerie R.; Cibin, Giannantonio; Griffin, John M.; Scanlon, David O.; Tapia‐Ruiz, Nuria

doi:10.1039/d1ta05137g

Cited by 12 publications

(12 citation statements)

References 80 publications

(169 reference statements)

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“…(d) pDOS, partial charge density and distribution of O−O bond lengths near unoccupied Mn sites before and after desodiation of Na 2 Mn 3 O 7 and Na 2.4 Al 0.4 Mn 2.6 O 7 . Reproduced with permission [69] . Copyright 2022, Royal Society of Chemistry.…”

Section: Tm Vacancies For Triggering Oxygen Redoxmentioning

confidence: 99%

Transition Metal Vacancy in Layered Cathode Materials for Sodium‐Ion Batteries

Zhou

2023

Chemistry A European J

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Anionic redox has been considered as a promising strategy to break the capacity limitation of cathode materials that solely relies on the intrinsic cationic redox in secondary batteries. Vacancy, as a kind of defect, can be introduced into transition metal layer to trigger oxygen redox, thus enhancing the energy density of layer-structured cathode materials for sodium-ion batteries. Herein, the formation process, recent progress in working mechanisms of triggering oxygen redox, as well as advanced characterization techniques for transition metal (TM) vacancy were overviewed and discussed. Strategies applied to stabilize the vacancy contained structures and harness the reversible oxygen redox were summarized. Furthermore, the challenges and prospects for further understanding TM vacancy were particularly emphasized.

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Section: Tm Vacancies For Triggering Oxygen Redoxmentioning

confidence: 99%

Transition Metal Vacancy in Layered Cathode Materials for Sodium‐Ion Batteries

Zhou

2023

Chemistry A European J

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“…The electronic structure analysis (DOS) and XPS analysis represent the active participation of oxygen in the redox process to achieve a high specific capacity of 190 mAh g –1 at a 4.2 V operating voltage (Figure d) . Soares et al used aliovalent doping to explain the important role of mixed-metal-based material for complete oxygen oxidation in Al 3+ - doped Na 2 Mn 3 O 7 material (Figure e). Additionally, a high specific capacity of 215 mAh g –1 was achieved (due to the participation of oxygen in anionic redox) with 90% capacity retention after 40 cycles.…”

Section: High-capacity Layered Cathodes For Sodium Ion Batteriesmentioning

confidence: 99%

“…(e) Schematic representation of Na + ion diffusion pathways at different concentrations of Na in Na x Al 0.4 Mn 2.6 O 7 cathode material. Reprinted with permission from ref . Copyright 2022 Royal Society of Chemistry.…”

Section: High-capacity Layered Cathodes For Sodium Ion Batteriesmentioning

confidence: 99%

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Opportunities and Challenges in the Development of Layered Positive Electrode Materials for High-Energy Sodium Ion Batteries: A Computational Perspective

Singh

Dixit

2022

Langmuir

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In recent years, high-energy-density sodium ion batteries (SIBs) have attracted enormous attention as a potential replacement for LIBs due to the chemical similarity between Li and Na, high natural abundance, and low cost of Na. Despite the promise of high energy, SIBs with layered cathode materials face several challenges including irreversible capacity loss, voltage hysteresis, voltage decay, irreversible TM migrations that lead to fast capacity fading, and structural degradation. However, their electrochemical performance can be improved by introducing reversible anionic redox along with conventional cationic redox. This Perspective systematically summarizes different factors that trigger the irreversible anionic redox in Na-based cathode materials. Additionally, this Perspective highlights the mechanistic understanding and key challenges for reversible anionic redox and proposes plausible solutions to overcome these limitations. The overview of various existing experimental and theoretical approaches presented here could provide a futuristic pathway to design Nabased cathode materials for high-energy-density SIBs.

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“…To improve the electrochemical properties of the layered materials, methods such as doping, − surface coating, and morphological control have been proposed, and among them, doping is an effective and simple approach that can stabilize the Mn–O structure in the transition metal layer (TM-layer). For example, nonmetallic dopants with high electronegativity reduce the covalency of M–O bonds and activity of oxygen atoms to improve the structural stability during the charging/discharging process. − Boron possessing the unique metalloid characteristics and high compatibility is an interesting dopant for layered materials, − but unfortunately, controlled incorporation of boron into selected sites in the layered structure of Na 2 Mn 3 O 7 is highly desirable, albeit challenging.…”

Section: Introductionmentioning

confidence: 99%

Modulation of Redox Chemistry of Na₂Mn₃O₇ by Selective Boron Doping Prompted by Na Vacancies

Wan

Qiu

Sun

et al. 2022

ACS Appl. Mater. Interfaces

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The small energy density and chemomechanical degradation of layered manganese oxide limit practical application to sodium-ion batteries (SIBs). Typically, Na2Mn3O7 shows a low redox plateau at 2.1 V versus Na/Na+, and the oxygen redox reaction at a high voltage causes structural collapse. Herein, a Na vacancy-induced boron doping strategy is demonstrated to improve the properties. Boron is incorporated into selective sites in the lattice in the center of the MnO6 octahedral ring at the O-layer. Bonding of boron in the TM layer enhances the electrochemical activity of low-valence Mn, giving rise to two reversible redox peaks at 2.45 and 2.55 V to enhance the average redox voltage. At the same time, the O 2p chemical state becomes weaker around the Fermi level, thus suppressing oxygen overoxidation for the high charge state and strengthening the layered structure during the redox reactions. The reduced Mn–O covalency and small diffusion barrier energy stemming from bonding of boron in the oxygen layer produce excellent rate characteristics. Modulation of the Mn 3d and O 2p orbital in Na2Mn3O7 by Na vacancies leads to selective doping of boron at different sites, and our results reveal that it is an important strategy for studying transition-metal-oxide-layered electrode materials.

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Na_2.4Al_0.4Mn_2.6O₇ anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism

Abstract: Here we report the synthesis via ceramic methods of the high-performance Mn-rich Na2.4Al0.4Mn2.6O7 oxygen-redox cathode material for Na-ion batteries which we use as a testbed material to study the effects...

Cited by 12 publications

References 80 publications

Transition Metal Vacancy in Layered Cathode Materials for Sodium‐Ion Batteries

Transition Metal Vacancy in Layered Cathode Materials for Sodium‐Ion Batteries

Opportunities and Challenges in the Development of Layered Positive Electrode Materials for High-Energy Sodium Ion Batteries: A Computational Perspective

Modulation of Redox Chemistry of Na₂Mn₃O₇ by Selective Boron Doping Prompted by Na Vacancies

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Na2.4Al0.4Mn2.6O7 anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism

Abstract: Here we report the synthesis via ceramic methods of the high-performance Mn-rich Na2.4Al0.4Mn2.6O7 oxygen-redox cathode material for Na-ion batteries which we use as a testbed material to study the effects...

Cited by 12 publications

References 80 publications

Transition Metal Vacancy in Layered Cathode Materials for Sodium‐Ion Batteries

Transition Metal Vacancy in Layered Cathode Materials for Sodium‐Ion Batteries

Opportunities and Challenges in the Development of Layered Positive Electrode Materials for High-Energy Sodium Ion Batteries: A Computational Perspective

Modulation of Redox Chemistry of Na2Mn3O7 by Selective Boron Doping Prompted by Na Vacancies

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Na_2.4Al_0.4Mn_2.6O₇ anionic redox cathode material for sodium-ion batteries – a combined experimental and theoretical approach to elucidate its charge storage mechanism

Modulation of Redox Chemistry of Na₂Mn₃O₇ by Selective Boron Doping Prompted by Na Vacancies