Anionic redox processes for electrochemical devices

Grimaud, Alexis; Hong, Wonbin; Shao‐Horn, Yang; Tarascon, Jean‐Marie

doi:10.1038/nmat4551

Cited by 628 publications

(639 citation statements)

References 65 publications

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“…High covalence was also supported by the Mn−O−Mn angle of 96.7° obtained by XRD analysis. It could lead to oxygen radicals,55 which are also discussed in the mechanism of natural photosynthesis (Figure 1, S 4 ) 10…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn₂O₄ in Comparison to Natural Photosynthesis

et al. 2017

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Targeted improvement of the low efficiency of water oxidation during the oxygen evolution reaction (OER) is severely hindered by insufficient knowledge of the electrocatalytic mechanism on heterogeneous surfaces. We chose LiMn2O4 as a model system for mechanistic investigations as it shares the cubane structure with the active site of photosystem II and the valence of Mn3.5+ with the dark‐stable S1 state in the mechanism of natural photosynthesis. The investigated LiMn2O4 nanoparticles are electrochemically stable in NaOH electrolytes and show respectable activity in any of the main metrics. At low overpotential, the key mechanistic parameters of Tafel slope, Nernst slope, and reaction order have constant values on the RHE scale of 62(1) mV dec−1, 1(1) mV pH−1, −0.04(2), respectively. These values are interpreted in the context of the well‐studied mechanism of natural photosynthesis. The uncovered difference in the reaction sequence is important for the design of efficient bio‐inspired electrocatalysts.

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Section: Resultsmentioning

confidence: 99%

Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn₂O₄ in Comparison to Natural Photosynthesis

et al. 2017

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“…Higher covalence shifts the O 2p band toward the Fermi level and thus facilitates the oxidation of surface lattice oxygen and the formation of point defects like V O and protonation. [34,39] Redox active lattice oxygen can therefore participate in OER mechanisms, creating an active state that is vulnerable to corrosion. [35,49] Specifically, lattice oxygen mediated OER mechanisms bear the risk of V O diffusion into the bulk of the catalyst, creating inhomogeneous strain.…”

Section: Corrosion Pathways and Driving Forcesmentioning

confidence: 99%

“…[6][7][8][9][10] Theoretical studies suggest that the catalytic activity of the four-electron transfer reaction forming molecular O 2 depends on strength and flexibility of the metal-oxygen bond, which can shift the redox activity from metal to lattice oxygen surface sites due to ligand hole formation. [7,28,34,39,40] Thus, an understanding of the underlying microscopic mechanisms, the nature of active sites, and catalyst stability is necessary to rationalize the search for active and stable catalysts.…”

Section: Introductionmentioning

confidence: 99%

Environmental TEM Investigation of Electrochemical Stability of Perovskite and Ruddlesden–Popper Type Manganite Oxygen Evolution Catalysts

Mierwaldt

Roddatis

Risch

et al. 2017

Advanced Sustainable Systems

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The sluggish kinetics of the oxygen evolution reaction (OER) is a grand challenge for energy storage technologies. Several perovskites and other oxides of earth‐abundant elements are found to exhibit improved catalytic OER activity. However, less attention is paid to the electrochemical stability, an important factor for large‐scale application. The ongoing search for stable catalysts calls for characterizing active catalyst surfaces and identifying mechanisms of deactivation, activation, or repair. In situ techniques are indispensable for these tasks. This study uses environmental transmission electron microscopy on the highly correlated perovskite Pr1–xCaxMnO3 and the Ruddlesden–Popper Pr0.5Ca1.5MnO4 as model electrodes to elucidate the underlying mechanisms of the stability trends identified on rotating ring disk electrodes. An electron beam at fluxes well below those that would cause radiation damage is used to induce positive local electrode potentials due to secondary electron emission, driving electrochemical reactions in H2O vapor. The stability of the model systems increases with increasing ionic character of the MnO bond, while more covalent bonds are prone to corrosion, which is triggered by formation of point defects in the oxygen sublattice.

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“…72 The research interest of the oxide ion redox for battery applications is triggered by studies with 4d transition metal elements, such as Ru 4+ and Nb 5+ , and now it has been extended to the Ti 4+ system as the 3d transition metal element. The material abundance of titanium is beneficial for battery applications, especially for electric vehicles and energy storage applications, and its reality is significantly enhanced.…”

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confidence: 99%

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

Yabuuchi¹

2017

Chem. Lett.

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Research interest for a solid-state redox reaction of oxide ions (oxygen) is rapidly increasing for rechargeable battery applications. This article reviews the history and development of charge compensation mechanisms with oxide ions for electrode materials of batteries. Reversible and irreversible processes are observed after the oxidation of oxide ions, and it highly depends on the natures of chemical bonds between transition metals and oxide ions. Future possibility of high-energy lithium/sodium batteries with the oxide ion redox is also discussed.

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Anionic redox processes for electrochemical devices

Abstract: Understanding and controlling the anionic redox processes is pivotal for the design of new Li-ion battery and water splitting materials.

Cited by 628 publications

References 65 publications

Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn₂O₄ in Comparison to Natural Photosynthesis

Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn₂O₄ in Comparison to Natural Photosynthesis

Environmental TEM Investigation of Electrochemical Stability of Perovskite and Ruddlesden–Popper Type Manganite Oxygen Evolution Catalysts

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

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Anionic redox processes for electrochemical devices

Abstract: Understanding and controlling the anionic redox processes is pivotal for the design of new Li-ion battery and water splitting materials.

Cited by 628 publications

References 65 publications

Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn2O4 in Comparison to Natural Photosynthesis

Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn2O4 in Comparison to Natural Photosynthesis

Environmental TEM Investigation of Electrochemical Stability of Perovskite and Ruddlesden–Popper Type Manganite Oxygen Evolution Catalysts

Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries

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Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn₂O₄ in Comparison to Natural Photosynthesis

Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn₂O₄ in Comparison to Natural Photosynthesis