Redox-Driven Spin Transition in a Layered Battery Cathode Material

Watanabe, Eriko; Zhao, Wenwen; Sugahara, Akira; Boisse, Benoit Mortemard de; Asakura, Daisuke; Okamoto, Yuri; Mizokawa, T.; Okubo, Masashi; Yamada, Atsuo

doi:10.1021/acs.chemmater.8b04775

Cited by 19 publications

(37 citation statements)

References 66 publications

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“…In the past, this relationship has been investigated mostly in the context of electron transfer processes accompanied by a change of the spin-state of the metal ion, 15 which are of particular relevance for a variety of biochemical reactions [16][17][18] and electrochemical devices. [19][20][21][22] Obviously, one of the most important factors determining mutually the redox potential, HOMO-LUMO levels and the spin state of transition metal complexes is the ligand field and there is an extensive literature dealing with these relationships among different complexes (for a recent example see ref. 23).…”

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confidence: 99%

“…In the past, this relationship has been investigated mostly in the context of electron transfer processes accompanied by a change of the spin-state of the metal ion, which are of particular relevance for a variety of biochemical reactions − and electrochemical devices. − Obviously, one of the most important factors determining mutually the redox potential, HOMO–LUMO levels, and the spin state of transition metal complexes is the ligand field, and there is an extensive literature dealing with these relationships among different complexes (for a recent example, see ref ). On the other hand, due primarily to experimental reasons, relatively few reports have been published on the concomitant investigation of redox and spin crossover properties of the same complex. − Yet, this provides a unique opportunity to investigate the influence of electronic effects on the redox potential, without the additional complexity brought into by ligand substitution.…”

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confidence: 99%

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On the Spin-State Dependence of Redox Potentials of Spin Crossover Complexes

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On the Spin-State Dependence of Redox Potentials of Spin Crossover Complexes

et al. 2020

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“…Redox-driven spin transitions are important processes that can greatly affect the operating potential of the electrodes. These experiments [101] predicted the existence of redox driven spin transition, which only occurs in the Co 3+ / Co 2 + redox coupling in layered transition metal oxides. By calculating the adiabatic free energy of Co ions in NaTi 0.5 Co 0.5 O 2 in each electronic state during discharging, as shown in Figure 9b, the Co 3+ LS during the discharge is reduced to a 1.1 V overpotent of Co 2+ LS.…”

Section: Spin-dependent Effects In Lithium/sodium-ion Batteries (Libs...mentioning

confidence: 92%

“…(b) Discharging process under calculated equilibrium potential between Co 3+LS and Co 2+ LS and under cathode cover potential (1.0 V vs. Na/Na + ). Reproduced with permission [101]. Copyright 2022, American Chemical Society.…”

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Research Progress of Spin-Dependent Effects in Catalysis and Energy Storage

Zhang¹

2022

MatLab

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Hydrogen fuel is highly valued as ideal clean energy to solve the environmental crisis. Electrolytic water splitting, as the most promising hydrogen production method, has been widely and deeply studied in recent ten years. On the other hand, lithium-ion batteries are considered the most popular energy storage equipment because of their high energy density, high working voltage, and long cycle life. However, the rapid development of society needs cheaper fuel, higher power density, and safer energy storage devices. Therefore, many new and efficient catalysts and electrode materials are being developed and explored. However, their electrochemical reaction mechanism must be clarified before they could be widely used in industry. In recent years, spin-dependent effects have been deeply studied in the field of catalysis and energy storage, which provides a theoretical foundation for analyzing the electrochemical reaction mechanism, preparing and screening promising catalytic and energy storage materials. This work summarizes the influence of spin-dependent effects on the physical and chemical properties of materials, mainly from four aspects, including electrocatalytic water splitting, metal-air batteries, lithium/sodium-sulfur batteries and lithium/sodium-ion batteries. Finally, we put forward some suggestions on the challenges and development of spin-dependent effects in catalysis and energy storage.

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“…Square-scheme electrochemistry in battery electrodes was demonstrated for redox-driven spin transition in layered transition-metal oxides Na x MO 2 (M: transition metal). 25 Na x MO 2 exhibits reversible Na + (de)intercalation (Figure 4a) 26 and thereby serves as a cathode material in sodium-ion batteries: 27 observed voltage hysteresis (3.0 V). The redox-driven spin transition of Co 3+ /Co 2+ has also been reported in other polytypes, such as P2-type Na 2/3 Ti 2/3 Co 1/3 O 2 .…”

Section: Redox-driven Spin Transitionmentioning

confidence: 99%

Square-Scheme Electrochemistry in Battery Electrodes

Okubo

Kawai

et al. 2021

Acc. Mater. Res.

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Conspectus Sustainable development cannot be achieved without substantial technological advancements. For instance, flexible electricity management requires smart power sourcing with advanced energy storage/conversion technologies. Remedies for abrupt power spikes/drops observed in renewable energy sources such as solar and wind require rapid load-leveling using high-power energy storage systems when they are integrated into a microgrid. Electrochemical energy storage devices efficiently convert electrical and chemical energy, which can potentially function as distributed power sources. Among these, lithium-ion batteries are a present de facto standard with their relatively high energy density and energy efficiencies that are based on topochemical intercalation chemistry, whereby guest lithium ions are (de)intercalated reversibly with simultaneous redox reactions and minimal structural changes. However, their energy density, power density, life-cycle cost, calendar life, and safety remain unsatisfactory for widespread use. When the storage capacity is maximized, as a result of which a labile deep charge/discharge state is generated, to develop batteries with high energy density, subsequent irreversible phase transformations or chemical reactions occur in many cases. The combination of the reversible electrode reactions and the subsequent irreversible phase transformations sometimes causes a charge/discharge curve characterized by a large voltage hysteresis with 100% Coulombic efficiency. Because a large voltage hysteresis significantly degrades the energy efficiency, unveiling the reaction mechanism is of primary importance in mitigating energy loss. In this Account, we comprehensively discuss the distinct and reversible charge/discharge reactions, generalized by the term “square scheme”, which includes both thermodynamic and kinetic processes. The difficulties encountered in analyzing the square scheme are that both energy efficient and inefficient processes coexist and compete with each other, where the latter involves the time-dependent phenomenon. Here, we provide the theoretical models and analytical expressions for kinetic square-scheme electrodes under several electrochemical conditions, including galvanostatic charge/discharge, the galvanostatic intermittent titration technique (GITT), the potentiostatic intermittent titration technique (PITT), and constant-current/constant-voltage (CC–CV) charge/discharge. The validity of the analytical models was confirmed for two typical square-scheme electrodes: Na1–x Ti0.5Co0.5O2 and Na2–x Mn3O7. Na1–x Ti0.5Co0.5O2, which is a sodium-ion battery cathode material, undergoes phase transitions between high-spin and low-spin states after transition-metal oxidation/reduction, while Na2–x Mn3O7, which is a large-capacity oxygen-redox cathode material, exhibits O–O bond formation after oxide-ion oxidation and O–O bond cleavage after peroxide reduction, both of which trigger large voltage hysteresis. This Account emphasizes the importance of the quantitative analyses of the...

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Redox-Driven Spin Transition in a Layered Battery Cathode Material

Cited by 19 publications

References 66 publications

On the Spin-State Dependence of Redox Potentials of Spin Crossover Complexes

On the Spin-State Dependence of Redox Potentials of Spin Crossover Complexes

Research Progress of Spin-Dependent Effects in Catalysis and Energy Storage

Square-Scheme Electrochemistry in Battery Electrodes

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