Kinetic square scheme in oxygen-redox battery electrodes

Kawai, Kazuki; Shi, Xiang‐Mei; Takenaka, Norio; Jang, Jeonguk; Boisse, Benoit Mortemard de; Tsuchimoto, Akihisa; Asakura, Daisuke; Kikkawa, Jun; Nakayama, Masanobu; Okubo, Masashi; Yamada, Atsuo

doi:10.1039/d1ee03503g

Cited by 40 publications

(47 citation statements)

References 72 publications

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“…The corresponding dQ / dV curves shown in Figure S7 also confirm the reduced redox polarization of the LMNLAO@BNT material, which indicates the enhanced delithiation/lithiation processes in LMNLAO@BNT. In addition, the oxidation peak at about 4.5 V and the reduction peak at about 3.4 V in the dQ / dV curves correspond to the redox of oxygen anions, and the sharper peaks in LMNLAO@BNT suggest the enhanced anion redox ability compared to LMNO and LMNLAO . As a result, the LMNLAO@BNT material can provide a higher specific charge capacity of 301.8 mAh g –1 and deliver a high specific capacity of 257.5 mAh g –1 during discharging, which is slightly higher than those of the LMNO material (231.9 mAh g –1 ), the La/Al codoped material LMNLAO material (244.8 mAh g –1 ; Figure a), increasing the Coulombic efficiency from 79.36% (LMNO) to 83.04% (LMNLAO) and then to 85.32% (LMNLAO@BNT; Table S2).…”

Section: Resultsmentioning

confidence: 97%

“…In addition, the oxidation peak at about 4.5 V and the reduction peak at about 3.4 V in the dQ/dV curves correspond to the redox of oxygen anions, and the sharper peaks in LMNLAO@BNT suggest the enhanced anion redox ability compared to LMNO and LMNLAO. 45 As a result, the LMNLAO@BNT material can provide a higher specific charge capacity of 301.8 mAh g −1 and deliver a high specific capacity of 257.5 mAh g −1 during discharging, which is slightly higher than those of the LMNO material (231.9 mAh g −1 ), the La/Al codoped material LMNLAO material (244.8 mAh g −1 ; Figure 3a), increasing the Coulombic efficiency from 79.36% (LMNO) to 83.04% (LMNLAO) and then to 85.32% (LMNLAO@BNT; Table S2). The rate capability tested at 0.1, 0.5, 1, 2, 5, and 10C further highlights the integrated advantages of the ferroelectric interface and La/Al codoping (Figure 3b).…”

Section: Electrochemical Performance Of the As-prepared Materials Fig...mentioning

confidence: 99%

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Integrating a Ferroelectric Interface with a Well-Tuned Electronic Structure in Lithium-Rich Layered Oxide Cathodes for Enhanced Lithium Storage

et al. 2022

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Li-rich layered oxides (LLOs) are considered promising candidates for new high-energy-density cathode materials for next-generation power batteries. However, their large-scale applications are largely hindered by irreversible Li/O loss, structural degradation, and interfacial side reactions during cycling. Herein, we demonstrate an integration strategy that tunes the electronic structure by La/Al codoping and constructs a ferroelectric interface on the LLOs surface through Bi0.5Na0.5TiO3 (BNT) coating. Experimental characterization reveals that the synergistic effect of the ferroelectric interface and the well-tuned electronic structure can not only promote the diffusion of Li+ and hinder the migration of O n– but also suppress the lattice volume changes and reduce interfacial side reactions at high voltages up to 4.9 V vs Li+/Li. As a result, the modified material shows enhanced initial capacities and retention rates of 224.4 mAh g–1 and 78.57% after 500 cycles at 2.0–4.65 V and 231.7 mAh g–1 and 85.76% after 200 cycles at 2.0–4.9 V at 1C, respectively.

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Section: Resultsmentioning

confidence: 97%

Section: Electrochemical Performance Of the As-prepared Materials Fig...mentioning

confidence: 99%

Integrating a Ferroelectric Interface with a Well-Tuned Electronic Structure in Lithium-Rich Layered Oxide Cathodes for Enhanced Lithium Storage

et al. 2022

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“…We employed random-forest regression to predict the energy density in the 2nd cycle (Fig. 4 15,36,37 while the moderate amount of excess Li maximizes a capacity (Fig. 5(b)).…”

Section: Resultsmentioning

confidence: 99%

“…Li1.3Nb0.3Mn0.4O2, 8 Na2RuO3, 9 and Na2Mn3O7. 10 However, several technical issues upon oxygen redox have been identified such as voltage hysteresis, voltage and capacity decay, [11][12][13] caused by oxygen dimer formation, 14,15 oxygen gas generation, 16,17 and transition metal migration. [18][19][20][21] Considering these kinetically competing side reactions, performance optimization needs simultaneous control of the synthesis conditions, charge/discharge protocols, chemical composition of Li1+xM1-xO2, crystallographic polymorphs, Crate, cut-off voltage, electrolyte, separator, electrode thickness, conducting carbon, binder, etc..…”

Section: Introductionmentioning

confidence: 99%

“…[18][19][20][21] Considering these kinetically competing side reactions, performance optimization needs simultaneous control of the synthesis conditions, charge/discharge protocols, chemical composition of Li1+xM1-xO2, crystallographic polymorphs, Crate, cut-off voltage, electrolyte, separator, electrode thickness, conducting carbon, binder, etc.. While researchers have attempted to reveal the relationship between the electrochemical property and these ACCEPTED MANUSCRIPT 4 intrinsic/extrinsic conditions, 15,18,[22][23][24][25] dominant factors in the performance of oxygen-redox cathodes are yet to be comprehensively understood.…”

Section: Introductionmentioning

confidence: 99%

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Machine Learning-based Comprehensive Survey on Lithium-rich Cathode Materials

2023

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The practical application of Li-rich cathode materials exhibiting higher energy density with oxygen redox activity requires improved cycle performance and energy efficiency. Since several conditions such as the amount of excess lithium, transition metal species, and cutoff voltage influence the electrochemical properties of Li-rich cathode materials, comprehensive determination of the optimal conditions often rely on repeating empirical try error processes. Here, the dominant factors in the energy density of Li-rich cathode materials were analyzed by constructing machine learning prediction models based on well-controlled experimental data for simplicity. Choosing a moderate amount of excess lithium and increasing the cobalt contents are the keys to achieve high energy density in longterm cycles.

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Voltage Hysteresis in Transition Metal Oxide Cathodes for Li/Na‐Ion Batteries

Liu

et al. 2023

Adv Funct Materials

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essential for the commercial application of Li/Na-ion batteries. The investigated cathode materials mainly include oxides, polyanion compounds, Prussian blue analogues, and organic salts. Among them, layered transition metal oxides contained in oxides are promising candidates due to their suitable operational potentials, 2D ions diffusion channels, and simple synthesis. Meanwhile, it was generally believed that to achieve a fast ions diffusion, the atomic configuration in the crystal structure of layered cathode materials must be well ordered. [7,8] However, this stereotype is now being reconsidered with the discovery of the percolation theory about 3D ions diffusion in a disordered rock-salt (DRX) structure. [9,10] This percolation occurs when Li-ions hop from one octahedral site to another through an intermediate tetrahedral site, where the Liions in the tetrahedral sites are identified as an active Li for the hopping. [11] In this regard, various new types of Li-rich DRX cathode materials with promising capacities (>250 mAh g −1 ) have been discovered. [12][13][14][15][16][17][18][19] Given their unique advantages, these oxide materials have attracted extensive attention from researchers worldwide.Although demonstrating a high capacity, application-wise, these oxide materials also exhibit voltage hysteresis and significant loss of energy density, since the voltage associated with this redox process on charge cannot be recovered on discharge, which represents a key challenge that inhibits exploiting the full potential of these materials. This voltage hysteresis persists throughout the electrochemical cycling, resulting in a continuous decrease of the average discharge voltage. Therefore, the understanding of voltage hysteresis is particularly important because it not only minimizes energy density and drastically reduces energy efficiency but also hinders further development and commercialization of Li/Na-ion batteries. When voltage hysteresis was discovered in LiFePO 4 materials in the early years, experimental limitations and the lack of a theoretical framework prevented researchers from drawing concrete conclusions about the phenomenon. With the development of increasingly sophisticated analytical techniques for studying voltage hysteresis, reassessing the understanding of the origin of voltage hysteresis can now be done from a mechanical perspective and even reveal new discoveries that were previously unavailable due to experimental limitations. [20]

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Kinetic square scheme in oxygen-redox battery electrodes

Abstract: Kinetic formation of the peroxo-like O22− dimer is identified as the origin of a voltage hysteresis in oxygen-redox battery electrodes.

Cited by 40 publications

References 72 publications

Integrating a Ferroelectric Interface with a Well-Tuned Electronic Structure in Lithium-Rich Layered Oxide Cathodes for Enhanced Lithium Storage

Integrating a Ferroelectric Interface with a Well-Tuned Electronic Structure in Lithium-Rich Layered Oxide Cathodes for Enhanced Lithium Storage

Machine Learning-based Comprehensive Survey on Lithium-rich Cathode Materials

Voltage Hysteresis in Transition Metal Oxide Cathodes for Li/Na‐Ion Batteries

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