How inactive d0 transition metal controls anionic redox in disordered Li-rich oxyfluoride cathodes

Li, Yining; Zhao, Xiaolin; Bao, Qisheng; Cui, Mengnan; Qiu, Wujie; Li, Jianjun

doi:10.1016/j.ensm.2020.07.013

Cited by 20 publications

(35 citation statements)

References 48 publications

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“…38 Accordingly, the boundary between reversible and irreversible anionic electrochemical reactions determines the upper limit of the reversible capacity of this electrode, which is much lower than the theoretical capacity. The accurate calculation of charge transfer limit, N e,max , requires thermodynamic and dynamic processes of electrochemical reactions, 35,39 which will be discussed in detail in Section 5.2.…”

Section: Specific Capacitymentioning

confidence: 99%

“…Combining with electrochemical activities contributed by post-TMs and anions, Li-rich cathodes can achieve a synergistic enhancement of specific capacity and cycling stability. 34,39,82 In identifying the critical state of OER, the central focus should be the evaluation of oxygen stability, which can be classified into two approaches of thermodynamics and dynamics. The thermodynamic approach mainly investigates the formation and stability of oxygen vacancies during delithiation.…”

Section: Capacity Decaymentioning

confidence: 99%

“…As shown by the red line in Figure 4, Li et al found that in the Li 2Àx Mn 0.5 Ti 0.5 O 2 F structure, the formation energy of oxygen vacancies is below zero when x > 0.78. 39 This suggests that oxygen loss is thermodynamically favorable when x > 0.78, and the electrochemical reaction in this stage would inevitably cause oxygen release. The reversible capacity of the material is thus limited to 193 mAhg À1 (x = 0.78), which is much lower than the theoretical capacity of 461 mAhg À1 .…”

Section: Capacity Decaymentioning

confidence: 99%

“…By employing this method, Li et al determined that the reversible capacity of Li 2 Mn 0.5 Ti 0.5 O 2 F is 245 mAhg À1 , which is much lower than its theoretical capacity of 461 mAhg À1 . 39 Because of extreme computational cost, this method is limited to case-by-case studies, rendering it much difficult to realize high-throughput calculations of reversible capacity and its decay. A breakthrough in realizing such a high-throughput technique might be the efficient sampling in phase space and the fast evolution of structural dynamics.…”

Section: Capacity Decaymentioning

confidence: 99%

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Multiscale computations and artificial intelligent models of electrochemical performance in Li‐ion battery materials

Qiu

Wang

Liu

2021

WIREs Comput Mol Sci

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Li-ion battery (LIB) is widely used as one of renewable energy resources for powerful electronics and electric vehicles. The main challenge in developing next-generation LIB is to further improve the energy density, rate capability, and cycling stability of electrode and electrolyte materials. With the rapid development of computational science, the material design has changed from the traditional trial-and-error approach to integrated database-based computation. Multiscale computational methods and machine learning (ML) not only speed up the development of new materials, but also provide insight into the intrinsic relationship between the microscopic composition and macroscopic performance of materials. In this review, we revealed the correlation of electrochemical activity of LIB materials with the response of energy to variable parameters such as charge-transfer number and Li-ion diffusion coordinates.Based on the structure-property relationship, we reviewed multiscale calculation and ML methods for electrochemical properties in LIB materials. A comparison for various applied methods was outlined to provide a methodselecting reference in LIB material design. It is expected that a deep combination of multiscale computations, experimental data, ML should be more powerful methods for discovering new LIB materials.

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Section: Specific Capacitymentioning

confidence: 99%

Section: Capacity Decaymentioning

confidence: 99%

Section: Capacity Decaymentioning

confidence: 99%

Section: Capacity Decaymentioning

confidence: 99%

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Multiscale computations and artificial intelligent models of electrochemical performance in Li‐ion battery materials

Qiu

Wang

Liu

2021

WIREs Comput Mol Sci

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“…[ 1 ] Exemplary intercalation anodes contain graphite, early transition metal oxides (TMO, e.g., TiO 2 , VO 2 and Nb 2 O 5 ) and transition metal (TM) compounds (e.g., Li 4 Ti 5 O 12 and MXene). [ 1f,2 ] These electrodes provide stable framework and empty sites for electron and lithium‐ion transport, thus possessing high reversibility with negligible volume change. [ 1e,3 ] For graphite, the side reaction triggered by co‐intercalation of electrolytes would form solid‐electrolyte interface (SEI), which severely retards long cyclic stability.…”

Section: Introductionmentioning

confidence: 99%

A Dual‐Functional Titanium Nitride Chloride Layered Matrix with Facile Lithium‐Ion Diffusion Path and Decoupled Electron Transport as High‐Capacity Anodes

Zhao

Dong

Wang

et al. 2022

Adv Funct Materials

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Intercalation typed electrodes are expected with low theoretical capacity, which falls behind their high rate performance and stability. In this work, α‐TiNCl, an isoelectronic system of TiO2, is designed as a promising high‐capacity intercalation anode. TiNCl features are layered TiN backbone terminated by Cl atoms. While the rocksalt TiN backbones function as electron conductors, the interlayer voids provide Cl‐coordinated Li+ sites without strong Li‐Ti repulsion, which proves to be a rapid diffusion path with a low energy barrier (0.06 vs 0.47 eV of TiO2). Therefore, a dual‐functional TiNCl matrix is established for Li+ and e– transport. To stabilize the layered structure, TiNCl is scaffolded by an in situ grown TiO2 coating, which also serves as an electron reservoir during lithiation. The TiNCl‐TiO2 anode exhibits significantly large Li+ intercalation capacity (243% of TiO2) and outstanding battery performance (231 mA h g–1 at ≈17 C for 2500 cycles, 94 mA h g–1 at ≈34 C for 10 000 cycles). The (+) LiCoO2 || TiNCl‐TiO2 (–) full battery maintains 170 mA h g–1 for 300 cycles. This work may shed light on the molecular engineering of new compounds for electrodes.

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A New Class of High‐Capacity Fe‐Based Cation‐Disordered Oxide for Li‐Ion Batteries: Li‐Fe‐Ti‐Mo Oxide

2023

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Low‐cost Fe can be used for forming cation‐disordered rocksalt Li‐excess (DRX) materials instead of high‐cost d0‐species and then the Fe‐based DRX can be promising electrode materials because they can theoretically achieve high capacity, resulting from additional oxygen redox reaction and stable cation‐disordered structure. However, Fe‐based DRX materials suffer from large voltage hysteresis, low electrochemical activity, and poor cyclability, so it is highly challenging to utilize them as practical electrode materials for a cell. Here, novel high‐capacity Li‐Fe‐Ti‐Mo electrode materials (LFTMO) with high average discharge voltage and reasonable stability are reported. The effect of Ti/Mo on electrochemical reactions in Fe‐based DRX materials (LFTMO) is studied by controlling its composition ratio and using techniques for analyzing the local environment to find the key factors that improve its activity. It is found out that the introduction of appropriate quantity of redox‐active Mo4+/5+ to Fe‐based DRX materials can help stabilize the oxygen redox reaction via changing a local structure and can suppress a Fe redox reaction, which can cause poor performance. The understandings will help develop high capacity and long cyclability Fe‐based DRX electrode materials.

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How inactive d0 transition metal controls anionic redox in disordered Li-rich oxyfluoride cathodes

Cited by 20 publications

References 48 publications

Multiscale computations and artificial intelligent models of electrochemical performance in Li‐ion battery materials

Multiscale computations and artificial intelligent models of electrochemical performance in Li‐ion battery materials

A Dual‐Functional Titanium Nitride Chloride Layered Matrix with Facile Lithium‐Ion Diffusion Path and Decoupled Electron Transport as High‐Capacity Anodes

A New Class of High‐Capacity Fe‐Based Cation‐Disordered Oxide for Li‐Ion Batteries: Li‐Fe‐Ti‐Mo Oxide

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