Efficient potential-tuning strategy through p-type doping for designing cathodes with ultrahigh energy density

Wang, Zhiqiang; Wang, Da; Zou, Zheyi; Song, Tao; Ni, Dixing; Li, Zhenzhu; Shao, Xuecheng; Yin, Wan‐Jian; Wang, Yanchao; Luo, Wenwei; Wu, Musheng; Avdeev, Maxim; Xu, Bo; Shi, Siqi; Ouyang, Chuying; Chen, Liquan

doi:10.1093/nsr/nwaa174

Cited by 55 publications

(29 citation statements)

References 34 publications

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“…Also, calculating vibrational properties and voltage behavior would be helpful to predict thermodynamic properties at finite temperatures and the electrochemical behavior of the system, respectively. [39] In total, by comprehensively evaluating the thermodynamic, kinetic, and electronic properties of layered CaTM 2 O 4 materials relevant to synthesis and electrochemical cycling, we show that this class of materials may open up a tremendous design space for the future of cathode materials for Ca batteries.…”

Section: Discussionmentioning

confidence: 98%

“…This design strategy will be further exploited in screening different TM combinations to identify novel Ca cathode materials with improved properties. To further deepen our understanding of layered CaTM 2 O 4 as a cathode for CIB and enhance the performance of this system, investigating possible anionic redox reactions [38] and optimizing CaTM 2 O 4 by doping [39] would be promising future directions. Also, calculating vibrational properties and voltage behavior would be helpful to predict thermodynamic properties at finite temperatures and the electrochemical behavior of the system, respectively.…”

Section: Discussionmentioning

confidence: 99%

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Layered Transition Metal Oxides as Ca Intercalation Cathodes: A Systematic First‐Principles Evaluation

Park

Bartel

Ceder

et al. 2021

Advanced Energy Materials

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to Mg, and they are much higher than Li (Ca: 4.2%, Mg: 2.3%, Li: 0.002% of Earth's crust), suggesting low materials cost and a secure supply chain. Despite the inherent advantages of Ca-based chemistry, much less research efforts have been put in Cathan in Mg-based chemistries.The emergence of Ca batteries has been hampered by the paucity of known materials functioning as electrolytes and electrodes. Recent development of electrolytes enabling facile Ca plating/ stripping [3] and fast Ca intercalation into graphite [4] sparked renewed interest in Ca-based energy storage. Recent studies found that such classes of materials as polyanionic phosphates, [5] Prussian Blue analogs, [6] and layered metal oxides [7,8] can reversibly accommodate Ca ions in nonaqueous systems; however, unlike for Mg, the design space for Ca cathode materials is still limited.In Mg ion chemistry, high-throughput computational studies discovered that the ability to modify spinel compounds by transition metal (TM) substitution results in promising Mg intercalation hosts with high voltage, energy density, and fast cation diffusion in both oxides [9] and sulfides. [10] Following these computational screening efforts, experiments demonstrated the promise of oxide spinels as cathode hosts allowing reversible Mg intercalation, [11][12][13] and ternary spinel chalcogenides even attracted interest as Mg solid electrolytes. [14] Also, the high compositional flexibility of spinel in forming TM solid solutions opens up a broader space for searching Mg cathodes. [12] However, the absence of such theory-based guidelines for Ca cathodes has hindered the development of Ca-ion batteries.Among the widely used structure types for conventional Li ion cathode materials (e.g., polyanion, layered, spinel), layered compounds with the nominal composition of CaTM 2 O 4 could be viable Ca cathode frameworks similar to spinel in Mg ion chemistry. Cabello et al. has shown that the P-type layered CaCo 2 O 4 , in which Ca cations are prismatically coordinated, can reversibly intercalate 0.35 mol of Ca and showed a capacity of 100 mAh g −1 . [7] Cushing et al. synthesized the two-layered (P2) or three-layered (P3) Ca x Co 2 O 4 at Ca concentrations x including 0.52, 0.54, 0.70, and 1, [15] indicating that partially Ca deintercalated CaCo 2 O 4 is not susceptible to chemical decomposition and maintains the original host framework. The phase diagram calculated by density functional theory (DFT) also confirmed that the partially deintercalated Ca x Co 2 O 4 (x = 0.5, 0.667, 0.7) compounds are stable. Beside the thermodynamic stability, Ca diffusivity in P3-CaCo 2 O 4 calculated by DFT using single ionic motion can be as low as 0.36 and 0.27 eV at the dilute and high Finding high-voltage Ca cathode materials is a critical step to unleashing the full potential of high-energy-density Ca-ion batteries. First-principles calculations are used to demonstrate that P-type layered calcium transition metal (TM) oxide materials (CaTM 2 O 4 ) with a range of TM substitutions (TM = Ti...

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Section: Discussionmentioning

confidence: 98%

Section: Discussionmentioning

confidence: 99%

Layered Transition Metal Oxides as Ca Intercalation Cathodes: A Systematic First‐Principles Evaluation

Park

Bartel

Ceder

et al. 2021

Advanced Energy Materials

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“…[8,9] Among them, FeS 2 (theoretical capacity,8 94.8 mAh g À1 )w ith attractive advantages of abundant resources,e nvironment-friend, especially stands out. [10] More importantly,F e-X (X, heteroatom) bonds generally display high-catalytic activity via asymmetric electron spin density and strong hybrid coordination, [11,12] which would benefit from the related reactions in…”

Section: Introductionmentioning

confidence: 99%

Ultra‐High Initial Coulombic Efficiency Induced by Interface Engineering Enables Rapid, Stable Sodium Storage

et al. 2021

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High initial coulombic efficiency is highly desired because it implies effective interface construction and few electrolyte consumption, indicating enhanced batteries life and power output. In this work, ah igh-capacity sodium storage material with FeS 2 nanoclusters ( % 1-2 nm) embedded in N, Sdoped carbon matrix (FeS 2 /N,S-C) was synthesized, the surface of which displays defects-repaired characteristic and detectable dot-matrix distributed Fe-N-C/Fe-S-C bonds.A fter the initial discharging process,t he uniform ultra-thin NaF-rich ( % 6.0 nm) solid electrolyte interphase was obtained, thereby achieving verifiable ultra-high initial coulombic efficiency ( % 92 %). The defects-repaired surface provides perfect platform, and the catalysis of dot-matrix distributed Fe-N-C/Fe-S-Cb onds to the rapid decomposing of NaSO 3 CF 3 and diethylene glycol dimethyl ether successfully accelerate the building of two-dimensional ultra-thin solid electrolyte interphase.D FT calculations further confirmed the catalysis mechanism. As ar esult, the constructed FeS 2 /N,S-C provides high reversible capacity (749.6 mAh g À1 at 0.1 Ag À1 )a nd outstanding cycle stability (92.7 %, 10 000 cycles,1 0.0 Ag À1 ). Especially,a tÀ15 8 8C, it also obtains ar eversible capacity of 211.7 mAh g À1 at 10.0 Ag À1 .A ssembled pouch-type cell performs potential application. The insight in this work provides abright way to interface design for performance improvement in batteries.

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“…For Li insertion into bulk materials, one approach is to estimate the energetics as a charge transfer process between different energy levels 35,36,37 , while leaving out other interactions, especially electrostatic due to their high complexity. Li adsorption on surfaces, including 2D materials, is considered to be a chemisorption process 38,39 , in which the Li 2s orbital hybridizes with surface valence levels, and the energy change depends on the degree of filling of the antibonding orbital.…”

Section: / 23mentioning

confidence: 99%

Screening and understanding Li adsorption on 2-dimensional metallic materials by learning physics

Gong

Wang

Zhu

et al. 2021

Preprint

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Two-dimensional (2D) materials have received considerable attention as possible electrodes in Li-ion batteries (LIBs), although a deeper understanding of the Li adsorption behavior as well as broad screening of the materials space is still needed. In this work, we build a high-throughput screening scheme that incorporates a learned interaction. First, density functional theory and graph convolution networks are utilized to calculate minimum Li adsorption energies for a small set of 2D metallic materials. The data is then used to find a dependence of the minimum Li adsorption energies on the sum of ionization potential, work function of the 2D metal, and coupling energy between Li+ and substrate. Our results show that variances of elemental properties and density are the most correlated features with coupling. To illustrate the applicability of this approach, the model is employed to show that some fluorides and chromium oxides are potential high-voltage materials with adsorption energies < -7 eV, and the found physics is used as the design principle to enhance the Li adsorption ability of graphene. This physics-driven approach shows higher accuracy and transferability compared with purely data-driven models.

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Efficient potential-tuning strategy through p-type doping for designing cathodes with ultrahigh energy density

Cited by 55 publications

References 34 publications

Layered Transition Metal Oxides as Ca Intercalation Cathodes: A Systematic First‐Principles Evaluation

Layered Transition Metal Oxides as Ca Intercalation Cathodes: A Systematic First‐Principles Evaluation

Ultra‐High Initial Coulombic Efficiency Induced by Interface Engineering Enables Rapid, Stable Sodium Storage

Screening and understanding Li adsorption on 2-dimensional metallic materials by learning physics

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