Investigating the Mechanism of Reversible Lithium Insertion into Anti-NASICON Fe2(WO4)3

Barım, Gözde; Cottingham, Patrick; Zhou, Shiliang; Melot, Brent C.; Brutchey, Richard L.

doi:10.1021/acsami.6b16216

Cited by 16 publications

(12 citation statements)

References 35 publications

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“…The reversible (de)insertion of Li ions into densely packed intercalation hosts is a complex process of fundamental importance to rechargeable batteries. As positively charged ions move in and out of a structure, redox-active transition-metal centers change their formal oxidation state and, in the process, adjust their bond lengths so as to maintain local charge neutrality. , These complex structural distortions generate substantial strain in the lattice that manifests itself as large changes to the unit-cell volume during cycling, which can result in cracking of the electrode and delamination from the current collector, ultimately shortening the life of the battery. , Developing a deeper understanding of these structural transformations and how they influence charge transport is therefore a critical open question for designing new intercalation hosts.…”

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confidence: 99%

Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO₃

et al. 2018

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Understanding the structural transformations that materials undergo during (de)insertion of Li ions is crucial for designing high-performance intercalation hosts as these deformations can lead to significant capacity fade. Herein, we present a study of the metallic defect perovskite ReO3 to determine whether these distortions are driven by polaronic charge transport (i.e., the electrons and ions moving through the lattice in a coupled way) due to the semiconducting nature of most oxide hosts. Employing numerous techniques, including electrochemical probes, operando X-ray diffraction, X-ray photoelectron spectroscopy, and density functional theory calculations, we find that the cubic structure of ReO3 experiences multiple phase changes involving the correlated twisting of rigid octahedral subunits upon lithiation. This results in exceptionally poor long-term cyclability due to large strains upon lithiation, even though metallic character is maintained throughout. This suggests that phase transformations during alkali ion intercalation are the result of local strains in the lattice and not exclusively due to polaron migration.

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Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO₃

et al. 2018

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“…Related non-NTE materials, such as anti-NASICON Fe 2 (WO 4 ) 3 show a monoclinic to orthorhombic phase transition during lithium intercalation. Lithium insertion was facilitated via a concerted rotation of the rigid polyhedra in the host lattice driven by electrostatic interactions with the Li + ions …”

Section: Introductionmentioning

confidence: 99%

“…Lithium insertion was facilitated via a concerted rotation of the rigid polyhedra in the host lattice driven by electrostatic interactions with the Li + ions. 22 In addition to electrochemical activity, recent work has investigated the consequence of electrochemical treatment on thermal properties of various families of NTE materials, which is referred to as electrochemically activated thermal treatment. Here the terminology is given by a % of discharge or % of insertion of a cation into the electrode.…”

Section: ■ Introductionmentioning

confidence: 99%

Thermal Evolution and Phase Transitions in Electrochemically Activated Sc₂(MoO₄)₃

Liu

Sharma

2019

Inorg. Chem.

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Sc2(MoO4)3 shows negative thermal expansion (NTE) properties between −93 and +750 °C. Recently, electrochemical activation has been demonstrated to dramatically alter the phase evolution of structurally analogous Sc2(WO4)3. Electrochemical activation involves placing the material of choice in an electrochemical cell with Li, Na or K counter electrodes and discharging (or reacting Li+, Na+ and K+) which is followed by extraction of the activated electrode and subsequent thermal treatment. Here such a process is applied to Sc2(MoO4)3 and the results compared with the evolution of Sc2(WO4)3. For 12.5% lithium discharged Sc2(MoO4)3(12.5% of fully discharge capacity) the coefficient of thermal expansion (CTE) below 425 °C is −13.83(1) × 10–6/°C which is larger than parent material, and a new Li x MoO2 phase forms at about 425 °C. The 25% lithium discharged Sc2(MoO4)3 shows the formation of a new Li2MoO4 phase after discharging (electrochemical-based structural change) and on subsequent heat treatment the electrode mix transforms to Li3ScMo3O12. Interestingly, a range of new phases at various temperatures in the sodium and potassium discharged samples appear during heat treatment. For example, Na0.9Mo2O4 forms during thermal treatment of the 50% sodium discharged Sc2(MoO4)3 while KMo4O6 and K2MoO4 form with thermal treatment of 100% potassium discharged Sc2(MoO4)3. This work showcases the rich diversity in the phases that can be accessed during and post thermal treatment of Li, Na, and K discharged Sc2(MoO4)3 electrodes.

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“…Consequently, the design of structures that can reversibly and continuously accommodate large concentrations of Li-ions without substantial distortion or transformation of the framework has emerged as a critical imperative for realization of efficient high-rate cycling. Such design requires consideration of both geometric and electronic structure. − …”

Section: Introductionmentioning

confidence: 99%

Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V₂O₅

et al. 2017

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The design of cathodes for intercalation batteries requires consideration of both atomistic and electronic structure to facilitate redox at specific transition metal sites along with the concomitant diffusion of cations and electrons. Cation intercalation often brings about energy dissipative phase transformations that give rise to substantial intercalation gradients as well as multiscale phase and strain inhomogeneities. The layered α-V 2 O 5 phase is considered to be a classical intercalation host but is plagued by sluggish diffusion kinetics and a series of intercalation-induced phase transitions that require considerable lattice distortion. Here, we demonstrate that a 1D tunnel-structured ζ-phase polymorph of V 2 O 5 provides a stark study in contrast and can reversibly accommodate Li-ions without a large distortion of the structural framework and with substantial mitigation of polaronic confinement. Entirely homogeneous lithiation is evidenced across multiple cathode particles (in contrast to α-V 2 O 5 particles wherein lithiation-induced phase transformations induce phase segregation). Barriers to Li-ion as well as polaron diffusion are substantially diminished for metastable ζ-V 2 O 5 in comparison to the thermodynamically stable α-V 2 O 5 phase. The rigid tunnel framework, relatively small changes in coordination environment of intercalated Li-ions across the diffusion pathways defined by the 1D tunnels, and degeneracy of V 3d states at the bottom of the conduction band reduce electron localization that is a major impediment to charge transport in α-V 2 O 5 . The 1D ζ-phase thus facilitates a continuous lithiation pathway that is markedly different from the successive intercalation-induced phase transitions observed in α-V 2 O 5 . The results here illustrate the importance of electronic structure in mediating charge transport in oxide cathode materials and demonstrates that a metastable polymorph with higher energy bonding motifs that define frustrated coordination environments can serve as an attractive intercalation host.

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Investigating the Mechanism of Reversible Lithium Insertion into Anti-NASICON Fe₂(WO₄)₃

Cited by 16 publications

References 35 publications

Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO₃

Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO₃

Thermal Evolution and Phase Transitions in Electrochemically Activated Sc₂(MoO₄)₃

Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V₂O₅

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Investigating the Mechanism of Reversible Lithium Insertion into Anti-NASICON Fe2(WO4)3

Cited by 16 publications

References 35 publications

Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO3

Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO3

Thermal Evolution and Phase Transitions in Electrochemically Activated Sc2(MoO4)3

Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V2O5

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Investigating the Mechanism of Reversible Lithium Insertion into Anti-NASICON Fe₂(WO₄)₃

Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO₃

Correlated Polyhedral Rotations in the Absence of Polarons during Electrochemical Insertion of Lithium in ReO₃

Thermal Evolution and Phase Transitions in Electrochemically Activated Sc₂(MoO₄)₃

Mitigating Cation Diffusion Limitations and Intercalation-Induced Framework Transitions in a 1D Tunnel-Structured Polymorph of V₂O₅