Dynamic impedance spectroscopy of LiMn2O4 thin films made by multi-layer pulsed laser deposition

Erinmwingbovo, Collins; Siller, Valerie; Nuñez, Marc; Trócoli, Rafael; Brogioli, Doriano; Morata, Álex; Mantia, Fabio La

doi:10.1016/j.electacta.2019.135385

Cited by 14 publications

(35 citation statements)

References 61 publications

(103 reference statements)

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“…Examples of DEIS application to study temporal evolution of charge transfer and diffusion parameters in intercalation materials such as LiMn 2 O 4 and nickel hexacyanoferrate are available in the literature. [ 64–66 ]…”

Section: Rate‐determining Steps In Ion Intercalation Processesmentioning

confidence: 99%

Metal‐Ion Coupled Electron Transfer Kinetics in Intercalation‐Based Transition Metal Oxides

Nikitina

Vassiliev

Stevenson

2020

Advanced Energy Materials

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Intensive research in the field of lithium ion intercalating systems over the last several decades resulted in the design of hundreds of active material and electrolyte systems for practical battery applications. [1][2][3] Given the high priority of achieving maximum capacity, energy density, and rate capability characteristics of the Li-ion batteries, as well as emerging Na-ion and K-ion batteries, the focus of the majority of studies on the Electrochemical metal-ion intercalation systems are acknowledged to be a critical energy storage technology. The kinetics of the intercalation processes in transition-metal based oxides determine the practical characteristics of metal-ion batteries, such as the energy density, power, and cyclability. With the emergence of post lithium-ion batteries, such as sodium-ion and potassium-ion batteries, which function predominately in nonaqueous electrolytes of special formulation and exhibit quite varied material stability with regard to their surface chemistries and reactivity with electrolytes, the practical routes for the optimization of metal-ion battery performance become essential. Electrochemical methods offer a variety of means to quantitatively study the diffusional, charge transfer, and phase transformation rates in complex systems, which are, however, rather rarely fully adopted by the metal-ion battery community, which slows down the progress in rationalizing the ratecontrolling factors in complex intercalation systems. Herein, several practical approaches for diagnosing the origin of the rate limitations in intercalation materials based on phenomenological models are summarized, focusing on the specifics of charge transfer, diffusion, and nucleation phenomena in redox-active solid electrodes. It is demonstrated that information regarding rate-determining factors can be deduced from relatively simple analysis of experimental methods including cyclic voltammetry, chronoamperometry, and impedance spectroscopy.

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Section: Rate‐determining Steps In Ion Intercalation Processesmentioning

confidence: 99%

Metal‐Ion Coupled Electron Transfer Kinetics in Intercalation‐Based Transition Metal Oxides

Nikitina

Vassiliev

Stevenson

2020

Advanced Energy Materials

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“…So, it is expected that different

l o g (v)

‐

l o g (d)

zone diagrams emerge in each case. Taking

k^{0}

=3×10 −6 cm s −1 for aqueous media with 1 M Li 2 SO 4 as electrolyte, [45] we thus constructed the zone diagram shown in Figure 7a. The grey dotted line shows one of the lines of the zone diagram for the organic electrolyte, to emphasize the shift with respect to the aqueous media line (pink dashed lines).…”

Section: Resultsmentioning

confidence: 99%

Voltammetric Behaviour of LMO at the Nanoscale: A Map of Reversibility and Diffusional Limitations

et al. 2021

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Understanding and optimizing single particle rate behaviour is normally challenging in composite commercial lithium‐ion electrode materials. In this regard, recent experimental research has addressed the electrochemical Li‐ion intercalation in individual nanosized particles. Here, we present a thorough theoretical analysis of the Li+ intercalation voltammetric behaviour in single nano/micro‐scale LiMn2O4 (LMO) particles, incorporating realistic interactions between inserted ions. A transparent 2‐dimensional zone diagram representation of kinetic‐diffusional behaviour is provided that allows rapid diagnosis of the reversibility and diffusion length of the system depending on the particle geometry. We provide an Excel file where the boundary lines of the zone diagram can be rapidly recalculated by setting input values of the rate constant, k0 and diffusion coefficient,D . The model framework elucidates the heterogeneous behaviour of nanosized particles with similar sizes but different shapes. Hence, we present here an outlook for realistic multiscale modelling of real materials.

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“…Improved techniques are being developed in this space targeted to the challenges of thin film batteries, ranging from the small currents and the need for accuracy and control, to methods such as dynamic impedance spectroscopy, or performing multi-frequency analysis during CV sweeps. [230] 8. The future An excellent piece of work showcasing the electrodes in use, growth mechanisms (e. g., from physical to chemical vapour techniques) and the importance of converting simple 2D structures into more complex 3D structures thereby increasing surface area and taking advantage of surface-based effects has recently been reported.…”

Section: Techniques To Probe Microbatteries and Their Interfacesmentioning

confidence: 99%

“…Modelling of the circuit elements with impedance spectroscopy can provide information on the role of the interfaces and charge transfer processes and their weighting. Improved techniques are being developed in this space targeted to the challenges of thin film batteries, ranging from the small currents and the need for accuracy and control, to methods such as dynamic impedance spectroscopy, or performing multi‐frequency analysis during CV sweeps …”

Section: Techniques To Probe Microbatteries and Their Interfacesmentioning

confidence: 99%

Pulsed Laser Deposition‐based Thin Film Microbatteries

Fenech

Sharma

2020

Chemistry An Asian Journal

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Emerging applications for robust small format or distributed devices feature a need for power and rechargeable lithium-ion batteries could play a significant role. This review focuses on a high precision technique to controllably grow thin-film electrodes or full all-solid-state batteries, that is, pulsed laser deposition (PLD). The technique and solidstate batteries are introduced followed by a detailed showcase of the depth of PLD-based growth undertaken on cathodes, electrolytes, anodes and whole microbatteries. Emphasis is placed on the various characterization techniques available to study PLD grown components and devices, and how interfaces become both critical and arguably easier to probe in PLD grown films or devices. This work provides a perspective on the techniques, its opportunities for electrodes and devices, and how to probe the resulting growth and its evolution in batteries.

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Dynamic impedance spectroscopy of LiMn2O4 thin films made by multi-layer pulsed laser deposition

Cited by 14 publications

References 61 publications

Metal‐Ion Coupled Electron Transfer Kinetics in Intercalation‐Based Transition Metal Oxides

Metal‐Ion Coupled Electron Transfer Kinetics in Intercalation‐Based Transition Metal Oxides

Voltammetric Behaviour of LMO at the Nanoscale: A Map of Reversibility and Diffusional Limitations

Pulsed Laser Deposition‐based Thin Film Microbatteries

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