Li transport in fresh and aged LiMn2O4 cathodes via electrochemical strain microscopy

Luchkin, Sergey Yu.; Romanyuk, Konstantin; Ivanov, Maxim; Kholkin, A. L.

doi:10.1063/1.4927816

Cited by 51 publications

(44 citation statements)

References 38 publications

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“…9(d). In this case, because the hysteresis loop area represents the degree of redistribution of lithium ions and is directly proportional to the magnitude of the electrochemical strain, [106,107] it is inferred that the large hysteresis loop can be obtained from the strong redistribution of lithium ions. Whereas the hysteresis loop with a small area does not show clear hysteric behavior, the large loop indicates ferroelectric-like hysteric behavior.…”

Section: Electrochemical Strainmentioning

confidence: 99%

Non-piezoelectric effects in piezoresponse force microscopy

Seol¹,

Kim²,

Kim³

2017

Current Applied Physics

135

114

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Piezoresponse force microscopy (PFM) has been used extensively for exploring nanoscale ferro/piezoelectric phenomena over the past two decades. The imaging mechanism of PFM is based on the detection of the electromechanical (EM) response induced by the inverse piezoelectric effect through the cantilever dynamics of an atomic force microscopy. However, several non-piezoelectric effects can induce additional contributions to the EM response, which often lead to a misinterpretation of the measured PFM response. This review aims to summarize the non-piezoelectric origins of the EM response that impair the interpretation of PFM measurements. We primarily discuss two major non-piezoelectric origins, namely, the electrostatic effect and electrochemical strain. Several approaches for differentiating the ferroelectric contribution from the EM response are also discussed. The review suggests a fundamental guideline for the proper utilization of the PFM technique, as well as for achieving a reasonable interpretation of observed PFM responses.

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Section: Electrochemical Strainmentioning

confidence: 99%

Non-piezoelectric effects in piezoresponse force microscopy

Seol¹,

Kim²,

Kim³

2017

Current Applied Physics

135

114

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“…248,257 The original description of ESM mechanism considered purely diffusional dynamics with fast voltage controlled generation-recombination of ionic species on the surface and near surface regions. 258 Subsequently, the model was extended to include both migration transport [259][260][261] and electrostrictive effects. 118,262,263 Finally, it was shown that ESM mechanism can be present even in the absence of a surface reaction.…”

Section: B Electrochemical Strain Microscopy (Esm)mentioning

confidence: 99%

Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale

Vasudevan

Balke

Maksymovych

et al. 2017

Applied Physics Reviews

270

206

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Ferroelectric materials have remained one of the foci of condensed matter physics and materials science for over 50 years. In the last 20 years, the development of voltage-modulated scanning probe microscopy techniques, exemplified by Piezoresponse force microscopy (PFM) and associated time-and voltage spectroscopies, opened a pathway to explore these materials on a single-digit nanometer level. Consequently, domain structures, walls and polarization dynamics can now be imaged in real space. More generally, PFM has allowed studying electromechanical coupling in a broad variety of materials ranging from ionics to biological systems. It can also be anticipated that the recent Nobel prize 1 in molecular electromechanical machines will result in rapid growth in interest in PFM as a method to probe their behavior on single device and device assembly levels. However, the broad introduction of PFM also resulted in a growing number of reports on nearly-ubiquitous presence of ferroelectric-like phenomena including remnant polar states and electromechanical hysteresis loops in materials which are non-ferroelectric in the bulk, or in cases where size effects are expected to suppress ferroelectricity. While in certain cases plausible physical mechanisms can be suggested, there is remarkable similarity in observed behaviors, irrespective of the materials system. In this review, we summarize the basic principles of PFM, briefly discuss the features of ferroelectric surfaces salient to PFM imaging and spectroscopy, and summarize existing reports on ferroelectric-like responses in non-classical ferroelectric materials. We further discuss possible mechanisms behind observed behaviors, and possible experimental strategies for their identification.3

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“…5 At the same time, ESM experiments on commercial Li-ion battery electrodes comprising the particles of ionic conductors embedded in a polymer binder matrix represent non-trivial problem due to complex geometry of the samples 6 and consequent difficulties 7 resulting in less predictable contributions of different origin into the strain response. 8,9 From that point of view, we can generally talk about strain-based SPM (s-SPM) with a number of contributions, which must be separated in the experiments. 10 Understanding and separation of these contributions is an important step from purely qualitative to quantitative data interpretation and analysis.…”

mentioning

confidence: 99%

Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

Аликин

Ievlev

Luchkin

et al. 2016

Applied Physics Letters

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Electrochemical strain microscopy (ESM) is a scanning probe microscopy (SPM) method in which the local electrodiffusion is probed via application of AC voltage to the SPM tip and registration of resulting electrochemical strain. Here, we implemented ESM to measure local strain in bulk LiMn2O4 cathodes of a commercial Li-battery in different states of charge to investigate distribution of Li-ion mobility and concentration. Ramped AC ESM imaging and voltage spectroscopy were used to find the most reliable regime of measurements allowing separating and diminishing different contributions to ESM. This is not a trivial task due to complex geometry of the sample and various obstacles resulting in less predictable contributions of different origins into ESM response: electrostatic tip–surface interactions, charge injection, electrostriction, and flexoelectricity. Understanding and control of these contributions is an important step towards quantitative interpretation of ESM data.

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Li transport in fresh and aged LiMn2O4 cathodes via electrochemical strain microscopy

Cited by 51 publications

References 38 publications

Non-piezoelectric effects in piezoresponse force microscopy

Non-piezoelectric effects in piezoresponse force microscopy

Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale

Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

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