Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

Аликин, Д. О.; Ievlev, Anton V.; Luchkin, Sergey Yu.; Турыгин, А. П.; Shur, V. Ya.; Kalinin, Sergei V.; Kholkin, A. L.

doi:10.1063/1.4943944

Cited by 25 publications

(23 citation statements)

References 25 publications

(26 reference statements)

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“…3 ), especially the conversion of the I – V resistance shift in relevant ionic parameters, e.g., local ionic mobility or diffusivity. This is an ongoing activity and represents the topic of state-of-the-art studies [ 18 ]. However, the observations reported in Fig.…”

Section: Resultsmentioning

confidence: 99%

Nanoscale electrochemical response of lithium-ion cathodes: a combined study using C-AFM and SIMS

Beeck¹,

Labyedh²,

Sepúlveda³

et al. 2018

Beilstein J. Nanotechnol.

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The continuous demand for improved performance in energy storage is driving the evolution of Li-ion battery technology toward emerging battery architectures such as 3D all-solid-state microbatteries (ASB). Being based on solid-state ionic processes in thin films, these new energy storage devices require adequate materials analysis techniques to study ionic and electronic phenomena. This is key to facilitate their commercial introduction. For example, in the case of cathode materials, structural, electrical and chemical information must be probed at the nanoscale and in the same area, to identify the ionic processes occurring inside each individual layer and understand the impact on the entire battery cell. In this work, we pursue this objective by using two well established nanoscale analysis techniques namely conductive atomic force microscopy (C-AFM) and secondary ion mass spectrometry (SIMS). We present a platform to study Li-ion composites with nanometer resolution that allows one to sense a multitude of key characteristics including structural, electrical and chemical information. First, we demonstrate the capability of a biased AFM tip to perform field-induced ionic migration in thin (cathode) films and its diagnosis through the observation of the local resistance change. The latter is ascribed to the internal rearrangement of Li-ions under the effect of a strong and localized electric field. Second, the combination of C-AFM and SIMS is used to correlate electrical conductivity and local chemistry in different cathodes for application in ASB. Finally, a promising starting point towards quantitative electrochemical information starting from C-AFM is indicated.

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Section: Resultsmentioning

confidence: 99%

Nanoscale electrochemical response of lithium-ion cathodes: a combined study using C-AFM and SIMS

Beeck¹,

Labyedh²,

Sepúlveda³

et al. 2018

Beilstein J. Nanotechnol.

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“…As the last step, the sample surface was treated by Ar plasma to thin and possibly remove the damaged surface layer. A more detailed procedure of sample preparation can be found elsewhere [17,18].…”

Section: Methodsmentioning

confidence: 99%

“…The strain is believed to be caused by the Vegard expansion induced by the local change of the ion concentration [9,10]. The corresponding response was observed in a wide range of ionically active materials, such as lithium battery materials: lithium manganites [11] and cobaltites [7,12], amorphous silicon (used as an anode material in lithium-ion batteries) [6], nanocrystalline LiFePO 4 [13], a high-temperature ionic conductor cerium oxide in the form of thin films [14,15] and bulk ceramics [16], lithium manganate extracted from commercial lithium batteries [17,18], solid state electrolytes [19], and even organic transistors [20]. A special case proving the possibility to induce large rearrangements of ions under the action of the tip-induced electric field is the formation of metal islands on the surface of some Li- and Ag-conducting glasses [21,22].…”

Section: Introductionmentioning

confidence: 99%

“…Nevertheless, in most of the cases, the nature of the ESM response is still under discussion because of a variety of other parasitic processes accompanying the electromechanical strain in the voltage modulated AFM measurements. Most of the parasitic contribution are associated with the application of a DC voltage, such as charge injection as well as local electrochemical reactions and phase transitions [18,23]. Recently, Seol et al demonstrated an alternative approach based on implementation of the ESM without application of a DC bias in a low-frequency AC range in Li-ion conductive glass ceramics [24].…”

Section: Introductionmentioning

confidence: 99%

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Correlative Confocal Raman and Scanning Probe Microscopy in the Ionically Active Particles of LiMn2O4 Cathodes

et al. 2019

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In this contribution, a correlative confocal Raman and scanning probe microscopy approach was implemented to find a relation between the composition, lithiation state, and functional electrochemical response in individual micro-scale particles of a LiMn2O4 spinel in a commercial Li battery cathode. Electrochemical strain microscopy (ESM) was implemented both at a low-frequency (3.5 kHz) and in a high-frequency range of excitation (above 400 kHz). It was shown that the high-frequency ESM has a significant cross-talk with topography due to a tip-sample electrostatic interaction, while the low-frequency ESM yields a response correlated with distributions of Li ions and electrochemically inactive phases revealed by the confocal Raman microscopy. Parasitic contributions into the electromechanical response from the local Joule heating and flexoelectric effect were considered as well and found to be negligible. It was concluded that the low-frequency ESM response directly corresponds to the confocal Raman microscopy data. The analysis implemented in this work is an important step towards the quantitative measurement of diffusion coefficients and ion concentration via strain-based scanning probe microscopy methods in a wide range of ionically active materials.

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“…The sample sections were embedded in a commercial epoxy resin and then polished step-by-step, first, mechanically by diamond abrasive and silica suspension, and, second, by Ar ion beam milling. A more detailed procedure of sample preparation can found elsewhere [38,39]. electrolyte.…”

Section: Sample Preparationmentioning

confidence: 99%

Local Study of Lithiation and Degradation Paths in LiMn2O4 Battery Cathodes: Confocal Raman Microscopy Approach

et al. 2018

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Lithium manganese-based cathodes are widely used in rechargeable batteries due to their low cost, safety, and ecological stability. On the other hand, fast capacity fade occurs in LiMn 2 O 4 mainly because of the induced manganese dissolution and formation of additional phases. Confocal Raman microscopy provides many opportunities for sensitive and spatially resolved structural studies of micro-and nanoscale phenomena. Here, we demonstrate advantages of confocal Raman spectroscopy approach for uncovering the mechanisms of lithiation/delithiation and degradation in LiMn 2 O 4 commercial cathodes. The analysis of Raman spectra for inspecting local lithiation state and phase composition is proposed and exploited for the visualization of the inhomogeneous distribution of lithium ions. The cycling of cathodes is shown to be followed by the formation and dissolution of the Mn 3 O 4 phase and local disturbance of the lithiation state. These processes are believed to be responsible for the capacity fade in the commercial batteries.

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Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

Cited by 25 publications

References 25 publications

Nanoscale electrochemical response of lithium-ion cathodes: a combined study using C-AFM and SIMS

Nanoscale electrochemical response of lithium-ion cathodes: a combined study using C-AFM and SIMS

Correlative Confocal Raman and Scanning Probe Microscopy in the Ionically Active Particles of LiMn2O4 Cathodes

Local Study of Lithiation and Degradation Paths in LiMn2O4 Battery Cathodes: Confocal Raman Microscopy Approach

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