DOI: 10.1063/1.4943944. Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

Characterization of LiMn2O4 cathodes by electrochemical strain microscopy

10.1063/1.4943944

Crossref journal-article

AIP Publishing

Applied Physics Letters (317)

Abstract

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.

Bibliography

Alikin, D. O., Ievlev, A. V., Luchkin, S. Yu., Turygin, A. P., Shur, V. Ya., Kalinin, S. V., & Kholkin, A. L. (2016). Characterization of LiMn2O4 cathodes by electrochemical strain microscopy. Applied Physics Letters, 108(11).

Authors 7

D. O. Alikin (first)
A. V. Ievlev (additional)
S. Yu. Luchkin (additional)
A. P. Turygin (additional)
V. Ya. Shur (additional)
S. V. Kalinin (additional)
A. L. Kholkin (additional)

References 27 Referenced 27

10.1002/adma.201001190 / Adv. Mater. / Local electrochemical functionality in energy storage materials and devices by scanning probe microscopies: Status and perspectives (2010)
10.1088/0957-4484/24/42/420201 / Nanotechnology / Nanoscience and nanotechnology in next generation lithium batteries (2013)
10.1063/1.3460637 / J. Appl. Phys. / Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms (2010)
10.1063/1.3446838 / Appl. Phys. Lett. / Electromechanical probing of ionic currents in energy storage materials (2010)
10.1007/s10832-013-9819-7 / J. Electroceram. / Electrochemical strain microscopy of local electrochemical processes in solids: Mechanism of imaging and spectroscopy in the diffusion limit (2014)
10.1016/j.jpowsour.2010.04.066 / J. Power Sources / Measurement of three-dimensional microstructure in a LiCoO2 positive electrode (2011)
10.1016/j.msea.2013.11.044 / Mater. Sci. Eng. A / Mechanical property measurements of heterogeneous materials by selective nanoindentation: Application to LiMn2O4 cathode (2014)
10.1063/1.4927816 / J. Appl. Phys. / Li transport in fresh and aged LiMn2O4 cathodes via electrochemical strain microscopy (2015)
10.1063/1.4927747 / J. Appl. Phys. / Electrochemical strain microscopy time spectroscopy: Model and experiment on LiMn2O4 (2015)
10.1016/j.jmat.2015.03.001 / J. Mater. / Strain-based scanning probe microscopies for functional materials, biological structures, and electrochemical systems (2015)
10.1016/j.actamat.2015.01.074 / Acta Mater. / Mechanical properties of commercial LixMn2O4 cathode under different states of charge (2015)
10.1088/0957-4484/18/43/435503 / Nanotechnology / The band excitation method in scanning probe microscopy for rapid mapping of energy dissipation on the nanoscale (2007)
10.1038/nchem.1112 / Nat. Chem. / Measuring oxygen reduction/evolution reactions on the nanoscale (2011)
10.1021/nn3020757 / ACS Nano / Ionically mediated electromechanical hysteresis in transition metal oxides (2012)
10.1088/0022-3727/44/46/464006 / J. Phys. D: Appl. Phys. / Band excitation in scanning probe microscopy: Sines of change (2011)
10.1063/1.4882861 / Appl. Phys. Lett. / Electrostrictive and electrostatic responses in contact mode voltage modulated scanning probe microscopies (2014)
10.1021/ja3091438 / J. Am. Chem. Soc. / The Li-ion rechargeable battery: A perspective (2013)
10.1063/1.4873386 / Appl. Phys. Lett. / Voltage induced local hysteretic phase switching in silicon (2014)
10.1088/0957-4484/25/44/445701 / Nanotechnology / Self-consistent modeling of electrochemical strain microscopy of solid electrolytes (2014)
10.1038/ncomms8572 / Nat. Commun. / Strong piezoelectricity in single-layer graphene deposited on SiO2 grating substrates (2015)
See supplementary material at http://dx.doi.org/10.1063/1.4943944 for Figure 1 which shows topography evolution under the DC voltage pulses. Figure 2 shows application of contour analysis to the ESM image of distinct particle. Figure 3 shows eigen vectors and main components obtained by PCA analysis.
10.1039/a905575d / J. Mater. Chem. / Electronic structure and stability of the LixMn2O4 (0 < x < 2) system (1999)
{'volume-title': 'Multivariate Observations', 'year': '2004', 'key': '2023061722554786600_c23'} / Multivariate Observations (2004)
10.1046/j.1365-2818.1998.3250876.x / J. Microsc. / Multivariate statistical methods for the analysis of microscope image series: Applications in materials science (1998)
10.1088/0957-4484/20/8/085714 / Nanotechnology / Principal component and spatial correlation analysis of spectroscopic-imaging data in scanning probe microscopy (2009)
10.1021/acsnano.5b05818 / ACS Nano (2015)
10.1088/0957-4484/27/12/125302 / Nanotechnology / Graphene engineering by neon ion beams (2016)

Dates

Type	When
Created	9 years, 5 months ago (March 15, 2016, 1 p.m.)
Deposited	2 years, 2 months ago (June 17, 2023, 6:55 p.m.)
Indexed	10 minutes ago (Aug. 27, 2025, 5:03 a.m.)
Issued	9 years, 5 months ago (March 14, 2016)
Published	9 years, 5 months ago (March 14, 2016)
Published Online	9 years, 5 months ago (March 15, 2016)
Published Print	9 years, 5 months ago (March 14, 2016)

Funders 2

FP7 Marie Curie Initial Training Network
Awards1
1. Grant Agreement No. 290158
Centro de Investigação em Materiais Cerâmicos e Compósitos 10.13039/100007889
Region: Europe
gov (Local government)
Labels2
1. Centre for Research in Ceramics and Composite Materials
2. CICECO
Awards1
1. FCT UID/CTM/50011/2013

BibTeX

@article{Alikin_2016, title={Characterization of LiMn2O4 cathodes by electrochemical strain microscopy}, volume={108}, ISSN={1077-3118}, url={http://dx.doi.org/10.1063/1.4943944}, DOI={10.1063/1.4943944}, number={11}, journal={Applied Physics Letters}, publisher={AIP Publishing}, author={Alikin, D. O. and Ievlev, A. V. and Luchkin, S. Yu. and Turygin, A. P. and Shur, V. Ya. and Kalinin, S. V. and Kholkin, A. L.}, year={2016}, month=mar }

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