RT Journal Article
T1 Imaging phase segregation in nanoscale LixCoO2 single particles
A1 Fuller, Elliot J
A1 Ashby, David S
A1 Polop, Celia
A1 Salagre, Elena
A1 Bhargava, Bhuvsmita
A1 Song, Yueming
A1 Vasco, Enrique
A1 Sugar, Joshua D
A1 Albertus, Paul
A1 Mentes, Tevfik Onur
A1 Locatelli, Andrea
A1 Segovia, Pilar
A1 González Barrio, Miguel Ángel
A1 Mascaraque Susunaga, Arantzazu
A1 Michel, Enrique G
A1 Talin, A. Alec
AB Li xCoO2 (LCO) is a common battery cathode material that has recently emerged as a promising material for other applications including electrocatalysis(1, 2) and as electrochemical random access memory (ECRAM)(3). During charge-discharge cycling LCO exhibits pase transformations that are significantly complicated by electron correlation. While the bulk pase diagram for an ensemble of battery particles has been studied extensively, it remains unclear how these phases scale to nanometer dimensions and the effects of strain and diffusional anisotropy at the single particle scale. Understanding these effects is critical to modeling battery performance and for predicting the scalability and performance of electrocatalysts and ECRAM. Here we investigate isolated, epitaxial LiCoO2 islands grown by pulsed laser deposition (PLD). After electrochemical cycling of the islands, conductive atomic force microscopy (c-AFM) is used to image the spatial distribution of conductive and insulating phases. Above 20 nm island thicknesses, we observe a kinetically arrested state in which the phase boundary is perpendicular to the Li-planes; we propose a model and present image analysis results that show smaller LCO islands have a higher conductive fraction than larger area islands, and the overall conductive fraction is consistent with lithiation state. Thinner islands (14 nm), with a larger surface to volume ratio, are found to exhibit a striping pattern which suggests surface energy can dominate below a critical dimension. When increasing force is applied through the AFM tip to strain the LCO islands, significant shifts in current flow are observed, and underlying mechanisms for this behavior are discussed. The c-AFM images are compared with photoemission electron microscopy (PEEM) images which are used to acquire statistics across hundreds of particles. The results indicate that strain and morphology become more critical to electrochemical performance as particles approach nanometer dimensions.
PB American Chemical Society
SN 1936-0851
YR 2022
FD 2022
LK https://hdl.handle.net/20.500.14352/112831
UL https://hdl.handle.net/20.500.14352/112831
LA eng
NO Fuller, E. J.; Ashby, D. S.; Polop, C.; Salagre, E.; Bhargava, B.; Song, Y.; Vasco, E.; Sugar, J. D.; Albertus, P.; Menteş, T. O.; Locatelli, A.; Segovia, P.; Gonzalez-Barrio, M. Á.; Mascaraque, A.; Michel, E. G.; Talin, A. A. Imaging Phase Segregation in Nanoscale Li x CoO2 Single Particles. ACS Nano 2022, 16 (10), 16363–16371. https://doi.org/10.1021/acsnano.2c05594.
NO DE-NA-0003525DE-SC0021070PRX19/00486
NO Sandia National Laboratories
NO Department of Energy (United States)
NO Ministerio de Ciencia e Innovación (España)
NO Comunidad de Madrid
NO Agencia Estatal de Investigación (España)
NO European Commission
DS Docta Complutense
RD 10 abr 2025