Team uses x-ray tomography to visualize and to quantify degradation of tin-oxide Li-ion electrode under operation
|Screenshot from 3D movie of evolution of particle fracture. Preferential crack initiation and growth in the (001) planes leading to zig-zag morphology is shown for multiple particles. Click here to view movie.|
Materials in certain high energy density lithium-ion battery electrodes—specifically, materials that undergo conversion and alloying reactions with lithium—expand and contract during charge and discharge; these volume changes drive particle fracture, which shortens battery lifetime.
Researchers from ETH Zurich and the Paul Scherrer Institute have visualized and quantified the origins and evolution of this electrochemical and mechanical degradation of Li-ion batteries during battery operation using high-resolution 3D movies recorded using using x-ray tomography at the Swiss Light Source. A paper on their work is published in the journal Science.
|Particles of a tin oxide electrode experiencing structural changes during charging (1-3) and discharging (3-4). (Graphic: Martin Ebner, Laboratory for Nanoelectronics, ETH Zurich) Click to enlarge.|
The insights gleaned from the work provide the basis for developing new electrode materials and electrode structures that are tolerant to volume expansion.
Current commercial Li-ion battery electrodes contain active materials known as intercalation compounds. These materials store charge in their chemical structure without undergoing substantial structural change, making them comparatively long-lived and safe. However, intercalation materials have limited energy density.
In the search for higher energy density batteries, scientists have experimented for more than 20 years with materials capable of repetitively alloying and de-alloying with lithium. Laboratory-scale experiments have shown that batteries with such materials have energy densities multiple times that of intercalation materials; however, these alloying materials are not yet exploited in industry because their lifetime is limited.
This is attributed to an up to threefold expansion of the electrode material during charging. During discharge, the materials contract again, but do not reach their original state. Electrode particles break apart, the electrode structure disintegrates, and the fragments loose contact to the rest of the cell.
To better understand this complex electrochemical and mechanical degradation of the electrode and to gain insight into how to develop better batteries, Martin Ebner, a PhD student at ETH and ETH Professor Vanessa Wood, head of the Laboratory for Nanoelectronics at D-ITET, recognized the need to study a battery electrode non-invasively during operation.
|X-Ray Tomography Group at PSI|
|The Swiss Light Source (SLS) at the Paul Scherrer Institut is a third-generation synchrotron light source. With an energy of 2.4 GeV, it provides photon beams of high brightness for research in materials science, biology and chemistry.|
|The 2.4 GeV electron storage ring of 288 m circumference is formed by 36 dipole magnets of 1.4 tesla magnetic field, combined in 12 groups of three for achromatic deflection of the electron beam. 12 straight sections between the TBAs (triple bend achromat) of different lengths accommodate the undulator magnets to generate ultraviolet and X-ray light of extreme brightness.|
|3 of the dipoles have an increased center field of 3 teslas to produce hard X-rays. A total of 177 quadrupole magnets (magnetic lenses) focuses the beam to provide an emittance of 5.5 nm rad. 120 sextupole magnets correct the chromatic focusing errors of the quadrupoles. 73 horizontal and vertical beam steerers are used to continuously correct the position of the electron beam. Finally 24 skew quadrupole magnets are adjusted to correct any torsion of the beam and to minimize the vertical emittance: a world record low value of 3 pm rad has been achieved in 2008.|
|The operation of the beamlines at the SLS is split into three thematic areas: Macromolecules and Bioimaging (LSB); Condensed Matter (LSC); and Catalysis and Sustainable Chemistry (LSK).|
|Prof. Stampanoni heads a group of 19 focused on the development of tools (instruments and algorithms) for tomographic X-ray imaging, both exploiting synchrotron and laboratory sources.|
To do so, they turned to an imaging tool developed by ETH Professor Marco Stampanoni who holds a faculty position at the Institute for Biomedical Engineering at D-ITET. He also runs the tomographic x-ray microscopy beamline at the Swiss Light Source, the synchrotron facility at the Paul Scherrer Institute (PSI).
The spectrally pure and intense synchrotron x-ray radiation enables the fast acquisition of high-resolution x-ray images that can be computationally assembled into three-dimensional movies.
The researchers chose crystalline tin oxide as a model material because it undergoes a series of complex transformations also present in other materials, enabling deeper understanding into the behavior of a variety of battery materials.
The researchers observed the inside of the battery as it charged and discharged over 15 hours. They gathered unique, three-dimensional movies that capture the degradation mechanisms occurring in the battery and quantified the processes occurring within every particle for the thousands of particles in the electrode.
The data illustrate that tin oxide (SnO) particles expand during charging due to the influx of lithium ions causing an increase in particle volume. The scientists demonstrate that material lithiation happens as a core-shell process, progressing uniformly from the particle surface to the core. The material undergoing this reaction expands linearly with the stored charge.
The x-ray images show that charging destroys the particle structure irreversibly with cracks forming within the particles. “This crack-formation is not random,” emphasizes Ebner. Cracks grow at locations where the crystal lattice contains pre-existing defects. During discharge, the particle volume decreases; however, the material does not reach its original state again; the process is therefore not completely reversible.
The volume change of the individual particles drives expansion of the entire electrode from 50 micrometers to 120 micrometers. However, during discharge, the electrode contracts only to 80 micrometers. This permanent deformation of the electrode demonstrates that the polymer binder that holds the electrode together is not yet optimized for high volume expansion materials. This is critical for battery performance because deformation of the binder causes individual particles to become disconnected from the electrode and the battery loses capacity.
In addition to demonstrating that x-ray tomographic microscopy provides insight into morphological changes in the particles and electrodes, the researchers show that this technique can also be used to obtain quantitative and spatially resolved chemical information.
For example, the researchers analyse chemical composition throughout the battery electrode to look at differences in lithiation dynamics at the single particle level and compare this to the average particle behavior. This approach is essential to understanding the influence of particle size, shape, and electrode homogeneity on battery performance.
Tomography provides the time resolved, three-dimensional chemical composition and morphology within individual particles and throughout the electrode. In the model material SnO, we witness distributions in onset and rate of core-shell lithiation, crack initiation and growth along preexisting defects, and irreversible distortion of the electrode, highlighting tomography as tool to guide the development of durable materials and strain-tolerant electrodes.—Ebner et al.
Martin Ebner, Federica Marone, Marco Stampanoni, and Vanessa Wood (2013) “Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries”, Science doi: 10.1126/science.1241882