Materials in lithium ion battery electrodes expand and contract during charge and discharge. These volume changes drive particle fracture, which shortens battery lifetime. A group of ETH and PSI scientists have quantified this effect for the first time using high-resolution 3D movies recorded using x-ray tomography at the Swiss Light Source.
Lithium-ion batteries are in our mobile phones, laptops, and digital cameras. Few portable electronic devices exist that do not rely on these energy sources. Currently battery electrodes contain active materials known as intercalation compounds. These materials store charge in their chemical structure without undergoing substantial structural change. That makes these batteries comparatively long-lived and safe. However, intercalation materials have one drawback: their limited energy density, the amount of energy they can store per volume and mass.
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.
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 micrometres to 120 micrometres. However, during discharge, the electrode contracts only to 80 micrometres. 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 behaviour. This approach is essential to understanding the influence of particle size, shape, and electrode homogeneity on battery performance.
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 behaviour of a variety of battery materials. The insights provide the basis for developing new electrode materials and electrode structures that are tolerant to volume expansion. For Wood the results of this work indicate the benefit of using amorphous or nanostructured materials instead of crystalline ones. “On the quest for new materials, one must also bear in mind that they are only of industrial interest if they can be produced in large quantities at a low cost. However, amorphous and nanostructured materials offer a sufficient playground for innovation.” emphasizes Wood.
This story is reprinted from material from ETH, with editorial changes made by Materials Today. The views expressed in this article do not necessarily represent those of Elsevier. Link to original source.