Mesoscale Battery Science: The Behavior of Electrode Particles Caught on a Multispectral X-ray Camera.

Functional materials and devices are usually morphologically complex and chemically heterogeneous. Their structures are often designed to be hierarchical because of the desired functionalities, which usually require many different components to work together in a coherent manner. The lithium ion battery, as an energy storage device, is a very typical example of this kind of structure. In a lithium ion battery, the cathode, anode, and separator are soaked in a liquid electrolyte, facilitating the back and forward shuttling of the lithium ions for energy storage and release. The desired performance of a lithium ion battery has many different aspects that need to be engineered and balanced depending on the targeted applications. In most cases, the cathode material has become the limiting factor for further improvements and, thus, has attracted intense attention from the research community. While the improvement in the overall performance of the lithium ion battery is the ultimate goal of the research in this field, understanding the relationship between the microscopic properties and the macroscopic behaviors of the materials/devices can inform the design of better battery chemistries for practical applications. As a result, it is of great fundamental and practical importance to investigate the electrode materials using experimental probes that can provide good chemical sensitivity and sufficient spatial resolution, ideally, under operating conditions. With this motivation, our group has been focusing on the development of the nanoscale full-field X-ray spectro-microscopy, which has now become a well-recognized tool for imaging battery electrode materials at the particle level. With nanoscale spatial resolution, this technique can effectively and efficiently tackle the intrinsically complicated mesoscale chemistry. It allows us to monitor the particles' morphological and chemical evolution upon battery operation, providing valuable insights that can be incorporated into the design of new battery chemistries. In this Account, we review a series of our recent studies of battery electrode materials using nanoscale full-field X-ray spectro-microscopy. The materials that are the subjects of our studies, including layer-structured and spinel-structured oxide cathodes, are technically very important as they not only play an important role in today's devices but also possess promising potential for future developments. We discuss how the subparticle level compositional and state-of-charge heterogeneity can be visualized and linked to the bulk performance through systematic quantification of the imaging data. Subsequently, we highlight recent ex situ and in situ observations of the cathode particles' response to different reaction conditions, including the spontaneously adjusted reaction pathways and the morphological changes for the mechanical strain release. The important role of surface chemistry in the system is also discussed. While the microscopic investigation at the particle level provides useful insights, the degree to which this represents the overall properties of the battery is always a question for further generalizing the conclusions. In order to address this concern, we finally discuss a high throughput experimental approach, in which a large number of cathode particles are scanned. We discuss a case study that demonstrates the identification and analysis of functionally important minority phases in an operating battery cell through big data mining methods. With an emphasis on the data/information mining aspect of the nanoscale X-ray spectro-microscopic study of battery cathode particles, we anticipate that this Account will attract more research to this field.