Operando Stress Evolution in Hard Carbon Anodes – Insight into the Mechanical Degradation Induced Failure Mode in Rechargeable Sodium Ion Batteries
Authors: Pakhare Akshay , La Sungwon , Karan Naba , Guduru Pradeep 
Published: August 2024

Microstructural instabilities in electrodes arising from cycling induced stress is a primary failure mode in rechargeable batteries. Therefore, a quantitative knowledge of the cycling induced stress evolution in rechargeable battery electrodes is important for understanding the electrode microstructural instabilities during cycling that can potentially inform the electrode design to prolong battery cycle life. The cycling induced stress in electrodes typically arises from the volume changes associated with insertion/extraction of the electroactive species in the electrode matrix. For example, operando measurement of lithiation-delithiation induced stress in graphite electrodes that typically show 10% volume change has previously resulted in useful information that correlates well with the lithiation-delithiation mechanism in graphite anodes1. The size of the shuttling-electroactive species can be taken as an indicator of the cycling induced stress magnitude that drives the electrode microstructural instabilities. In this regard, quantification of the cycling induced stress in rechargeable Na-ion battery electrodes is warranted for understanding mechanical degradation induced failure modes owing to the larger size of the electroactive species, i.e., Na ions (vs. Li-ion).
Hard carbons as potential anodes in rechargeable sodium ion batteries has gained considerable attention in the recent past due to their superior Na-ion storage capability (vs. graphite that is a canonical anode in rechargeable lithium-ion batteries). However, hard carbon anodes typically show significant capacity fade that can potentially arise from cycling induced mechanical degradation of the anodes. Operando stress measurements coupled with comprehensive electrode microstructural characterization will provide valuable insights in this context. Here we report on the operando stress evolution in hard carbon anodes in rechargeable sodium ion batteries as probed by Multiple Optical-beam Sensing (MOS) technique that basically involves monitoring the spacings among a group of laser spot (Fig. 1). Preliminary measurements have shown that the stress correlates with the potential with a maximum around 12 MPa in compression during sodiation and tensile stress of ~ 2MPa during desodiation. Operando stress measurements are performed in hard carbon anodes in two different electrode configurations – typical composite anodes (with binder and conductive agents) and hard carbon thin film anodes (without binder and conductive agents). The thin film configuration is considered to evaluate intrinsic stress response in hard carbon anodes in absence of any secondary phase. A comparison of operando stress response in these two types of hard carbon anodes along with comprehensive electrode microstructural characterization will be presented. Additionally, attempts will be made to shed light on the current debate in the mechanism of sodium storage in hard carbon anodes by comparing operando stress response of hard carbons from multiple sources along with their structural characterization (Raman, XPS, surface area etc.).

V. A. Sethuraman, N. Van Winkle, D. P. Abraham, A. F. Bower, and P. R. Guduru, Journal of Power Sources, 206, 334–342 (2012).

Figure 1