In Situ Operando Electrochemical Dilatometry as a Method to Distinguish Charge Storage Mechanisms and Metal Plating Processes for Sodium and Lithium Ions in Hard Carbon Battery Electrodes

In situ operando electrochemical dilatometry ECD provides information on the expansion shrinkage of an electrode during cell cycling. It is shown that the ECD signal can be used as descriptor to characterize the charge storage behavior of lithium and sodium ions in hard carbon electrodes. It is found that sodium storage in hard carbons occurs by a three step mecha nism, namely I insertion, II pore filling, and III plating. Step III can be seen from a sudden increase in electrode thickness for potentials below around 36 mV versus Na Na and is assigned to plating on the hard carbon surface. Interestingly, this last step is absent in the case of lithium which demon strates that the storage behavior between both alkali metals is different. The plating mechanism is also supported by reference experiments in which bulk plating is enforced. Bulk plating on hard carbon electrodes can be detected more easily for sodium compared to lithium. It is also found that the type of binder strongly influences the dilatometry results. A comparison between the binders sodium salt of carboxymethyl cellulose and poly vinylidene difluoride shows that the use of the former leads to notably smaller first electrode expansion as well as a higher initial Coulomb efficienc

A Practical Guide for Using Electrochemical Dilatometry as Operando Tool in Battery and Supercapacitor Research

Lithium ion batteries and related battery concepts show an expansion and shrinkage breathing of the electrodes during cell cycling. The dimensional changes of an individual electrode or a complete cell can be continuously measured by electrochemical dilatometry ECD . The obtained data provides information on the electrode cell reaction itself but can be also used to study side reactions or other relevant aspects, e.g., how the breathing is influenced by the electrode binder and porosity. The method spans over a wide measurement range and allows the determination of macroscopic as well as nanoscopic changes. It has also been applied to supercapacitors. The method has been developed already in the 1970s but recent advancements and the availability of commercial setups have led to an increasing interest in ECD. At the same time, there is no best practice on how to evaluate the data and several pitfalls exist that can complicate the comparison of literature data. This review highlights the recent development and future trends of ECD and its use in battery and supercapacitor research. A practical guide on how to evaluate the data is provided along with a discussion on various factors that influence the measurement result