Three-Electrode Cell Calorimeter for Electrical Double Layer Capacitors

TL;DR

This paper introduces a specialized three-electrode calorimeter designed to measure heat production in porous electrodes of electrical double layer capacitors, providing insights into ion behavior and energy storage mechanisms.

Contribution

It presents a novel calorimeter setup capable of distinguishing heat effects during charging and discharging in supercapacitor electrodes.

Findings

Calorimeter accurately measures heat during electrochemical cycles.

Heat measurements reveal differences between cathodic and anodic processes.

Provides data on internal energy changes related to ion arrangements.

Abstract

A calorimeter was built to measure the heat from a porous capacitive working electrode connected in a three-electrode configuration. This makes it possible to detect differences between cathodic and anodic heat production. The electrochemical cell contains a large electrolyte solution reservoir, ensuring a constant concentration of the salt solution probed by the reference electrode via a Luggin tube. A heat flux sensor is used to detect the heat, and its calibration as a gauge of the total amount of heat produced by the electrode is done on the basis of the net electrical work performed on the working electrode during a full charging-discharging cycle. In principle, from the measured heat and the electrical work, the change in internal energy of the working electrode can be determined as a function of applied potential. Such measurements inform about the potential energy and average electric potential of ions inside the pores, giving insight into the electrical double layer inside electrode micropores. Example measurements of the heat are shown for porous carbon electrodes in aqueous salt solution.