In situ and continuous monitoring of electrochemical activity is key to understanding and evaluating the operation mechanism and efficiency of energy storage devices. However, this task remains challenging. For example, the present methods are not capable of providing the real-time information about the state of charge (SOC) of the energy storage devices while in operation. To address this, a novel approach based on an electrochemical surface plasmon resonance (SPR) optical fiber sensor is proposed here. This approach offers the capability of in situ comprehensive monitoring of the electrochemical activity (the electrode potential and the SOC) of supercapacitors (used as an example). The sensor adopted is a tilted fiber Bragg grating imprinted in a commercial single-mode fiber and coated with a nanoscale gold film for high-efficiency SPR excitation. Unlike conventional “bulk” detection methods for electrode activity, our approach targets the “localized” (sub-μm-scale) charge state of the ions adjacent to the electrode interface of supercapacitors by monitoring the properties of the SPR wave on the fiber sensor surface located adjacent to the electrode. A stable and reproducible correlation between the real-time charge–discharge cycles of the supercapacitors and the optical transmission of the optical fiber has been found. Moreover, the method proposed is inherently immune to temperature cross-talk because of the presence of environmentally insensitive reference features in the optical transmission spectrum of the devices. Finally, this particular application is ideally suited to the fundamental qualities of optical fiber sensors, such as their compact size, flexible shape, and remote operation capability, thereby opening the way for other opportunities for electrochemical monitoring in various hard-to-reach spaces and remote environments.

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