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Berkeley Lab
/ / Science Highlights / Spectroscopy of Supercapacitor Electrodes In Operando

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Future technology will require energy storage systems that have much larger storage capability, rapid charge/discharge cycling, and improved endurance. Progress in these areas demands a more complete understanding of the processes involved in energy storage, from the atomic scale to the device level. Now, using soft x-ray absorption spectroscopy (XAS) under operating conditions (“in operando”), researchers have found that the interfacial electric fields generated during charging of the electrode/electrolyte interface of a supercapacitor can induce changes in the structure and bonding of its graphitic carbon electrodes. The research could lead to better, more reliable strategies for improving the capacity and efficiency of electrical energy storage systems needed to meet the burgeoning demands of consumer, industrial, and green technologies.

3D Nanographene Supercapacitors

Like a battery, a capacitor is a device for storing electrical energy. It consists of two electrodes separated by a solid-state dielectric insulator. In a “supercapacitor,” the solid-state dielectric is replaced by a liquid electrolyte with mobile ions. This effectively creates two capacitors in series, each formed by a solid-state electrode and a potential-induced ion layer in the electrolyte. Because the ion layer forms within nanometers of the electrode, the charge storage capacity per unit area can be much higher than in a traditional capacitor with its thicker dielectric layer.

Materials for supercapacitor electrodes should be porous, enabling high ion mobility in the liquid electrolyte for fast charging, and have very high surface areas, increasing the charge storage capacity at the electrode/electrolyte interface. Here, the researchers used 3D nanographene, which they recently developed and consists of interconnected graphene sheets providing a hierarchical pore structure with a high surface-to-volume ratio.

Because supercapacitors charge and discharge faster than batteries and can handle more cycles, they are attractive for high-power applications such as recovering braking energy and supplying short-burst power (e.g., in cars and elevators) or for backing up static random-access memory (SRAM). In this work, Bagge-Hansen et al. describe results from a newly developed x-ray spectroscopy capability at the ALS that allowed them to detect complex, electric-field-induced changes that graphene-based supercapacitor electrodes undergo during operation.

Electrode/electrolyte interfaces are critical to all electrochemical energy storage technologies, including supercapacitors, yet we still don’t fully understand how the physiochemical properties of these devices are altered by the interfacial electric field generated during charging. While the structural and dynamical responses of the electrolyte to an applied potential have been extensively studied, the analogous responses of the electrode material during operation remain largely unexplored, even for widely used materials such as graphitic electrodes. The electronic structure of the electrode is conventionally considered to be static, with charge accumulation or depletion as the only response to polarization of the interface. This lack of understanding of the dynamic physiochemical changes of the electrode is largely due to the paucity of experimental and theoretical methods for characterization of the electrode electronic structure during operation.

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