Andrés González-Banciella

Owing to the increasing demand for wearable electronics, flexible energy storage devices, such as supercapacitors, have gained interest in the electronic industry. In this context, asymmetric configurations have emerged as a promising strategy for the development of wider potential window supercapacitors. On the other hand, MOF-derived synthesis of transition metal oxides is known to result in porous materials, which exhibit better electrochemical performance. In this work, a MOF-derived Fe₂O₃ coating on carbon fiber woven substrate is proposed as a negative supercapacitor electrode for asymmetric flexible devices. Moreover, the MOF calcination time was evaluated in order to ensure the best electrochemical performance possible, achieving for the sample calcined for 2 h a specific capacitance of 18.8 F/g at a current density of 200 mA/g and an excellent rate capability. In addition, not only was this promising material obtained, but an asymmetric flexible supercapacitor based on two MOF-derived TMO coatings on carbon fiber woven electrodes was manufactured and characterized as a proof of concept. This supercapacitor displayed a specific capacitance of 229 mF/cm², an energy density of 0.067 mWh/cm² and a power density of 0.11 mW/cm² at 0.15 mA/cm². Moreover, the flexible supercapacitor retained 94.1% of its capacitance even after being bent to 90°.

Carbon fiber, with its strong mechanical properties and electrical conductivity, is ideal as a fiber electrode in wearable or structural energy storage devices. However, its energy storage capacity is limited, and coatings like transition metal oxides (TMOs) enhance its electrochemical performance. Metal–organic frameworks (MOFs) are commonly used to grow TMOs on carbon fibers, increasing the surface area for better energy storage. Despite this, TMOs have limited electrical conductivity, so ion exchange is often used to dope them with additional cations, improving both conductivity and energy storage capacity. This study compares different ion-exchange cations in ZIF-L-derived TMO coatings on carbon fiber. Testing both supercapacitor and Li-ion battery applications, Ni-doped samples showed superior results, attributed to their higher exchange ratio with cobalt. As a supercapacitor electrode, the Ni-doped material achieved 13.3 F/g at 50 mA/g—66% higher than undoped samples. For Li-ion battery anodes, it reached a specific capacity of 410.5 mAh/g at 25 mA/g, outperforming undoped samples by 21.4%.

Nowadays, owing to the new technological and industrial requirements for equipment, such as flexibility or multifunctionally, the development of all-solid-state supercapacitors and Li-ion batteries has become a goal for researchers. For these purposes, the composite material approach has been widely proposed due to the promising features of woven carbon fiber as a substrate material for this type of material. Carbon fiber displays excellent mechanical properties, flexibility, and high electrical conductivity, allowing it to act as a substrate and a collector at the same time. However, carbon fiber’s energy-storage capability is limited. Several coatings have been proposed for this, with nanostructured transition metal oxides being one of the most popular due to their high theoretical capacity and surface area. In this overview, the main techniques used to achieve these coatings—such as solvothermal synthesis, MOF-derived obtention, and electrochemical deposition—are summarized, as well as the main strategies for alleviating the low electrical conductivity of transition metal oxides, which is the main drawback of these materials.

Different modifications of woven carbon fiber (WCF) based on carbon aerogel (CAG), copper oxide nanoparticles (CuO-NPs), and lignin (LIG) has been tested and used to study their effect on the fabrication and performance of a flexible supercapacitor. New symmetric flexible supercapacitors (SFSCs) were fabricated using different separators. According to the electrochemical results, the device fabricated using CAG and woven glass fiber (WGF) in a sandwich type configuration CAG/WGF/CAG embedded in H₃PO₄/PVA exhibited the best performance (1.4 F/g, 0.961 W/kg, 0.161 Wh/kg). A proof of concept based on a LED powered on and a bending test was done, and the capacitor demonstrated excellent electrochemical values even during and after bending. The new device was able to recover 96.12% of its capacitance when returned to its original unbent position. The manufacturing process was critical, as the fibers or layers must be completely embedded in the gel electrolyte to function effectively. A double flexible supercapacitor connected in parallel was fabricated and it showed higher stability, in the same voltage window, yielding 311 mF/cm² of areal capacitance.