Ionogels are a new class of promising materials for use in all‐solid‐state energy storage devices in which they can function as an integrated separator and electrolyte. However, their performance is limited by the presence of a crosslinking polymer, which is needed to improve the mechanical properties, but compromises their ionic conductivity. Here, directional freezing is used followed by a solvent replacement method to prepare aligned nanocomposite ionogels which exhibit enhanced ionic conductivity, good mechanical strength, and thermal stability simultaneously. The aligned ionogel based supercapacitor achieves a 29% higher specific capacitance (176 F g −1 at 25 °C and 1 A g −1 ) than an equivalent nonaligned form. Notably, this thermally stable aligned ionogel has a high ionic conductivity of 22.1 mS cm −1 and achieves a high specific capacitance of 167 F g −1 at 10 A g −1 and 200 °C. Furthermore, the diffusion simulations conducted on 3D reconstructed tomography images are employed to explain the improved conductivity in the relevant direction of the aligned structure compared to the nonaligned. This work demonstrates the synthesis, analysis, and use of aligned ionogels as supercapacitor separators and electrolytes, representing a promising direction for the development of wearable electronics coupled with image based process and simulations.

We developed a simple and versatile way to prepare aligned hydrogel electrolytes for ultrahigh-capacity supercapacitors by building aligned pores via “hot ice” templates and copolymerizing with amphoteric monomers.

“All-in-gel” supercapacitor is designed via ionogel composite electrolyte and Bucky gel electrodes. These flexible, conductive and shape-conformable gels represent a step change in the design of safe energy storage devices for wearable electronics, in particular those facing the increased demands of hazardous operational environments.

The controllable preparation of eggshell-hydrogels provides a new insight into composite material preparation from bio-waste eggshell membrane in energy devices with thickness-dependent electrochemical performances.