Nowadays, research on electrochemical storage systems moves into the direction of post-lithium-ion batteries, such as aluminum-ion batteries, and the exploration of suitable materials for such batteries. Vanadium pentoxide (V₂O₅) is one of the most promising host materials for the intercalation of multivalent ions. Here, we report on the fabrication of a binder-free and self-supporting V₂O₅ micrometer-thick paper-like electrode material and its use as the cathode for rechargeable aluminum-ion batteries. The electrical conductivity of the cathode was significantly improved by a novel in-situ and self-limiting copper migration approach into the V₂O₅ structure. This process takes advantage of the dissolution of Cu by the ionic liquid-based electrolyte, as well as the presence of two different accommodation sites in the nanostructured V₂O₅ available for aluminum-ions and the migrated Cu. Furthermore, the advanced nanostructured cathode delivered a specific discharge capacity of up to ~170 mAh g⁻¹ and the reversible intercalation of Al³⁺ for more than 500 cycles with a high Coulomb efficiency reaching nearly 100%. The binder-free concept results in an energy density of 74 Wh kg⁻¹, which shows improved energy density in comparison to the so far published V₂O₅-based cathodes. Our results provide valuable insights for the future design and development of novel binder-free and self-supporting electrodes for rechargeable multivalent metal-ion batteries associating a high energy density, cycling stability, safety and low cost.

The synthesis of ceramic materials combining high porosity and permeability with good mechanical stability is challenging, as optimising the latter requires compromises regarding the first two properties. Nonetheless, significant progress can be made in this direction by taking advantage of the structural design principles evolved by nature. Natural cellular solids achieve good mechanical stability via a defined hierarchical organisation of the building blocks they are composed of. Here, we report the first synthetic, ceramic-based scaffold whose architecture closely mimics that of cuttlebone –a structural biomaterial whose porosity exceeds that of most other natural cellular solids, whilst preserving an excellent mechanical strength. The nanostructured, single-component scaffold, obtained by ice-templated assembly of V₂O₅ nanofibres, features a highly sophisticated and elaborate architecture of equally spaced lamellas, which are regularly connected by pillars as lamella support. It displays an unprecedented porosity of 99.8 %, complemented by an enhanced mechanical stability. This novel bioinspired, functional material not only displays mechanical characteristics similar to natural cuttlebone, but the multifunctionality of the V₂O₅ nanofibres also renders possible applications, including catalysts, sensors and electrodes for energy storage.