The reversible electrochemical insertion of multivalent ions into materials has promising applications in many fields, including batteries, seawater desalination, element purification, and wastewater treatment. However, finding materials that allow for the insertion of multivalent ions with fast kinetics and stable cycling has proven difficult because of strong electrostatic interactions between the highly charged insertion ions and atoms in the host framework. Here, an open framework nanomaterial, copper hexacyanoferrate, in the Prussian Blue family is presented that allows for the reversible insertion of a wide variety of monovalent, divalent, and trivalent ions (such as Rb⁺, Pb²⁺, Al³⁺, and Y³⁺) in aqueous solution beyond that achieved in previous studies. Electrochemical measurements demonstrate the unprecedented kinetics of multivalent ion insertion associated with this material. Synchrotron X-ray diffraction experiments point toward a novel vacancy-mediated ion insertion mechanism that reduces electrostatic repulsion and helps to facilitate the observed rapid ion insertion. The results suggest a new approach to multi­valent ion insertion that may help to advance the understanding of this complex phenomenon.

High-performance flexible energy-storage devices have great potential as power sources for wearable electronics. One major limitation to the realization of these applications is the lack of flexible electrodes with excellent mechanical and electrochemical properties. Currently employed batteries and supercapacitors are mainly based on electrodes that are not flexible enough for these purposes. Here, a three-dimensionally interconnected hybrid hydrogel system based on carbon nanotube (CNT)-conductive polymer network architecture is reported for high-performance flexible lithium ion battery electrodes. Unlike previously reported conducting polymers (e.g., polyaniline, polypyrrole, polythiophene), which are mechanically fragile and incompatible with aqueous solution processing, this interpenetrating network of the CNT-conducting polymer hydrogel exibits good mechanical properties, high conductivity, and facile ion transport, leading to facile electrode kinetics and high strain tolerance during electrode volume change. A high-rate capability for TiO₂ and high cycling stability for SiNP electrodes are reported. Typically, the flexible TiO₂ electrodes achieved a capacity of 76 mAh g^–1 in 40 s of charge/discharge and a high areal capacity of 2.2 mAh cm^–2 can be obtained for flexible SiNP-based electrodes at 0.1C rate. This simple yet efficient solution process is promising for the fabrication of a variety of high performance flexible electrodes.

Alloying anodes such as silicon are promising electrode materials for next-generation high energy density lithium-ion batteries because of their ability to reversibly incorporate a high concentration of Li atoms. However, alloying anodes usually exhibit a short cycle life due to the extreme volumetric and structural changes that occur during lithium insertion/extraction; these transformations cause mechanical fracture and exacerbate side reactions. To solve these problems, there has recently been significant attention devoted to creating silicon nanostructures that can accommodate the lithiation-induced strain and thus exhibit high Coulombic efficiency and long cycle life. In parallel, many experiments and simulations have been conducted in an effort to understand the details of volumetric expansion, fracture, mechanical stress evolution, and structural changes in silicon nanostructures. The fundamental materials knowledge gained from these studies has provided guidance for designing optimized Si electrode structures and has also shed light on the factors that control large-volume change solid-state reactions. In this paper, we review various fundamental studies that have been conducted to understand structural and volumetric changes, stress evolution, mechanical properties, and fracture behavior of nanostructured Si anodes for lithium-ion batteries and compare the reaction process of Si to other novel anode materials.

The high theoretical specific capacity of Si as an anode material is attractive in lithium-ion batteries, although the issues caused by large volume changes during cycling have been a major challenge. Efforts have been devoted to understanding how diffusion-induced stresses cause fracture, but recent observations of anisotropic volume expansion in single-crystalline Si nanostructures require new theoretical considerations of expansion behavior during lithiation. Further experimental investigation is also necessary to better understand the anisotropy of the lithiation process. Here, we present a method to reveal the crystalline core of partially lithiated Si nanopillars with three different crystallographic orientations by using methanol to dissolve the Li atoms from the amorphous Li-Si alloy. The exposed crystalline cores have flat {110} surfaces at the pillar sidewalls; these surfaces represent the position of the reaction front between the crystalline core and the amorphous Li-Si alloy. It was also found that an amorphous Si structure remained on the flat surfaces of the crystalline core after dissolution of the Li, which was presumed to be caused by the accumulation of Si atoms left over from the removal of Li from the Li-Si alloy.

Nanostructured Si is a promising anode material for the next generation of Li-ion batteries, but few studies have focused on the electrical properties of the Li-Si alloy phase, which are important for determining power capabilities and ensuring sufficient electrical conduction in the electrode structure. Here, we demonstrate an electrochemical device framework suitable for testing the electrical properties of single Si nanowires (NWs) at different lithiation states and correlating these properties with structural changes via transmission electron microscopy (TEM). We find that single Si NWs usually exhibit Ohmic I–V response in the lithiated state, with conductivities two to three orders of magnitude higher than in the delithiated state. After a number of sequential lithiation/delithiation cycles, the single NWs show similar conductivity after each lithiation step but show large variations in conductivity in the delithiated state. Finally, devices with groups of NWs in physical contact were fabricated, and structural changes in the NWs were observed after lithiation to investigate how the electrical resistance of NW junctions and the NWs themselves affect the lithiation behavior. The results suggest that electrical resistance of NW junctions can limit lithiation. Overall, this study shows the importance of investigating the electronic properties of individual components of a battery electrode (single nanostructures in this case) along with studying the nature of interactions within a collection of these component structures.