The search for lead‐free alternatives to lead‐halide perovskite photovoltaic materials resulted in the discovery of copper(I)‐silver(I)‐bismuth(III) halides exhibiting promising properties for optoelectronic applications. The present work demonstrates a solution‐based synthesis of uniform CuxAgBiI4+x thin films and scrutinizes the effects of x on the phase composition, dimensionality, optoelectronic properties, and photovoltaic performance. Formation of pure 3D CuAgBiI5 at x = 1, 2D Cu2AgBiI6 at x = 2, and a mix of the two at 1 < x < 2 is demonstrated. Despite lower structural dimensionality, Cu2AgBiI6 has broader optical absorption with a direct bandgap of 1.89 ± 0.05 eV, a valence band level at ‐5.25 eV, improved carrier lifetime, and higher recombination resistance as compared to CuAgBiI5. These differences are mirrored in the power conversion efficiencies of the CuAgBiI5 and Cu2AgBiI6 solar cells under 1 sun of 1.01 ± 0.06% and 2.39 ± 0.05%, respectively. The latter value is the highest reported for this class of materials owing to the favorable film morphology provided by the hot‐casting method. Future performance improvements might emerge from the optimization of the Cu2AgBiI6 layer thickness to match the carrier diffusion length of ≈40–50 nm. Nonencapsulated Cu2AgBiI6 solar cells display storage stability over 240 days.

We have investigated the sodium electrochemistry and the evolution and chemistry of the solid–electrolyte interphase (SEI) upon cycling Na metal electrodes in two ionic liquid (IL) electrolytes. The effect of the IL cation chemistry was determined by examining the behavior of a phosphonium IL (P111i4FSI) in comparison to its pyrrolidinium-based counterpart (C3mpyrFSI) at near-saturated NaFSI salt concentrations (superconcentrated ILs) in their dry state and with water additive. The differences in their physical properties are reported, with the P111i4FSI system having a lower viscosity, higher conductivity, and higher ionicity in comparison to the C3mpyrFSI-based electrolyte, although the addition of 1000 ppm (0.1 wt %) of water had a more dramatic effect on these properties in the latter case. Despite these differences, there was little effect in the ability to sustain stable cycling at moderate current densities and capacities (being nearly identical at 1 mA cm–2 and 1 mAh cm–2). However, the IL based on the phosphonium cation is shown to support more demanding cycling with high stability (up to 4 mAh cm–2 at 1, 2, and 4 mA cm–2 current density), whereas C3mpyrFSI rapidly failed (at 1 mA cm–2 /4 mAh cm–2). The SEI was characterized ex situ using solid-state 23Na NMR, XPS, and SEM and showed that the presence of a Na complex, identified in our previous work on C3mpyrFSI to correlate with stable, dendrite-free Na metal cycling, was also more prominent and coexisted with a NaF-rich surface. The results here represent a significant breakthrough in the development of high-capacity Na metal anodes, clearly demonstrating the superior performance and stability of the P111i4FSI electrolyte, even after the addition of water (up to 1000 ppm (0.1 wt %)), and show great promise to enable future higher-temperature (50 °C) Na-metal-based batteries.

While perovskite solar cell (PSC) efficiencies are soaring at a laboratory scale, these are most commonly achieved with evaporated gold electrodes, which would present a significant expense in large‐scale production. This can be remedied through the use of significantly cheaper carbon electrodes that, in contrast to metals, also do not migrate through the device. To this end, the present work investigates simple‐to‐prepare aluminum‐supported carbon electrodes derived from commercially available, inexpensive materials that can be applied onto various hole‐transporting materials and enable photovoltaic performances on par with those provided by gold electrodes. Successful integration of the new carbon‐based electrode into flexible devices produced by a roll‐to‐roll printing technology by both pressing and lamination is demonstrated. However, temperature cycling durability tests reveal that the use of carbon electrodes based on commercial pastes is hindered by incompatibility of adhesive additives with the key components of the PSCs under heating. Resolving this issue, tailor‐made graphite electrodes devoid of damaging additives are introduced, which improve the PSC stability under temperature cycling test protocol to the level provided by benchmark gold electrodes. The study highlights current challenges in developing laminated carbon electrodes in PSCs and proposes strategies toward the resolution thereof.

Densely assembled graphene‐based membranes have attracted substantial interest for their widespread applications, such as compact capacitive energy storage, ion/molecular separation, gas barrier films, and flexible electronics. However, the multiscale structure of densely packed graphene membranes remains ambiguously understood. This article combines X‐ray and light scattering techniques as well as dynamic electrosorption analysis to uncover the stacking structure of the densely stacked reduced graphene oxide (rGO) membranes. The membranes are produced by reducing graphene oxide (GO) membranes with hydrazine, during which the colloidal interactions between GO sheets are modulated by the electrolyte solution. In contrast to the common notion that direct reduction of densely assembled GO sheets in parallel tends to result in significant “graphitization”, this article unexpectedly discovers that the resultant densely packed rGO membrane can still retain the interconnected network nanochannels and show good capacitive performances. This inspires the development of a hierarchical structural model to describe the densely packed rGO membranes. This article further shows that the nanochannel network can be fine‐tuned at the sub‐nanometer level by tailoring the salt concentration and the reduction temperature to render exceptional volumetric capacitance and good rate performance for rGO membranes even with increased packing density.

Battery sustainability is often neglected in favor of higher performance and economic efficiency in battery technology. The standard electrode containing the use of binder and toxic solvent has a detrimental impact on the environment. For the first time, a sustainable and free‐standing carbonized silk battery anode is prepared from woven silk biomass waste. The unique mechanical structural properties and surface functionality make this material not only avoid the use of binder and organic solvent, but with the possibility of achieving high energy density batteries. An outstanding initial Coulombic efficiency of 75.6 % and a remarkable capacity retention of 100 % after 100 cycles are achieved for the electrode carbonized at 1300 °C (CS_1300 °C) when using a non‐volatile and non‐flammable superconcentrated ionic liquid electrolyte. A uniformly NaF‐distributed solid electrolyte interphase (SEI) layer is produced on the CS_1300 °C surface to facilitate Na+ transfer kinetics, and high capacity utilization. Surface functional groups are elucidated by X‐ray photoelectron spectroscopy (XPS), while density functional theory calculations reveal that these groups accelerate fast Na+ ion adsorption on the surface, but hinder Na+ intercalation kinetics due to the strong binding energy from the sodiophilic sites. This scalable and cost‐efficient strategy opens up a new avenue for mass‐production of battery anode materials, and proposes an argument for the role of surface functional groups in SEI formation and electrochemical performance.