Freestanding electrodes are a promising way to increase the energy density of the batteries by decreasing the overall amount of electrochemically inactive materials. Freestanding antimony doped tin oxide (ATO)‐based hybrid materials have not been reported so far, although this material has demonstrated excellent performance in conventionally designed electrodes. Two different strategies, namely electrospinning and freeze‐casting, are explored for the fabrication of ATO‐based hybrid materials. It is shown that the electrospinning of ATO/carbon based electrodes from polyvinyl pyrrolidone polymer (PVP) solutions was not successful, as the resulting electrode material suffers from rapid degradation. However, freestanding reduced graphene oxide (rGO) containing ATO/C/rGO nanocomposites prepared via a freeze‐casting route demonstrates an impressive rate and cycling performance reaching 697 mAh g−1 at a high current density of 4 A g−1, which is 40 times higher as compared to SnO2/rGO and also exceeds the freestanding SnO2‐based composites reported so far. Antimony doping of the nanosized tin oxide phase and carbon coating are thereby shown to be essential factors for appealing electrochemical performance. Finally, the freestanding ATO/C/rGO anodes are combined with freestanding LiFe0.2Mn0.8PO4/rGO cathodes to obtain a full freestanding cell operating without metal current collector foils showing nonetheless an excellent cycling stability.
Heteroatom alloying of lead-free perovskite derivatives is a highly promising route to tailor their optoelectronic properties and stability for multiple applications. Here, we demonstrate the facile solution-based synthesis of Sn-alloyed layered MA 3 Sb 2 I 9 thin films by precursor engineering, combining acetate and halide salts. An increasing concentration of tin halides in different oxidation states leads to a strong boost in absorption over the whole visible spectrum. We demonstrate phase-pure synthesis and elucidate the heterovalent incorporation of Sn into the MA 3 Sb 2 I 9 lattice, proving the formation of additional electronic states in the bandgap by theoretical calculations. On this basis, we dissect the strong absorption increase into three components that we attribute to intervalence and heteroatom-induced interband absorption. Finally, we show the charge-stabilizing effect of the system through robustness toward precursors in mixed oxidation states and trace the improved ambient stability of this material back to this feature.
In the field of perovskite solar cells, explorations of new lead-free all-inorganic perovskite materials are of great interest to address the instability and toxicity issues of lead-based hybrid perovskites. Recently, copper-antimony-based double perovskite materials have been reported with ideal band gaps, which possess great potential as absorbers for photovoltaic applications. Here, we synthesize Cs2CuSbCl6 double perovskite nanocrystals (DPNCs) at ambient conditions by a facile and fast synthesis method, namely, a modified ligand-assisted reprecipitation method. We choose methanol as a solvent for precursor salts as it is less toxic and easily removed in contrast to widely used dimethylformamide. Our computational structure search shows that the Cs2CuSbCl6 structure containing alternating [CuCl6]5− and [SbCl6]3− octahedral units is a metastable phase that is 30 meV/atom higher in energy compared to the ground state structure with [CuCl3]2− and [SbCl6]3− polyhedra. However, this metastable Cs2CuSbCl6 double perovskite structure can be stabilized through solution-based nanocrystal synthesis. Using an anion-exchange method, Cs2CuSbBr6 DPNCs are obtained for the first time, featuring a narrow bandgap of 0.9 eV. Finally, taking advantage of the solution processability of DPNCs, smooth and dense Cs2CuSbCl6 and Cs2CuSbBr6 DPNC films are successfully fabricated.
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