Sweetening Lithium Metal Interface by High Surface and Adhesive Energy Coating of Crystalline α-d-Glucose Film to Inhibit Dendrite Growth.

The notorious growth of lithium (Li) dendrites and the instability of the solid electrolyte interface (SEI) during cycling make Li metal anodes unsuitable for use in commercial Li-ion batteries. Herein, the use of simple sugar coating (α-d-glucose) is demonstrated on top of Li metal to halt the growth of Li dendrites and stabilize the SEI. The α-d-glucose layer possesses high surface and adhesive energies toward Li, which promote the homogenous stripping and plating of Li ions on top of the Li metal. Density functional theory reveals that Li-ion diffusion within the α-d-glucose layer is governed by hopping around the bare sides of the O atoms and along the apparent passages formed by the glucose molecules. Stable cycling performance is achieved when combining α-d-glucose-coated Li (G|Li) anodes with sulfur- and LiFePO4 -based cathodes in both LiTFSI (ether) and LiPF6 (carbonate) electrolyte systems. A G|Li-based symmetrical cell operates at a current density of 1 mA cm-2 and areal capacity of 1 mAh cm-2 displays a stable overpotential profile for over 9 months (7000 h) of continuous charge/discharge cycling.

High-Performance Organic Solar Cells Featuring Double Bulk Heterojunction Structures with Vertical-Gradient Selenium Heterocyclic Nonfullerene Acceptor Concentrations.

In this study, we prepared organic photovoltaics (OPVs) featuring an active layer comprising double bulk heterojunction (BHJ) structures, featuring binary blends of a polymer donor and concentration gradients of two small-molecule acceptors. After forming the first BHJ structure by spin-coating, the second BHJ layer was transfer-printed onto the first using polydimethylsiloxane stamps. A specially designed selenium heterocyclic small-molecule acceptor (Y6-Se-4Cl) was employed as the second acceptor in the BHJ. X-ray photoelectron spectroscopy revealed that the two acceptors formed a gradient concentration profile across the active layer, thereby facilitating charge transportation. The best power conversion efficiencies (PCEs) for the double-BHJ-structured devices incorporating PM6:Y6-Se-4Cl/PM6:Y6 and PM6:Y6-Se-4Cl/PM6:IT-4Cl were 16.4 and 15.8%, respectively; these values were higher than those of devices having one-BHJ structures based on PM6:Y6-Se-4Cl (15.0%), PM6:Y6 (15.4%), and PM6:IT-4Cl (11.6%), presumably because of the favorable vertical concentration gradient of the selenium-containing small-molecule Y6-Se-4Cl in the active layer as well as some complementary light absorption. Thus, combining two BHJ structures with a concentration gradient of the two small-molecule acceptors can be an effective approach for enhancing the PCEs of OPVs.

High-Performance Organic Photovoltaics Incorporating an Active Layer with a Few Nanometer-Thick Third-Component Layer on a Binary Blend Layer.

In this paper, a universal approach toward constructing a new bilayer device architecture, a few-nanometer-thick third-component layer on a bulk-heterojunction (BHJ) binary blend layer, has been demonstrated in two different state-of-the-art organic photovoltaic (OPV) systems. Through a careful selection of a third component, the power conversion efficiency (PCE) of the device based on PM6/Y6/layered PTQ10 layered third-component structure was 16.8%, being higher than those of corresponding devices incorporating the PM6/Y6/PTQ10 BHJ ternary blend (16.1%) and the PM6/Y6 BHJ binary blend (15.5%). Also, the device featuring PM7/Y1-4F/layered PTQ10 layered third-component structure gave a PCE of 15.2%, which is higher than the PCEs of the devices incorporating the PM7/Y1-4F/PTQ10 BHJ ternary blend and the PM7/Y1-4F BHJ binary blend (14.2 and 14.0%, respectively). These enhancements in PCE based on layered third-component structure can be attributed to improvements in the charge separation and charge collection abilities. This simple concept of the layered third-component structure appears to have great promise for achieving high-performance OPVs.

Modulating Performance and Stability of Inorganic Lead-Free Perovskite Solar Cells via Lewis-Pair Mediation.

Fully inorganic perovskites based on Bi3+ and Sb3+ are emerging as alternatives that overcome the toxicity and low stability of their Pb-based perovskite counterparts. Nevertheless, the thin film fabrication of Pb-free perovskites remains a struggle, with poor morphologies and incomplete conversions greatly inhibiting device performance. In this study, we modulated the crystallization of an all-inorganic dimer phase of a Sb perovskite (d-Cs3Sb2I9) through gradual increase in the annealing temperature, accompanied by the use of Lewis bases for adduct formation. Here, the role of Lewis pairing in the crystallization of the resulting Pb-free Cs3Sb2I9 thin films has been investigated. Both, "S-donor" (thiourea) and "O-donor" [N-methylpyrrolidone (NMP)] Lewis bases are examined for their abilities to form adducts with Cs+ and Sb3+ cations. Furthermore, density functional theory has been used to estimate the binding energies of these Lewis bases with the Cs3Sb2I9 lattice. Temperature-dependent photoluminescence spectroscopy revealed the nature of the band gap of d-Cs3Sb2I9. The efficiency of the resulting perovskite solar cells was enhanced to 1.8%, with excellent stability observed, when using NMP to form the adduct film. To the best of our knowledge, this is the best solar cell efficiency for the dimer phase of the inorganic Sb-based perovskite. The effects of both S- and O-donors are studied under various environmental stresses to reveal the stability responses of the devices.

Lead-Free Antimony-Based Light-Emitting Diodes through the Vapor-Anion-Exchange Method.

Hybrid lead halide perovskites continue to attract interest for use in optoelectronic devices such as solar cells and light-emitting diodes. Although challenging, the replacement of toxic lead in these systems is an active field of research. Recently, the use of trivalent metal cations (Bi3+ and Sb3+) that form defect perovskites A3B2X9 has received great attention for the development of solar cells, but their light-emissive properties have not previously been studied. Herein, an all-inorganic antimony-based two-dimensional perovskite, Cs3Sb2I9, was synthesized using the solution process. Vapor-anion-exchange method was employed to change the structural composition from Cs3Sb2I9 to Cs3Sb2Br9 or Cs3Sb2Cl9 by treating CsI/SbI3 spin-coated films with SbBr3 or SbCl3, respectively. This novel method facilitates the fabrication of Cs3Sb2Br9 or Cs3Sb2Cl9 through solution processing without the need of using poorly soluble precursors (e.g., CsCl and CsBr). We go on to demonstrate electroluminescence from a device employing Cs3Sb2I9 emitter sandwiched between ITO/PEDOT:PSS and TPBi/LiF/Al as the hole and electron injection electrodes, respectively. A visible-infrared radiance of 0.012 W·Sr-1·m-2 was measured at 6 V when Cs3Sb2I9 was the active emitter layer. These proof-of-principle devices suggest a viable path toward low-dimensional, lead-free A3B2X9 perovskite optoelectronics.

A lithium passivated MoO3 nanobelt decorated polypropylene separator for fast-charging long-life Li-S batteries.

Dissolution of lithium polysulfide (LiPS) into the electrolyte during discharging, causing shuttling of LiPS from the cathode to the lithium (Li) metal, is mainly responsible for the capacity decay and short battery life of lithium-sulfur batteries (LSBs). Herein, we designed a separator comprising polypropylene (PP) coated with MoO3 nanobelts (MNBs), prepared through facile grinding of commercial MoO3 powder. The formation of Li2Sn-MoO3 during discharging inhibited the polysulfide shuttling; during charging, Li passivated LixMoO3 facilitated ionic transfer during the redox reaction by decreasing the charge transfer resistance. This dual-interaction mechanism of LiPS-with both Mo and the formation of LixMoO3-resulted in a substantially high initial discharge capacity at a very high current density of 5C, with 29.4% of the capacity retained after 5000 cycles. The simple fabrication approach and extraordinary cycle life observed when using this MNB-coated separator suggest a scalable solution for future commercialization of LSBs.

Top Illuminated Hysteresis-Free Perovskite Solar Cells Incorporating Microcavity Structures on Metal Electrodes: A Combined Experimental and Theoretical Approach.

Further technological development of perovskite solar cells (PSCs) will require improvements in power conversion efficiency and stability, while maintaining low material costs and simple fabrication. In this Research Article, we describe top-illuminated ITO-free, stable PSCs featuring microcavity structures, wherein metal layers on both sides on the active layers exerted light interference effects in the active layer, potentially increasing the light path length inside the active layer. The optical constants (refractive index and extinction coefficient) of each layer in the PSC devices were measured, while the optical field intensity distribution was simulated using the transfer matrix method. The photocurrent densities of perovskite layers of various thicknesses were also simulated; these results mimic our experimental values exceptionally well. To modify the cavity electrode surface, we deposited a few nanometers of ultrathin MoO3 (2, 4, and 6 nm) in between the Ag and poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) layers provide hydrophobicity to the Ag surface and elevate the work function of Ag to match that of the hole transport layer. We achieved a power conversion efficiency (PCE) of 13.54% without hysteresis in the device containing a 4 nm-thick layer of MoO3. In addition, we fabricated these devices on various cavity electrodes (Al, Ag, Au, Cu); those prepared using Cu and Au anodes displayed improved device stability of up to 72 days. Furthermore, we prepared flexible PSCs having a PCE of 12.81% after incorporating the microcavity structures onto poly(ethylene terephthalate) as the substrate. These flexible solar cells displayed excellent stability against bending deformation, maintaining greater than 94% stability after 1000 bending cycles and greater than 85% after 2500 bending cycles performed with a bending radius of 5 mm.

Photovoltaic Performance of Vapor-Assisted Solution-Processed Layer Polymorph of Cs3Sb2I9.

The presence of toxic lead (Pb) remains a major obstruction to the commercial application of perovskite solar cells. Although antimony (Sb)-based perovskite-like structures A3M2X9 can display potentially useful photovoltaic behavior, solution-processed Sb-based perovskite-like structures usually favor the dimer phase, which has poor photovoltaic properties. In this study, we prepared a layered polymorph of Cs3Sb2I9 through solution-processing and studied its photovoltaic properties. The exciton binding energy and exciton lifetime of the layer-form Cs3Sb2I9 were approximately 100 meV and 6 ns, respectively. The photovoltaic properties of the layered polymorph were superior to those of the dimer polymorph. A solar cell incorporating the layer-form Cs3Sb2I9 exhibited an open-circuit voltage of 0.72 V and a power conversion efficiency of 1.5%-the highest reported for an all-inorganic Sb-based perovskite.

Modified Separator Performing Dual Physical/Chemical Roles to Inhibit Polysulfide Shuttle Resulting in Ultrastable Li-S Batteries.

In this paper we describe a modified (AEG/CH) coated separator for Li-S batteries in which the shuttling phenomenon of the lithium polysulfides is restrained through two types of interactions: activated expanded graphite (AEG) flakes interacted physically with the lithium polysulfides, while chitosan (CH), used to bind the AEG flakes on the separator, interacted chemically through its abundance of amino and hydroxyl functional groups. Moreover, the AEG flakes facilitated ionic and electronic transfer during the redox reaction. Live H-cell discharging experiments revealed that the modified separator was effective at curbing polysulfide shuttling; moreover, X-ray photoelectron spectroscopy analysis of the cycled separator confirmed the presence of lithium polysulfides in the AEG/CH matrix. Using this dual functional interaction approach, the lifetime of the pure sulfur-based cathode was extended to 3000 cycles at 1C-rate (1C = 1670 mA/g), decreasing the decay rate to 0.021% per cycle, a value that is among the best reported to date. A flexible battery based on this modified separator exhibited stable performance and could turn on multiple light-emitting diodes. Such modified membranes with good mechanical strength, high electronic conductivity, and anti-self-discharging shield appear to be a scalable solution for future high-energy battery systems.