RESUMEN
A novel WS2-graphite dual-ion battery (DIB) is developed by combining a conventional graphite cathode and a high-capacity few-layer WS2-flake anode. The WS2 flakes are produced by exploiting wet-jet milling (WJM) exfoliation, which allows large-scale and free-material loss production (i.e., volume up to 8 L h-1 at concentration of 10 g L-1 and exfoliation yield of 100%) of few-layer WS2 flakes in dispersion. The WS2 anodes enable DIBs, based on hexafluorophosphate (PF6-) and lithium (Li+) ions, to achieve charge-specific capacities of 457, 438, 421, 403, 295, and 169 mAh g-1 at current rates of 0.1, 0.2, 0.3, 0.4, 0.8, and 1.0 A g-1, respectively, outperforming conventional DIBs. The WS2-based DIBs operate in the 0 to 4 V cell voltage range, thus extending the operating voltage window of conventional WS2-based Li-ion batteries (LIBs). These results demonstrate a new route toward the exploitation of WS2, and possibly other transition-metal dichalcogenides, for the development of next-generation energy-storage devices.
RESUMEN
Interface engineering of organic-inorganic halide perovskite solar cells (PSCs) plays a pivotal role in achieving high power conversion efficiency (PCE). In fact, the perovskite photoactive layer needs to work synergistically with the other functional components of the cell, such as charge transporting/active buffer layers and electrodes. In this context, graphene and related two-dimensional materials (GRMs) are promising candidates to tune "on demand" the interface properties of PSCs. In this work, we fully exploit the potential of GRMs by controlling the optoelectronic properties of molybdenum disulfide (MoS2) and reduced graphene oxide (RGO) hybrids both as hole transport layer (HTL) and active buffer layer (ABL) in mesoscopic methylammonium lead iodide (CH3NH3PbI3) perovskite (MAPbI3)-based PSCs. We show that zero-dimensional MoS2 quantum dots (MoS2 QDs), derived by liquid phase exfoliated MoS2 flakes, provide both hole-extraction and electron-blocking properties. In fact, on one hand, intrinsic n-type doping-induced intraband gap states effectively extract the holes through an electron injection mechanism. On the other hand, quantum confinement effects increase the optical band gap of MoS2 (from 1.4 eV for the flakes to >3.2 eV for QDs), raising the minimum energy of its conduction band (from -4.3 eV for the flakes to -2.2 eV for QDs) above the one of the conduction band of MAPbI3 (between -3.7 and -4 eV) and hindering electron collection. The van der Waals hybridization of MoS2 QDs with functionalized reduced graphene oxide (f-RGO), obtained by chemical silanization-induced linkage between RGO and (3-mercaptopropyl)trimethoxysilane, is effective to homogenize the deposition of HTLs or ABLs onto the perovskite film, since the two-dimensional nature of RGO effectively plugs the pinholes of the MoS2 QD films. Our "graphene interface engineering" (GIE) strategy based on van der Waals MoS2 QD/graphene hybrids enables MAPbI3-based PSCs to achieve a PCE up to 20.12% (average PCE of 18.8%). The possibility to combine quantum and chemical effects into GIE, coupled with the recent success of graphene and GRMs as interfacial layer, represents a promising approach for the development of next-generation PSCs.
RESUMEN
Nanomaterials may be contaminated with bacterial endotoxin during production and handling, which may confound toxicological testing of these materials, not least when assessing for immunotoxicity. In the present study, we evaluated the conventional Limulus amebocyte lysate (LAL) assay for endotoxin detection in graphene based material (GBM) samples, including graphene oxide (GO) and few-layered graphene (FLG). Our results showed that some GO samples interfered with various formats of the LAL assay. To overcome this problem, we developed a TNF-α expression test (TET) using primary human monocyte-derived macrophages incubated in the presence or absence of the endotoxin inhibitor, polymyxin B sulfate, and found that this assay, performed with non-cytotoxic doses of the GBM samples, enabled unequivocal detection of endotoxin with a sensitivity that is comparable to the LAL assay. FLG also triggered TNF-α production in the presence of the LPS inhibitor, pointing to an intrinsic pro-inflammatory effect. Finally, we present guidelines for the preparation of endotoxin-free GO, validated by using the TET.
