Andrea Capasso

Binder-free graphene as an advanced anode for lithium batteries

We report the fabrication of binder-free anodes for lithium-ion batteries (LIBs) based on graphene nanoflakes on-demand designed and produced by liquid phase exfoliation of graphite. A solvent exchange process is exploited to first remove the N-methyl-2-pyrrolidone used for the exfoliation of graphite and then to re-disperse the exfoliated single-(SLG) and few-layer (FLG) graphene flakes, at a high concentration (∼5 g L−1), in an environmentally friendly solvent, i.e., ethanol. Anodes are realized by drop-casting the SLG- and FLG-based ink in ethanol under ambient conditions on a Cu foil without any binder or conductive agents, typically used for the fabrication of conventional LIBs. We tested our SLG- and FLG-based anodes in a half-cell configuration, achieving a reversible specific capacity of ∼500 mA h g−1 after 100 cycles at a current density of 0.1 A g−1, with coulombic efficiency >99.5%. We also tested the SLG- and FLG-based anode in a full-cell configuration, exploiting commercial LiNi0.5Mn1.5O4 as a cathode. The battery operates around 4.7 V with a flat-plateau voltage profile and a reversible specific capacity of ∼100 mA h g−1. The proposed electrode fabrication process is fast, low cost and industrially scalable opening the way to the optimization of energy and power densities, lifetime and safety of LIBs, while minimizing their cost and environmental impact.

Few-layer MoS2 flakes as a hole-selective layer for solution-processed hybrid organic hydrogen-evolving photocathodes

High-efficiency organic photocathodes, based on a regioregular poly(3-hexylthiophene) and phenyl-C61-butyric acid methyl ester (rr-P3HT:PCBM) bulk heterojunction sandwiched between charge-selective layers, are emerging as efficient and low-cost devices for solar hydrogen production by water splitting. Nevertheless, stability issues of the materials used as charge-selective layers are hampering the realization of long-lasting photoelectrodes, pointing out the need to investigate novel and stable materials. Here, we propose MoS2 flakes, produced by Li-aided exfoliation of the bulk counterpart, as an efficient atomic-thick hole-selective layer for rr-P3HT:PCBM-based photocathodes. We carried out p-type chemical doping to tune on-demand the MoS2 Fermi level in order to match the highest occupied molecular orbital level of the rr-P3HT, thus easing the hole collection at the electrode. The as-prepared p-doped MoS2-based photocathodes reached a photocurrent of 1.21 mA cm−2 at 0 V vs. RHE, a positive onset potential of 0.56 V vs. RHE and a power-saved figure of merit of 0.43%, showing a 6.1-fold increase with respect to pristine MoS2-based photocathodes, under simulated 1 sun illumination. Operational activity of the photocathodes over time and under 1 sun illumination revealed a progressive stabilization of the photocurrents at 0.49 mA cm−2 at 0 V vs. RHE. These results pave the way towards the exploitation of layered crystals as efficiency-boosters for scalable hybrid organic H2-evolving photoelectrochemical cells.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: Influence of process parameters on the electrical and optical properties

Summary Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp2 carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 105 S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Low-temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

Summary The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multiwall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultrathin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge-carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open-circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.

Cyclododecane as support material for clean and facile transfer of large-area few-layer graphene

The transfer of chemical vapor deposited graphene is a crucial process, which can affect the quality of the transferred films and compromise their application in devices. Finding a robust and intrinsically clean material capable of easing the transfer of graphene without interfering with its properties remains a challenge. We here propose the use of an organic compound, cyclododecane, as a transfer material. This material can be easily spin coated on graphene and assist the transfer, leaving no residues and requiring no further removal processes. The effectiveness of this transfer method for few-layer graphene on a large area was evaluated and confirmed by microscopy, Raman spectroscopy, x-ray photoemission spectroscopy, and four-point probe measurements. Schottky-barrier solar cells with few-layer graphene were fabricated on silicon wafers by using the cyclododecane transfer method and outperformed reference cells made by standard methods.

Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries

The liquid-phase exfoliation (LPE) of black phosphorus (BP) is a strategic route for the large-scale production of phosphorene and few-layer BP (FL-BP) flakes. The exploitation of this exfoliated material in cutting-edge technologies, e.g., in flexible electronics and energy storage, is however limited by the fact that the LPE of BP is usually carried out at a high boiling point and in toxic solvents. In fact, the solvent residual is detrimental to device performance in real applications; thus, complete solvent removal is critical. Here, we tackle these issues by exfoliating BP in different low-boiling-point solvents. Among these solvents, we find that acetone also provides a high concentration of exfoliated BP, leading to the production of FL-BP flakes with an average lateral size and thickness of ∼30 and ∼7 nm, respectively. The use of acetone to produce less defective few-layer BP flakes (FL-BPacetone) from bulk crystals is a straightforward process which enables the rapid preparation of homogeneous th...

Chemical Vapor Deposited Graphene-Based Derivative As High-Performance Hole Transport Material for Organic Photovoltaics

UNLABELLED The development of efficient charge transport layers is a key requirement for the fabrication of efficient and stable organic solar cells. A graphene-based derivative with planar resistivity exceeding 10(5) Ω/□ and work function of 4.9 eV is here produced by finely tuning the parameters of the chemical vapor deposition process on copper. After the growth, the film is transferred to glass/indium tin oxide and used as hole transport layer in organic solar cells based on a PBDTTT-C-T:[70]PCBM blend. The cells attained a maximum power conversion efficiency of 5%, matching reference cells made with state-of-the-art PEDOT PSS as the hole transport layer. Our results indicate that functionalized graphene could represent an effective alternative to PEDOT PSS as hole transport/electron blocking layer in solution-processed organic photovoltaics.

Fast growth of polycrystalline graphene by chemical vapor deposition of ethanol on copper

High conductive graphene films can be grown on metal foils by chemical vapor deposition (CVD). We here analyzed the use of ethanol, an economic precursor, which results also safer than commonly-used methane. A comprehensive range of process parameters were explored in order to obtain graphene films with optimal characteristics in view of their use in optoelectronics and photovoltaics. Commercially-available and electro-polished copper foils were used as substrates. By finely tuning the CVD conditions, we obtained few-layer (2-4) graphene films with good conductivity (~500 Ohm/sq) and optical transmittance around 92-94% at 550 nm on unpolished copper foils. The growth on electro-polished copper provides instead predominantly mono-layer films with lower conductivity (≥1000 Ohm/sq) and with a transmittance of 97.4% at 550 nm. As for the device properties, graphene with optimal properties as transparent conductive film were produced by CVD on standard copper with specific process conditions.

Spray deposition of exfoliated MoS2 flakes as hole transport layer in perovskite-based photovoltaics

We propose the use of solution-processed molybdenum disulfide (MoS₂) flakes as hole transport layer (HTL) for metal-organic perovskite solar cells. MoS₂ bulk crystals are exfoliated in 2-propanol and deposited on perovskite layers by spray coating. We fabricated cells with glass/FTO/compact-TiO₂/mesoporous-TiO₂/CH₃NH₃PbI₃/spiro-OMeTAD/Au structure and cells with the same structure but with MoS₂ flakes as HTL instead of spiro-OMeTAD, the most widely used HTL. The electrical characterization of the cells with MoS₂ as HTL show promising power conversion efficiency -η- of 3.9% with respect to cells with pristine spiro-OMeTAD (η=3.1%). Endurance test on 800-hour shelf life has shown higher stability for the MoS₂-based cells (ΔPCE/PCE=-17%) with respect to the doped spiro-OMeTAD-based one (ΔPCE/PCE =-45%). Further improvements are expected with the optimization of the MoS₂ deposition process

Interface of graphane with copper: a van der Waals density-functional study

Various forms of hydrogenated graphene have been produced to date by several groups, while the synthesis of pure graphane has not been achieved yet. The study of the interface between graphane, in all its possible hydrogenation configurations, and catalyst metal surfaces can be pivotal to assess the feasibility of direct CVD growth methods for this material. We investigated the adhesion of graphane to a Cu(111) surface by adopting the vdW-DF2-C09 exchange-correlation functional, which is able to describe dispersion forces. The results are further compared with the PBE and the LDA exchange-correlation functionals. We calculated the most stable geometrical configurations of the slab/graphane interface and evaluated how graphanes geometrical parameters are modified. We show that dispersion forces play an important role in the slab/graphane adhesion. Band structure calculations demonstrated that in the presence of the interaction with copper, the band gap of graphane is not only preserved, but also enlarged, and this increase can be attributed to the electronic charge accumulated at the interface. We calculated a substantial energy barrier at the interface, suggesting that CVD graphane films might act as reliable and stable insulating thin coatings, or also be used to form compound layers in conjunction with metals and semiconductors.