Mauro Pasta

Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers

Layered materials consist of molecular layers stacked together by weak interlayer interactions. They often crystallize to form atomically smooth thin films, nanotubes, and platelet or fullerene-like nanoparticles due to the anisotropic bonding. Structures that predominately expose edges of the layers exhibit high surface energy and are often considered unstable. In this communication, we present a synthesis process to grow MoS2 and MoSe2 thin films with vertically aligned layers, thereby maximally exposing the edges on the film surface. Such edge-terminated films are metastable structures of MoS2 and MoSe2, which may find applications in diverse catalytic reactions. We have confirmed their catalytic activity in a hydrogen evolution reaction (HER), in which the exchange current density correlates directly with the density of the exposed edge sites.

A phosphorene–graphene hybrid material as a high-capacity anode for sodium-ion batteries

Sodium-ion batteries have recently attracted significant attention as an alternative to lithium-ion batteries because sodium sources do not present the geopolitical issues that lithium sources might. Although recent reports on cathode materials for sodium-ion batteries have demonstrated performances comparable to their lithium-ion counterparts, the major scientific challenge for a competitive sodium-ion battery technology is to develop viable anode materials. Here we show that a hybrid material made out of a few phosphorene layers sandwiched between graphene layers shows a specific capacity of 2,440 mA h g(-1) (calculated using the mass of phosphorus only) at a current density of 0.05 A g(-1) and an 83% capacity retention after 100 cycles while operating between 0 and 1.5 V. Using in situ transmission electron microscopy and ex situ X-ray diffraction techniques, we explain the large capacity of our anode through a dual mechanism of intercalation of sodium ions along the x axis of the phosphorene layers followed by the formation of a Na3P alloy. The presence of graphene layers in the hybrid material works as a mechanical backbone and an electrical highway, ensuring that a suitable elastic buffer space accommodates the anisotropic expansion of phosphorene layers along the y and z axial directions for stable cycling operation.

Symmetrical MnO2-carbon nanotube-textile nanostructures for wearable pseudocapacitors with high mass loading

While MnO(2) is a promising material for pseudocapacitor applications due to its high specific capacity and low cost, MnO(2) electrodes suffer from their low electrical and ionic conductivities. In this article, we report a structure where MnO(2) nanoflowers were conformally electrodeposited onto carbon nanotube (CNT)-enabled conductive textile fibers. Such nanostructures effectively decrease the ion diffusion and charge transport resistance in the electrode. For a given areal mass loading, the thickness of MnO(2) on conductive textile fibers is much smaller than that on a flat metal substrate. Such a porous structure also allows a large mass loading, up to 8.3 mg/cm(2), which leads to a high areal capacitance of 2.8 F/cm(2) at a scan rate of 0.05 mV/s. Full cells were demonstrated, where the MnO(2)-CNT-textile was used as a positive electrode, reduced MnO(2)-CNT-textile as a negative electrode, and 0.5 M Na(2)SO(4) in water as the electrolyte. The resulting pseudocapacitor shows promising results as a low-cost energy storage solution and an attractive wearable power.

Three-Dimensional Carbon Nanotube−Textile Anode for High-Performance Microbial Fuel Cells

Microbial fuel cells (MFCs) harness the metabolism of microorganisms, converting chemical energy into electrical energy. Anode performance is an important factor limiting the power density of MFCs for practical application. Improving the anode design is thus important for enhancing the MFC performance, but only a little development has been reported. Here, we describe a biocompatible, highly conductive, two-scale porous anode fabricated from a carbon nanotube-textile (CNT-textile) composite for high-performance MFCs. The macroscale porous structure of the intertwined CNT-textile fibers creates an open 3D space for efficient substrate transport and internal colonization by a diverse microflora, resulting in a 10-fold-larger anolyte-biofilm-anode interfacial area than the projective surface area of the CNT-textile. The conformally coated microscale porous CNT layer displays strong interaction with the microbial biofilm, facilitating electron transfer from exoelectrogens to the CNT-textile anode. An MFC equipped with a CNT-textile anode has a 10-fold-lower charge-transfer resistance and achieves considerably better performance than one equipped with a traditional carbon cloth anode: the maximum current density is 157% higher, the maximum power density is 68% higher, and the energy recovery is 141% greater.

A high-rate and long cycle life aqueous electrolyte battery for grid-scale energy storage

New types of energy storage are needed in conjunction with the deployment of solar, wind and other volatile renewable energy sources and their integration with the electric grid. No existing energy storage technology can economically provide the power, cycle life and energy efficiency needed to respond to the costly short-term transients that arise from renewables and other aspects of grid operation. Here we demonstrate a new type of safe, fast, inexpensive, long-life aqueous electrolyte battery, which relies on the insertion of potassium ions into a copper hexacyanoferrate cathode and a novel activated carbon/polypyrrole hybrid anode. The cathode reacts rapidly with very little hysteresis. The hybrid anode uses an electrochemically active additive to tune its potential. This high-rate, high-efficiency cell has a 95% round-trip energy efficiency when cycled at a 5C rate, and a 79% energy efficiency at 50C. It also has zero-capacity loss after 1,000 deep-discharge cycles.

Manganese hexacyanomanganate open framework as a high-capacity positive electrode material for sodium-ion batteries

Potential applications of sodium-ion batteries in grid-scale energy storage, portable electronics and electric vehicles have revitalized research interest in these batteries. However, the performance of sodium-ion electrode materials has not been competitive with that of lithium-ion electrode materials. Here we present sodium manganese hexacyanomanganate (Na2MnII[MnII(CN)6]), an open-framework crystal structure material, as a viable positive electrode for sodium-ion batteries. We demonstrate a high discharge capacity of 209 mAh g(-1) at C/5 (40 mA g(-1)) and excellent capacity retention at high rates in a propylene carbonate electrolyte. We provide chemical and structural evidence for the unprecedented storage of 50% more sodium cations than previously thought possible during electrochemical cycling. These results represent a step forward in the development of sodium-ion batteries.

Full open-framework batteries for stationary energy storage

New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.

Tunable reaction potentials in open framework nanoparticle battery electrodes for grid-scale energy storage.

The electrical energy grid has a growing need for energy storage to address short-term transients, frequency regulation, and load leveling. Though electrochemical energy storage devices such as batteries offer an attractive solution, current commercial battery technology cannot provide adequate power, and cycle life, and energy efficiency at a sufficiently low cost. Copper hexacyanoferrate and nickel hexacyanoferrate, two open framework materials with the Prussian Blue structure, were recently shown to offer ultralong cycle life and high-rate performance when operated as battery electrodes in safe, inexpensive aqueous sodium ion and potassium ion electrolytes. In this report, we demonstrate that the reaction potential of copper-nickel alloy hexacyanoferrate nanoparticles may be tuned by controlling the ratio of copper to nickel in these materials. X-ray diffraction, TEM energy dispersive X-ray spectroscopy, and galvanostatic electrochemical cycling of copper-nickel hexacyanoferrate reveal that copper and nickel form a fully miscible solution at particular sites in the framework without perturbing the structure. This allows copper-nickel hexacyanoferrate to reversibly intercalate sodium and potassium ions for over 2000 cycles with capacity retentions of 100% and 91%, respectively. The ability to precisely tune the reaction potential of copper-nickel hexacyanoferrate without sacrificing cycle life will allow the development of full cells that utilize the entire electrochemical stability window of aqueous sodium and potassium ion electrolytes.

Entrapment of Polysulfides by a Black-Phosphorus-Modified Separator for Lithium-Sulfur Batteries.

A bifunctional separator modified by black-phosphorus nanoflakes is prepared to overcome the challenges associated with the polysulfide diffusion in lithium-sulfur batteries. It brings the benefits of the entrapment of various sulfur species via the strong binding energy and re-activation of the trapped sulfur species due to its high electron conductivity as well as Li-ion diffusivity.

Alkaline glucose oxidation on nanostructured gold electrodes

The electrocatalytic properties of nanostructured gold electrodes for glucose electro-oxidation in KOH were investigated by cyclic voltammetry and compared with a commercially available polycrystalline gold electrode. These electrodes were prepared by depositing gold nanoparticles from a sol onto different carbonaceous conductive supports: glassy carbon, carbon cloth and graphite paper. The gold sol was prepared reducing an aqueous solution of tetrachloroauric acid with sodium borohydride. In order to improve gold nanoparticle adhesion, the substrate surfaces were treated with warm concentrated nitric acid. Gold on treated carbon cloth turned out to be a very promising anode for glucose electro-oxidation. In order to better understand the glucose oxidation its pH dependence as well as sorbitol (the glucose reduction product) electroxidation were investigated.