Curious Case of Positive Current Collectors: Corrosion and Passivation at High Temperature.

In the evaluation of compatibility of different components of cell for high-energy and extreme-conditions applications, the highly focused are positive and negative electrodes and their interaction with electrolyte. However, for high-temperature application, the other components are also of significant influence and contribute toward the total health of battery. In present study, we have investigated the behavior of aluminum, the most common current collector for positive electrode materials for its electrochemical and temperature stability. For electrochemical stability, different electrolytes, organic and room temperature ionic liquids with varying Li salts (LiTFSI, LiFSI), are investigated. The combination of electrochemical and spectroscopic investigations reflects the varying mechanism of passivation at room and high temperature, as different compositions of decomposed complexes are found at the surface of metals.

Low-Cost, Large-Area, Facile, and Rapid Fabrication of Aligned ZnO Nanowire Device Arrays.

Well aligned nanowires of ZnO have been made with an electrospinning technique using zinc acetate precursor solutions. Employment of two connected parallel collector plates with a separating gap of 4 cm resulted in a very high degree of nanowire alignment. By adjusting the process parameters, the deposition density of the wires could be controlled. Field effect transistors were prepared by depositing wires between two gold electrodes on top of a heavily doped Si substrate covered with a 300 nm oxide layer. These devices showed good FET characteristics and photosensitivity under UV-illumination. The method provides a fast and scalable fabrication route for functional nanowire arrays with a high degree of alignment and control over nanowire spacing.

Ionic Liquid-Organic Carbonate Electrolyte Blends To Stabilize Silicon Electrodes for Extending Lithium Ion Battery Operability to 100 °C.

Fabrication of lithium-ion batteries that operate from room temperature to elevated temperatures entails development and subsequent identification of electrolytes and electrodes. Room temperature ionic liquids (RTILs) can address the thermal stability issues, but their poor ionic conductivity at room temperature and compatibility with traditional graphite anodes limit their practical application. To address these challenges, we evaluated novel high energy density three-dimensional nano-silicon electrodes paired with 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide (Pip) ionic liquid/propylene carbonate (PC)/LiTFSI electrolytes. We observed that addition of PC had no detrimental effects on the thermal stability and flammability of the reported electrolytes, while largely improving the transport properties at lower temperatures. Detailed investigation of the electrochemical properties of silicon half-cells as a function of PC content, temperature, and current rates reveal that capacity increases with PC content and temperature and decreases with increased current rates. For example, addition of 20% PC led to a drastic improvement in capacity as observed for the Si electrodes at 25 °C, with stability over 100 charge/discharge cycles. At 100 °C, the capacity further increases by 3-4 times to 0.52 mA h cm(-2) (2230 mA h g(-1)) with minimal loss during cycling.

Quasi-Solid Electrolytes for High Temperature Lithium Ion Batteries.

Rechargeable batteries capable of operating at high temperatures have significant use in various targeted applications. Expanding the thermal stability of current lithium ion batteries requires replacing the electrolyte and separators with stable alternatives. Since solid-state electrolytes do not have a good electrode interface, we report here the development of a new class of quasi-solid-state electrolytes, which have the structural stability of a solid and the wettability of a liquid. Microflakes of clay particles drenched in a solution of lithiated room temperature ionic liquid forming a quasi-solid system has been demonstrated to have structural stability until 355 °C. With an ionic conductivity of ∼3.35 mS cm(-1), the composite electrolyte has been shown to deliver stable electrochemical performance at 120 °C, and a rechargeable lithium battery with Li4Ti5O12 electrode has been tested to deliver reliable capacity for over several cycles of charge-discharge.

Supercapacitor operating at 200 degrees celsius.

The operating temperatures of current electrochemical energy storage devices are limited due to electrolyte degradation and separator instability at higher temperatures. Here we demonstrate that a tailored mixture of materials can facilitate operation of supercapacitors at record temperatures, as high as 200°C. Composite electrolyte/separator structures made from naturally occurring clay and room temperature ionic liquids, with graphitic carbon electrodes, show stable supercapacitor performance at 200°C with good cyclic stability. Free standing films of such high temperature composite electrolyte systems can become versatile functional membranes in several high temperature energy conversion and storage applications.

Three-dimensionally engineered porous silicon electrodes for Li ion batteries.

The ultimate goal of Li ion battery design should consist of fully accessible metallic current collectors, possibly of nanoscale dimensions, intimately in contact with high capacity stable electrode materials. Here we engineer three-dimensional porous nickel based current collector coated conformally with layers of silicon, which typically suffers from poor cycle life, to form high-capacity electrodes. These binder/conductive additive free silicon electrodes show excellent electrode adhesion resulting in superior cyclic stability and rate capability. The nickel current collector design also allows for an increase in silicon loading per unit area leading to high areal discharge capacities of up to 0.8 mAh/cm(2) without significant loss in rate capability. An excellent electrode utilization (∼85%) and improved cyclic stability for the metal/silicon system is attributed to reduced internal stresses/fracture upon electrode expansion during cycling and shorter ionic/electronic diffusion pathways that help in improving the rate capability of thicker silicon layers.

Wetting transparency of graphene.

We report that graphene coatings do not significantly disrupt the intrinsic wetting behaviour of surfaces for which surface-water interactions are dominated by van der Waals forces. Our contact angle measurements indicate that a graphene monolayer is wetting-transparent to copper, gold or silicon, but not glass, for which the wettability is dominated by short-range chemical bonding. With increasing number of graphene layers, the contact angle of water on copper gradually transitions towards the bulk graphite value, which is reached for ~6 graphene layers. Molecular dynamics simulations and theoretical predictions confirm our measurements and indicate that graphene's wetting transparency is related to its extreme thinness. We also show a 30-40% increase in condensation heat transfer on copper, as a result of the ability of the graphene coating to suppress copper oxidation without disrupting the intrinsic wettability of the surface. Such an ability to independently tune the properties of surfaces without disrupting their wetting response could have important implications in the design of conducting, conformal and impermeable surface coatings.

Harvesting energy from water flow over graphene.

Water flow over carbon nanotubes has been shown to generate an induced voltage in the flow direction due to coupling of ions present in water with free charge carriers in the nanotubes. However, the induced voltages are typically of the order of a few millivolts, too small for significant power generation. Here we perform tests involving water flow with various molarities of hydrochloric acid (HCl) over few-layered graphene and report order of magnitude higher induced voltages for graphene as compared to nanotubes. The power generated by the flow of ∼0.6 M HCl solution at ∼0.01 m/sec was measured to be ∼85 nW for a ∼30 × 16 µm size graphene film, which equates to a power per unit area of ∼175 W/m(2). Molecular dynamics simulations indicate that the power generation is primarily caused by a net drift velocity of adsorbed Cl(-) ions on the continuous graphene film surface.

Flexible ZnO-cellulose nanocomposite for multisource energy conversion.

Materials with the ability to harness multiple sources of energy from the ambient environment could lead to new types of energy-harvesting systems. It is demonstrated that nanocomposite films consisting of zinc oxide nanostructures embedded in a common paper matrix can be directly used as energy-conversion devices to transform mechanical and thermal energies to electric power. These mechanically robust and flexible devices can be fabricated over large areas and are capable of producing an output voltage and power up to 80 mV and 50 nW cm(-2) , respectively. Furthermore, it is shown that by integrating a certain number of devices (in series and parallel) the output voltage and the concomitant output power can be significantly increased. Also, the output voltage and power can be enhanced by scaling the size of the device. This multisource energy-harvesting system based on ZnO nanostructures embedded in a flexible paper matrix provides a simplified and cost-effective platform for capturing trace amounts of energy for practical applications.

Graphene growth via carburization of stainless steel and application in energy storage.

A modified version of the carburization process, a widely established technique used in the steel industry for case hardening of components, is used for the growth of graphene on stainless steel. Controlled growth of high-quality single- and few-layered graphene on stainless steel (SS) foils through a liquid-phase chemical vapor deposition (CVD) technique is reported. Reversible Li intercalation in these graphene-on-SS structures is demonstrated, where graphene and SS act as electrode and current collector, respectively, providing very good electrical contact. Direct growth of an active electrode material, such as graphene, on current-collector substrates makes this a feasible and efficient process for developing thin-film battery devices.

Synthesis of nitrogen-doped graphene films for lithium battery application.

We demonstrate a controlled growth of nitrogen-doped graphene layers by liquid precursor based chemical vapor deposition (CVD) technique. Nitrogen-doped graphene was grown directly on Cu current collectors and studied for its reversible Li-ion intercalation properties. Reversible discharge capacity of N-doped graphene is almost double compared to pristine graphene due to the large number of surface defects induced due to N-doping. All the graphene films were characterized by Raman spectroscopy, transmission electron microscopy, and X-ray photoemission spectroscopy. Direct growth of active electrode material on current collector substrates makes this a feasible and efficient process for integration into current battery manufacture technology.

Flexible piezoelectric ZnO-paper nanocomposite strain sensor.

The fabrication of a mechanically flexible, piezoelectric nanocomposite material for strain sensing applications is reported. Nanocomposite material consisting of zinc oxide (ZnO) nanostructures embedded in a stable matrix of paper (cellulose fibers) is prepared by a solvothermal method. The applicability of this material as a strain sensor is demonstrated by studying its real-time current response under both static and dynamic mechanical loading. The material presented highlights a novel approach to introduce flexibility into strain sensors by embedding crystalline piezoelectric material in a flexible cellulose-based secondary matrix.