Directing Highly Ordered and Dense Li Deposition to Achieve Stable Li Metal Batteries.

Li metal anode is promising to achieve high-energy-density battery. However, it has rapid capacity fading due to the generation of inactive Li (dead Li), especially at high current density. This study reveals that the random distribution of Li nuclei leads to large uncertainty for the further growth behavior on Cu foil. Here, periodical regulation of Li nucleation sites on Cu foil by ordered lithiophilic micro-grooves is proposed to precisely manipulate the Li deposition morphology. The management of Li deposits in the lithiophilic grooves can induce high pressure on the Li particles, leading to the formation of dense Li structure and smooth surface without dendrite growth. Li deposits comprising tightly packed large Li particles largely reduce the side reaction and the generation of isolated metallic Li at high current density. Less dead Li accumulating on the substrate significantly prolongs the cycling life of full cells with limited Li inventory. The precise manipulation of the Li deposition on Cu is promising for high-energy and stable Li metal batteries.

Flexible layer-structured Bi2Te3 thermoelectric on a carbon nanotube scaffold.

Inorganic chalcogenides are traditional high-performance thermoelectric materials. However, they suffer from intrinsic brittleness and it is very difficult to obtain materials with both high thermoelectric ability and good flexibility. Here, we report a flexible thermoelectric material comprising highly ordered Bi2Te3 nanocrystals anchored on a single-walled carbon nanotube (SWCNT) network, where a crystallographic relationship exists between the Bi2Te3 <[Formula: see text]> orientation and SWCNT bundle axis. This material has a power factor of ~1,600 µW m-1 K-2 at room temperature, decreasing to 1,100 µW m-1 K-2 at 473 K. With a low in-plane lattice thermal conductivity of 0.26 ± 0.03 W m-1 K-1, a maximum thermoelectric figure of merit (ZT) of 0.89 at room temperature is achieved, originating from a strong phonon scattering effect. The origin of the excellent flexibility and thermoelectric performance of the Bi2Te3-SWCNT material is attributed, by experimental and computational evidence, to its crystal orientation, interface and nanopore structure. Our results provide insight into the design and fabrication of high-performance flexible thermoelectric materials.

Catalyzed oxidation for nanowire growth.

A simple, low-cost and scalable route to substrate-supported nanowire growth is reported based on catalyzed oxidation. The process shares common features with popular catalyzed nanowire growth techniques such as vapor-liquid-solid (VLS), vapor-solid-solid (VSS), or vapor-quasi-solid (VQS) that use catalyst nanoparticles to direct the deposition of reactants from the vapor phase. Catalyzed oxidation for nanowire growth (CONG) utilizes catalyzed anion (e.g. O2) reduction from the vapor phase and metal (e.g. Fe) oxidation from the substrate to produce oxide nanowires (e.g. Fe3O4). The approach represents a new class of nanowire growth methodology that may be applied to a broad range of systems. CONG does not require expensive chemical vapor deposition or physical vapor deposition equipment and can be implemented at intermediate temperatures (400-600 °C) in a standard laboratory furnace. This work also demonstrates a passive approach to catalyst deposition that allows the process to be implemented simply with no lithography or physical vapor deposition steps. This effort validates the general approach by synthesizing MnO, Fe3O4, WO3, MgO, TiO2, ZnO, ReO3, and NiO nanowires via CONG. The process produces single crystalline nanowires that can be grown to high aspect ratio and as high-density nanowire forests. Applications of the as-grown Fe3O4 and ReO3 nanowires for lithium ion battery systems are demonstrated to display high areal energy density and power.

In situ cryogenic transmission electron microscopy for characterizing the evolution of solidifying water ice in colloidal systems.

The details of ice interface dynamics in complex systems are critical to a variety of natural and commercial processes. A platform for low temperature environmental transmission electron microscopy is developed and applied to characterization of ice crystallization in colloidal solutions. The platform is utilized for studying the phase evolution in ice during crystallization and the dynamic interactions of Au nanoparticles at the crystallization front. The results indicate that models developed to treat ice-particle interactions at the micron scale extend well to the nanoscale.

Flexible temperature-pressure dual sensor based on 3D spiral thermoelectric Bi2Te3 films.

Dual-parameter pressure-temperature sensors are widely employed in personal health monitoring and robots to detect external signals. Herein, we develop a flexible composite dual-parameter pressure-temperature sensor based on three-dimensional (3D) spiral thermoelectric Bi2Te3 films. The film has a (000l) texture and good flexibility, exhibiting a maximum Seebeck coefficient of -181 µV K-1 and piezoresistance gauge factor of approximately -9.2. The device demonstrates a record-high temperature-sensing performance with a high sensing sensitivity (-426.4 µV K-1) and rapid response time (~0.95 s), which are better than those observed in most previous studies. In addition, owing to the piezoresistive effect in the Bi2Te3 film, the 3D-spiral deviceexhibits significant pressure-response properties with a pressure-sensing sensitivity of 120 Pa-1. This innovative approach achieves high-performance dual-parameter sensing using one kind of material with high flexibility, providing insight into the design and fabrication of many applications, such as e-skin.

Flexible Carbon Nanotube-Epitaxially Grown Nanocrystals for Micro-Thermoelectric Modules.

Flexible thermoelectric materials have attracted increasing interest because of their potential use in thermal energy harvesting and high-spatial-resolution thermal management. However, a high-performance flexible micro-thermoelectric device (TED) compatible with the microelectronics fabrication process has not yet been developed. Here a universal epitaxial growth strategy is reported guided by 1D van der Waals-coupling, to fabricate freestanding and flexible hybrids comprised of single-wall carbon nanotubes and ordered (Bi,Sb)2 Te3 nanocrystals. High power factors ranging from ≈1680 to ≈1020 µW m-1 K-2 in the temperature range of 300-480 K, combined with a low thermal conductivity yield a high average figure of merit of ≈0.81. The fabricated flexible micro-TED module consisting of two p-n couples of freestanding thermoelectric hybrids has an unprecedented open circuit voltage of ≈22.7 mV and a power density of ≈0.36 W cm-2 under ≈30 K temperature difference, and a net cooling temperature of ≈22.4 K and a heat absorption density of ≈92.5 W cm-2 .

In Situ Passivation on Rear Perovskite Interface for Efficient and Stable Perovskite Solar Cells.

Despite the rocketing rise in power conversion efficiencies (PCEs), the performance of perovskite solar cells (PSCs) is still limited by the carrier transfer loss at the interface between perovskite (PVSK) absorbers and charge transporting layers. Here, we propose a novel in situ passivation strategy by using [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) to improve the charge dynamics at the rear PVSK/CTL interface in the n-i-p structure device. A pre-deposited PCBM-doped PbI2 layer is redissolved during PVSK deposition in our routine, establishing a bottom-up PCBM gradient that is facile for charge extraction. Meanwhile, the surface defects are in situ-passivated via PCBM-PVSK interaction, which substantially suppresses the trap-assisted recombination at the rear interface. Due to the synergistic effect of charge-extraction promotion and trap passivation, the fabricated PSCs deliver a champion PCE of 20.10% with attenuated hysteresis and improved long-term stability, much higher than the 18.39% of the reference devices. Our work demonstrates a promising interfacial engineering strategy for further improving the performance of PSCs.

Tailoring Nanoporous Structures in Bi2Te3 Thin Films for Improved Thermoelectric Performance.

Thin-film thermoelectrics (TEs) with unique advantages have triggered great interest in thermal management and energy harvesting technology for ambient temperature microscale systems. Although they have exhibited a good prospect, their unsatisfactory performances still seriously hamper their widespread application. Tailoring the porous structure has been demonstrated to be a facile strategy to significantly reduce thermal conductivity and enhance the figure of merit (ZT) of bulk TE materials; however, it is challenging for thin-film TEs. Here, the nanoporous Bi2Te3 thin films with faceted pore shapes and various porosities, pore sizes, and pore intervals are carefully designed and fabricated by evacuating the over-stoichiometry Te atoms. The dependence of the carrier mobility and lattice thermal conductivity on the pore characteristics is investigated. In the case of the pore interval longer than the electron mean free path, the porous structure greatly reduces the lattice thermal conductivity without affecting the electrical conductivity obviously. Phonon specular backscattering that is highly related to the pore characteristics is suggested to be mainly responsible for thermal conductivity reduction, resulting in ∼60% enhancement in ZT at room temperature, that is, from ∼0.42 for the dense film to ∼0.67 for the nanoporous film. The enhanced ZT value is comparable to that of commercial bulk TEs and can be further improved by optimizing the carrier concentrations. This work provides a general approach to fabricate high-performance chalcogenide TE thin-film materials.

Cellulose Fiber-Based Hierarchical Porous Bismuth Telluride for High-Performance Flexible and Tailorable Thermoelectrics.

Porous modification is a general approach to endowing the rigid inorganic thermoelectric (TE) materials with considerable flexibility, however, by which the TE performances are severely sacrificed. Thus, there remains an ongoing struggle against the trade-off between TE properties and flexibility. Herein, we develop a novel strategy to combine Bi2Te3 thick film with ubiquitous cellulose fibers (CFs) via an unbalanced magnetron sputtering technique. Owing to the nano-micro hierarchical porous structures and the excellent resistance to crack propagation of the Bi2Te3/CF architectures, the obtained sample with a nominal Bi2Te3 deposition thickness of tens of micrometers exhibits excellent mechanically reliable flexibility, of which the bending deformation radius could be as small as a few millimeters. Furthermore, the Bi2Te3/CF with rational internal resistance and tailorable shapes and dimensions are successfully fabricated for practical use in TE devices. Enhanced Seebeck coefficients are observed in the Bi2Te3/CF as compared to the dense Bi2Te3 films, and the lattice thermal conductivity is remarkably reduced due to the strong phonon scattering effect. As a result, the TE figure of merit, ZT, is achieved as high as ∼0.38 at 473 K, which competes with the best flexible TEs and can be further improved by optimizing the carrier concentrations. We believe this developed technique not only opens up a new window to engineer flexible TE materials for practical applications but also promotes the robust development of the fields, such as paper-based flexible electronics and thin-film electronics.

Ultrahigh-performance transparent conductive films of carbon-welded isolated single-wall carbon nanotubes.

Single-wall carbon nanotubes (SWCNTs) are ideal for fabricating transparent conductive films because of their small diameter, good optical and electrical properties, and excellent flexibility. However, a high intertube Schottky junction resistance, together with the existence of aggregated bundles of SWCNTs, leads to a degraded optoelectronic performance of the films. We report a network of isolated SWCNTs prepared by an injection floating catalyst chemical vapor deposition method, in which crossed SWCNTs are welded together by graphitic carbon. Pristine SWCNT films show a record low sheet resistance of 41 ohm □-1 at 90% transmittance for 550-nm light. After HNO3 treatment, the sheet resistance further decreases to 25 ohm □-1. Organic light-emitting diodes using this SWCNT film as anodes demonstrate a low turn-on voltage of 2.5 V, a high current efficiency of 75 cd A-1, and excellent flexibility. Investigation of isolated SWCNT-based field-effect transistors shows that the carbon-welded joints convert the Schottky contacts between metallic and semiconducting SWCNTs into near-ohmic ones, which significantly improves the conductivity of the transparent SWCNT network. Our work provides a new avenue of assembling individual SWCNTs into macroscopic thin films, which demonstrate great potential for use as transparent electrodes in various flexible electronics.

The Oxygen Reduction Reaction Rate of Metallic Nanoparticles during Catalyzed Oxidation.

This work reports the oxygen reduction reaction (ORR) kinetics of metal nanoparticle catalysts between 500 and 600 °C at low oxygen partial pressures. Ex situ and in situ TEM measurements demonstrate catalyzed nanowire growth initially follows linear kinetics; characteristic of being ORR rate limited. The ORR rates of Ag, Au, Cu, Ni, Pd, Rh and Pt measured at 600 °C form a volcano plot versus relative oxidation potential. Cu nanoparticles produce the maximum ORR rate under these conditions.

Surface-restrained growth of vertically aligned carbon nanotube arrays with excellent thermal transport performance.

A vertically aligned carbon nanotube (VACNT) array is a promising candidate for a high-performance thermal interface material in high-power microprocessors due to its excellent thermal transport property. However, its rough and entangled free tips always cause poor interfacial contact, which results in serious contact resistance dominating the total thermal resistance. Here, we employed a thin carbon cover to restrain the disorderly growth of the free tips of a VACNT array. As a result, all the free tips are seamlessly connected by this thin carbon cover and the top surface of the array is smoothed. This unique structure guarantees the participation of all the carbon nanotubes in the array in the heat transport. Consequently the VACNT array grown on a Cu substrate shows a record low thermal resistance of 0.8 mm2 K W-1 including the two-sided contact resistances, which is 4 times lower than the best result previously reported. Remarkably, the VACNT array can be easily peeled away from the Cu substrate and act as a thermal pad with excellent flexibility, adhesive ability and heat transport capability. As a result the CNT array with a thin carbon cover shows great potential for use as a high-performance flexible thermal interface material.