A Bi2Te3-Filled Nickel Foam Film with Exceptional Flexibility and Thermoelectric Performance.

The past decades have witnessed surging demand for wearable electronics, for which thermoelectrics (TEs) are considered a promising self-charging technology, as they are capable of converting skin heat into electricity directly. Bi2Te3 is the most-used TE material at room temperature, due to a high zT of ~1. However, it is different to integrate Bi2Te3 for wearable TEs owing to its intrinsic rigidity. Bi2Te3 could be flexible when made thin enough, but this implies a small electrical and thermal load, thus severely restricting the power output. Herein, we developed a Bi2Te3/nickel foam (NiFoam) composite film through solvothermal deposition of Bi2Te3 nanoplates into porous NiFoam. Due to the mesh structure and ductility of Ni Foam, the film, with a thickness of 160 µm, exhibited a high figure of merit for flexibility, 0.016, connoting higher output. Moreover, the film also revealed a high tensile strength of 12.7 ± 0.04 MPa and a maximum elongation rate of 28.8%. In addition, due to the film's high electrical conductivity and enhanced Seebeck coefficient, an outstanding power factor of 850 µW m-1 K-2 was achieved, which is among the highest ever reported. A module fabricated with five such n-type legs integrated electrically in series and thermally in parallel showed an output power of 22.8 nW at a temperature gap of 30 K. This work offered a cost-effective avenue for making highly flexible TE films for power supply of wearable electronics by intercalating TE nanoplates into porous and meshed-structure materials.

Pencil graphite as electrode platform for free chlorine sensors and energy storage devices.

Multifunctional and low-cost electrode materials are desirable for the next-generation sensors and energy storage applications. This paper reports the use of pencil graphite as an electrode for dual applications that include the detection of free residual chlorine using electro-oxidation process and as an electrochemical energy storage cathode. The pencil graphite is transferred to cellulose paper by drawing ten times and applied for the detection of free residual chlorine, which shows a sensitivity of 27 µA mM-1 cm-2 with a limit of detection of 88.9 µM and linearity up to 7 mM. The sample matrix effect study for the commonly interfering ions such as NO3-, SO42-, CO32-, Cl-, HCO3- shows minimal impact on free residual chlorine detection. Pencil graphite then used after cyclic voltammogram treatment as a cathode in the aqueous Zn/Al-ion battery, showing an average discharge potential plateau of ~1.1 V, with a specific cathode capacity of ~54.1 mAh g-1 at a current of 55 mA g-1. It maintains ~95.8% of its initial efficiency after 100 cycles. Results obtained from the density functional theory calculation is consistent with the electro-oxidation process involved in the detection of free residual chlorine, as well as intercalation and de-intercalation behavior of Al3+ into the graphite layers of Zn/Al-ion battery. Therefore, pencil graphite due to its excellent electro-oxidation and conducting properties, can be successfully implemented as low cost, disposable and green material for both sensor and energy-storage applications.

Electrodeposited Thin-Film Micro-Thermoelectric Coolers with Extreme Heat Flux Handling and Microsecond Time Response.

Thin-film thermoelectric coolers are emerging as a viable option for the on-chip temperature management of electronic and photonic integrated circuits. In this work, we demonstrate the record heat flux handling capability of electrodeposited Bi2Te3 films of 720(±60) W cm-2 at room temperature, achieved by careful control of the contact interfaces to reduce contact resistance. The characteristic parameters of a single leg thin-film devices were measured in situ, giving a Seebeck coefficient of S = -121(±6) µV K-1, thermal conductivity of κ = 0.85(±0.08) W m-1 K-1, electrical conductivity of σ = 5.2(±0.32) × 104 S m-1, and electrical contact resistivity of ∼10-11 Ω m2. These thermoelectric parameters lead to a material ZT = 0.26(±0.04), which, for our device structure, allowed a net cooling of ΔTmax = 4.4(±0.12) K. A response time of τ = 20 µs was measured experimentally. This work shows that with the correct treatment of contact interfaces, electrodeposited thin-film thermoelectrics can compete with more complicated and expensive technologies such as metal organic chemical vapor deposition (MOCVD) multilayers.

Amorphous Framework in Electrodeposited CuBiTe Thermoelectric Thin Films with High Room-Temperature Performance.

Bismuth telluride-based alloys are the most efficient thermoelectric materials near room temperature and widely used in commercial thermoelectric devices. Nevertheless, their thermoelectric performance needs to be improved further for wide-scale implementation either as a thermoelectric generator or cooler. Here, we propose a simultaneous codeposition of CuBiTe thin films and their phase transition strategy via the traditional electrodeposition process. With just 13 atom % Cu doping, crystalline-to-amorphous phase transformation resulted for the electroplated CuBiTe alloy. A close look at the alloy composition revealed spike-shaped nanocrystalline Bi2Te3 embedded in the CuBiTe amorphous matrix. Our result shows an exceptionally high power factor (3.02 mW m-1 K-2), which comes from the enhanced Seebeck coefficient (-275 µV K-1) and high electrical conductivity (3.99 × 104 S m-1) of CuBiTe films. Therefore, it can be suggested that the adopted strategy to form a unique nanocrystallite-embedded amorphous framework provides a platform to develop next-generation high-performance thermoelectric materials with an extraordinary power factor.

Development of Tungsten Oxide Nanoparticle Modified Carbon Fibre Cloth as Flexible pH Sensor.

A reagent-less pH sensor based on disposable and low cost carbon fibre cloth (CFC) is demonstrated for the first time, where tungsten oxide nanoparticles were grown directly onto the CFC substrate. For comparison purpose, tungsten oxide nanoparticle modified glassy carbon electrode (GCE) was also fabricated as a pH sensor, where hydrothermally synthesized tungsten oxide nanoparticles were drop casted onto the GCE surface. The corresponding equilibrium potential using tungsten oxide/CFC as a pH sensor was measured using open circuit potential (OCP), and was found to be linear over the pH range of 3-10, with a sensitivity of 41.38 mVpH-1, and response time of 150 s. In the case of tungsten oxide/GCE as a pH sensor, square wave voltammetry (SWV) was used to measure the shifts in peak potential and was found to be linear with a pH range of 3-11, and a sensitivity of 60 mVpH-1 with a potential drift of 2.4-5.0% after 3 hour of continuous use. The advantages of tungsten oxide/CFC and tungsten oxide/GCE as pH sensing electrode have been directly compared with the commercial glass probe based electrode, and validated in real un-buffered samples. Thereby, tungsten oxide nanoparticles with good sensitivity and long term stability could be potentially implemented as a low cost and robust pH sensor in numerous applications for the Internet of Things (IoT).

Multifunctional Nickel Phosphate Nano/Microflakes 3D Electrode for Electrochemical Energy Storage, Nonenzymatic Glucose, and Sweat pH Sensors.

Multifunctional, low-cost electrodes and catalysts are desirable for next-generation electrochemical energy-storage and sensor applications. In this study, we demonstrate the fabrication of Ni3(PO4)2·8H2O nano/microflakes layer on nickel foam (NF) by a facile one-pot hydrothermal approach and investigate this electrode for multiple applications, including sweat-based glucose and pH sensor as well as hybrid energy-storage device, e.g., supercapattery. The electrode displays a specific capacity of 301.8 mAh g-1 (1552 F g-1) at an applied current of 5 mA cm-2 and can retain 84% of its initial capacity after 10 000 cycles. Furthermore, the supercapattery composed of Ni3(PO4)2·8H2O/NF as positive electrode and activated carbon as negative electrode can offer a high specific energy of 33.4 Wh kg-1 with the power of 165.5 W kg-1. As an electrocatalyst for nonenzymatic glucose sensor, Ni3(PO4)2·8H2O/NF shows an exceptional sensitivity (24.39 mA mM-1cm-2) with a low detection limit of 97 nM (S/N = 3). Moreover, as a sweat-based pH sensor, the electrode is capable of detecting human sweat pH values ranging from 4 to 7. Therefore, this three-dimensional nanoporous Ni3(PO4)2·8H2O/NF electrode, due to its excellent electrochemical performance, can be successfully applied in electrochemical energy-storage and biosensor applications.

Supercapattery Based on Binder-Free Co3(PO4)2·8H2O Multilayer Nano/Microflakes on Nickel Foam.

A binder-free cobalt phosphate hydrate (Co3(PO4)2·8H2O) multilayer nano/microflake structure is synthesized on nickel foam (NF) via a facile hydrothermal process. Four different concentrations (2.5, 5, 10, and 20 mM) of Co2+ and PO4-3 were used to obtain different mass loading of cobalt phosphate on the nickel foam. The Co3(PO4)2·8H2O modified NF electrode (2.5 mM) shows a maximum specific capacity of 868.3 C g-1 (capacitance of 1578.7 F g-1) at a current density of 5 mA cm-2 and remains as high as 566.3 C g-1 (1029.5 F g-1) at 50 mA cm-2 in 1 M NaOH. A supercapattery assembled using Co3(PO4)2·8H2O/NF as the positive electrode and activated carbon/NF as the negative electrode delivers a gravimetric capacitance of 111.2 F g-1 (volumetric capacitance of 4.44 F cm-3). Furthermore, the device offers a high specific energy of 29.29 Wh kg-1 (energy density of 1.17 mWh cm-3) and a specific power of 4687 W kg-1 (power density of 187.5 mW cm-3).

Disposable sensor based on enzyme-free Ni nanowire array electrode to detect glutamate.

Enzyme free electrochemical sensor platform based on a vertically aligned nickel nanowire array (NiNAE) and Pt coated nickel nanowire array (Pt/NiNAE) have been developed to detect glutamate. Morphological characterisation of Ni electrodes was carried out using scanning and transmission electron microscopy combined with energy dispersive X-ray (SEM-EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM). Cyclic voltammetry (CV) and amperometry were used to evaluate the catalytic activity of the NiNAE and the Pt/NiNAE for glutamate. It has been found that both NiNAE and Pt/NiNAE electrodes showed remarkably enhanced electrocatalytic activity towards glutamate compared to planar Ni electrodes, and showed higher catalytic activity when compared to other metallic nanostructure electrodes such as gold nanowire array electrodes (AuNAE) and Pt coated gold nanowire array electrode (Pt/AuNAE). The sensitivity of NiNAE and Pt/NiNAE has been found to be 65 and 96 µA mM(-1) cm(-2), respectively, which is approximately 6 to 9 times higher than the state of the art glutamate sensor. Under optimal detection conditions, the as prepared sensors exhibited linear behaviour for glutamate detection in the concentration up to 8mM for both NiNAE and Pt/NiNAE with a limit of detection of 68 and 83 µM, respectively. Experimental results show that the vertically aligned ordered nickel nanowire array electrode (NiNAE) has significant promise for fabricating cost effective, enzyme-less, sensitive, stable and selective sensor platform.

Ultra-long metal nanowire arrays on solid substrate with strong bonding.

Ultra-long metal nanowire arrays with large circular area up to 25 mm in diameter were obtained by direct electrodeposition on metalized Si and glass substrates via a template-based method. Nanowires with uniform length up to 30 µm were obtained. Combining this deposition process with lithography technology, micrometre-sized patterned metal nanowire array pads were successfully fabricated on a glass substrate. Good adhesion between the patterned nanowire array pads and the substrate was confirmed using scanning acoustic microscopy characterization. A pull-off tensile test showed strong bonding between the nanowires and the substrate. Conducting atomic force microscopy (C-AFM) measurements showed that approximately 95% of the nanowires were electrically connected with the substrate, demonstrating its viability to use as high-density interconnect.

Disposable biosensor based on immobilisation of glutamate oxidase on Pt nanoparticles modified Au nanowire array electrode.

Novel electrochemical platform based on Pt nanoparticle modified ordered three-dimensional gold nanowire arrays (PtNP/NAEs) for the amperometric sensing of H(2)O(2) and glutamate is developed. Pt nanoparticle (PtNP) is fabricated by electrodeposition onto the 3D nanowires and characterised using scanning electron microscopy (SEM) and cyclic voltammetry. The deposited nanoparticles have an average size of 20 nm. The PtNP/NAE shows a linear response of up to 20 mM for H(2)O(2) detection with a sensitivity of 194.60 µA mM(-1) cm(-2) at 20°C. It can detect 1 µM (S/N=3) of H(2)O(2) at normal condition without using any enzyme or mediator. Analytical performance of this electrode is tested by immobilising glutamate oxidase (GlutOx) through cross-linking in the matrix of bovine serum albumin (BSA), Nafion and glutaraldehyde. At physiological pH, the biosensor showed the sensitivity of 10.76 µA mM(-1) cm(-2), with a linear range of up to 0.8 mM.

Direct electrochemistry of horseradish peroxidase immobilized on a monolayer modified nanowire array electrode.

Vertically aligned nanowire array electrodes (NAEs) were prepared by electrodeposition of gold into an anodic aluminium oxide membrane (AAM), providing an ordered three-dimensional (3D) matrix for immobilization of redox proteins. Third-generation H(2)O(2) biosensors were prepared by covalent immobilization of horseradish peroxidase (HRP) on the self-assembled monolayer modified NAEs. Direct electron transfer and electrocatalytic performances of the HRP/NAEs with different nanowire lengths (deposition time of 2, 4 and 5h) were investigated. Results showed that with longer nanowires, better performances were achieved. The HRP/NAE(5h) (5h deposition time) exhibited remarkable sensitivity (45.86 microA mM(-1) cm(-2)) towards H(2)O(2) with a detection limit of 0.42 microM (S/N=3), linearity up to 15 mM and a response time of 4s. The ordered 3D gold nanowire array with high conductivity, excellent electron transfer capability and good biocompatibility proved promising for fabricating sensitive, selective, stable and mediator-free enzymatic biosensors.