Formation and characterization of Cu–Si nanocomposite electrodes for rechargeable Li batteries

We have investigated the structural and electrochemical properties of Cu–Si nanocomposite electrode fabricated by co-sputtering method. Reversible capacity of an amorphous Si electrode is degraded continuously with increasing cycle number up to 40 cycles. However, a Cu–Si nanocomposite electrode, where Cu nano-dots are embedded in an amorphous Si matrix, shows an excellent reversible capacity with a stable value of ca. 400 μA h cm⁻² μm⁻¹ up to 40 cycles. The improved reversible capacity of the Cu–Si nanocomposite electrodes is attributed to the enhanced structural stability of the electrodes due to the presence of the Cu nano-dots evenly distributed throughout the Si matrix.     

Development of a miniaturized polymer electrolyte membrane fuel cell with silicon separators

The fabrication process and electrochemical characterization of a miniaturized PEM fuel cell with silicon separators were investigated. Silicon separators were fabricated with silicon fabrication technologies such as by photolithography, anisotropic wet etching, anodic bonding and physical vapor deposition (PVD). A 400 μm × 230 μm flow channel was made with KOH wet etching on the front side of a silicon separator, and then a 550 nm gold current collector and 350 nm TiN_x thin film heater were respectively formed on the front side and the opposite side by PVD. Two separators were assembled with the membrane electrode assembly (MEA) having a 4 cm² active area for the single cell. With pure hydrogen and oxygen under atmospheric pressure without humidification, the performance of the single fuel cell was measured. A single cell operation led to generation of 203 mW cm⁻² at 0.6 V at room temperature, which corresponded to 360 mW cm⁻³ in terms of volumetric fuel cell power density, with 20 ccm of gas flow rate of hydrogen and oxygen at the inlet.     

Development of micro direct methanol fuel cells for high power applications

A micro direct methanol fuel cell (μDMFC) with active area of 1.625 cm² has been developed for high power portable applications and its electrochemical characterization carried out in this study. The fragility of the silicon wafer makes it difficult to compress the cell for good sealing and hence to reduce contact resistance in the Si-based μDMFC. We have instead used very thin stainless steel plates as bipolar plates with the flow field machined by photochemical etching technology. For both anode and cathode flow fields, widths of both the channel and rib were 750 μm, with a channel depth of 500 μm. A gold layer was deposited on the stainless steel plate to prevent corrosion. This study used an advanced MEA developed in-house featuring a modified anode backing structure with a compact microporous layer. Maximum power density of the micro DMFC reached 62.5 mW cm⁻² at 40 °C, and 100 mW cm⁻² at 60 °C at atmospheric pressure, which almost doubled the performance of our previous Si-based μDMFC.     

Li+ ion diffusion in LiMn2O4 thin film prepared by PVP sol–gel method

LiMn₂O₄ thin film (1 μm thick) was prepared on a gold substrate by the PVP sol–gel method. The electrochemical properties of the thin-film electrode were studied in an electrolyte 1 mol dm⁻³ LiClO₄/(ethylene carbonate + diethyl carbonate). The prepared LiMn₂O₄ showed a good charge–discharge performance, and the capacity fade was ca. 20% during 200 cycles. The Li⁺ ion diffusion in the LiMn₂O₄ thin film was investigated by means of potentiostatic intermittent titration technique and electrochemical impedance spectroscopy. The chemical diffusion coefficients were estimated to be 10⁻⁸ to 10⁻¹⁰ cm² s⁻¹.     

Cu5Si–Si/C composites for lithium-ion battery anodes

Cu₅Si–Si/C composites with precursor atomic ratio of Si:Cu = 1, 2 and 4.5 have been produced by high-energy ball-milling of a mixture of copper–silicon alloy and graphite powder for anode materials of lithium-ion battery. X-ray diffraction and scanning electron microscope measurements show that Cu₅Si alloy is formed after the intensive ball milling and alloy particles along with low-crystallite Si are interspersed in graphite uniformly. Cu₅Si–Si/C composite electrodes deliver a larger reversible capacity than commercialized graphite and better cyclability than silicon. The increase of copper amount in the composites decreases reversible capacity but improves cycling performance. Cu₅Si–Si/C composite with Si:Cu = 1 demonstrates an initial reversible capacity of 612 mAh g⁻¹ at 0.2 mA cm⁻² in the voltage range from 0.02 to 1.5 V. The capacity retention is respectively 74.5 and 70.0% at the 40th cycle at the current density of 0.2 and 1 mA cm⁻².     

Carbon anode for dry-polymer electrolyte lithium batteries

A spherical carbon material of meso-carbon microbead (MCMB) was examined as an anode in a polyethylene oxide (PEO) based polymer electrolyte lithium battery. The electrochemical performance of the carbon electrode with the polymer electrolyte depended on the electrode thickness and the particle size of MCMB. The 30 μm-thick electrode of MCMB with the particle size of 20–30 μm showed a reversible capacity comparable with that in a liquid electrolyte, but the 100 μm-thick electrode showed a half of the 30 μm-thick electrode. The smaller particle size of 5–8 μm exhibited a high irreversible capacity at the first charge–discharge cycle. The reaction heat between MCMB and the polymer electrolyte was 0.5 J mAh^?1, which was much lower compared to those between lithium metal and the polymer electrolyte, 1.2 J mAh^?1, and MCMB and conventional liquid electrolyte, 4.3 J mAh^?1.     

The capacitive characteristics of supercapacitors consisting of activated carbon fabric–polyaniline composites in NaNO3

A sandwich-type supercapacitor consisting of two similar activated carbon fabric–polyaniline (ACF–PANI) composite electrodes was demonstrated to exhibit excellent performance (i.e., highly reversibility and good stability) in NaNO₃. Polyaniline with the charge density of polymerization less than or equal to 9 C cm⁻² synthesized by means of a potentiostatic method showed a high specific capacitance of 300 F g⁻¹. Influences of the polymerization charge density (i.e., the polymer loading) on the capacitive characteristics of ACF–PANI composites were compared systematically. The capacity of an ACF–PANI electrode reach ca. 3.4 F cm⁻² (a 100% increase in total capacity) when the charge density of polymerization is equal to 9 C cm⁻². The surface morphology of these ACF–PANI composites was examined by a scanning electron microscope (SEM).     

Effect of poly(acrylic acid) on adhesion strength and electrochemical performance of natural graphite negative electrode for lithium-ion batteries

High-capacity natural graphite negative electrodes for use in prismatic lithium-ion batteries are fabricated from an aqueous suspension precursor. The effects of poly(acrylic acid) (PAA) on suspension stability and the resulting mechanical properties of the electrodes are investigated. Precursor suspensions consisting of graphite particles, sodium carboxymethyl cellulose (CMC), emulsified styrene-butadiene (SB) copolymer latex and PAA are prepared in an aqueous medium and tape-cast on to a copper foil. The addition of PAA enhances the stability of the suspension at low shear rates without compromising the solvent-thickening effect of CMC. Peel test results showed that the adhesion strength of the graphite electrode on the copper substrate is significantly improved by PAA. Graphite negative electrodes fabricated using PAA are characterized by gravimetric and volumetric energy densities of more than 340 mAh g⁻¹ and 560 mAh cm⁻³, respectively. The PAA formulation also leads to improved cycle life, with a discharge capacity exceeding 90% of initial capacity after 500 cycles.     

Resistance distribution in electrochemical capacitors with spiral-wound structure

The distribution of internal resistance in a Panasonic 10 F, 2.5 V electrochemical capacitor comprised of activated carbon electrode and organic electrolyte was analyzed. It was found that in the direction along the electrode surface, the resistance of the cell was mainly determined by the current collector and was 1.7 × 10⁻³ Ω cm⁻¹. In the direction perpendicular to the electrode surface, the resistance was dependent on the applied pressure and a minimum resistance of 13.66 Ω cm² was obtained at an applied pressure of about 1 kg cm⁻². The resistance distribution at the applied pressure of 1 kg cm⁻² was 0.86, 1.91 and 8.11 Ω cm² contributing to the electrode carbon material, contact between the current collector and electrode and separator/electrolyte, respectively. A transmission line model was used to describe the cell resistance with dependence parameters, electrode length and the location of the electrical leads.     

Performance of membrane electrode assemblies based on proton exchange membranes prepared by pre-irradiation induced grafting

Proton exchange membranes (PEMs) were prepared by pre-irradiation induced grafting of styrene (S) or styrene/divinylbenzene (S/DVB) into the radiation-crosslinked polytetrafluoroethylene (RX-PTFE) films and then sulfonated. The thicknesses of the obtained PEMs were lower than 20 μm and the ion exchange capacity (IEC) values were around 2 meq g⁻¹. The surfaces of the PEMs and carbon electrodes were coated with Nafion^® dispersion, and then membrane electrode assembles (MEAs) were prepared by hot-pressing them together. A MEA based on a Nafion^® 112 membrane was also prepared under same procedure for comparison. The performances of the MEAs in a single cell were tested under different cell temperatures and humidifications. Electrochemical impedance spectra (EIS) were measured with ac frequencies which ranged from 100 kHz to 1 Hz at a dc density of 0.5 A cm⁻². The obtained impedance curves in Nyquist representation were semicircular.     

Evaluation of different approaches for improving the cycle life of MgNi-based electrodes for Ni-MH batteries

Several methods have been investigated to enhance the cycle life of amorphous MgNi used as the negative electrode for Ni-MH batteries. The first approach involves modifying its surface composition in different ways, including the electroless deposition of a chromate conversion coating, the addition of chromate salt or NaF into the electrolyte and the mechanical coating of the particles with various compounds (e.g. TiO₂). Another approach consists of developing (MgNi + AB₅) composite materials. However, the cycle life of these modified MgNi electrodes remains unsatisfactory. On the other hand, the modification of the bulk composition of the MgNi alloy with elements such as Ti and Al appears to be more effective. For instance, a Mg_0.9Ti_0.1NiAl_0.05 electrode retains 67% of its initial discharge capacity (404 mAh g⁻¹) after 15 cycles compared to 29% for MgNi. The charging conditions also have a great influence on the electrode cycle life as demonstrated by the existence of a charge input threshold below which minor capacity decay occurs. In addition, the particle size has a major influence on the electrode performance. We have developed an optimized electrode constituted of Mg_0.9Ti_0.1NiAl_0.05 particles with the appropriate size (>150 μm) showing a capacity decay rate as low as ∼0.2% per cycle when charged at 300 mAh g⁻¹.     

Preparation,electrical, mechanical and thermal properties of composite bipolar plate for a fuel cell

A novel composite bipolar plate for a polymer electrolyte fuel cell has been prepared by a bulk-moulding compound (BMC) process. The electrical resistance of the composite material decreases from 20 000 to 5.8 mΩ as the graphite content is increased from 60 to 80 wt.%. Meanwhile, the electrical resistance of composite increases from 6.5 to 25.2 mΩ as the graphite size is decreased from 1000 to 177 μm to less than 53 μm. The thermal decomposition of 5% weight loss of composite bipolar plate is higher than 250 °C. The oxygen permeability of the composite bipolar plate is 5.82×10⁻⁸ (cm³/cm² s) when the graphite content is 75 wt.%, and increases from 6.76×10⁻⁸ to 3.28×10⁻⁵ (cm³/cm² s) as the graphite size is longer or smaller than 75 wt.%. The flexibility of the plate decreases with increasing graphite content. The flexural strength of the plate decreases with decrease in graphite size from 31.25 MPa (1000–177 μm) to 15.96 MPa (53 μm). The flexural modulus decreases with decrease of graphite size from 6923 MPa (1000–177 μm) to 4585 MPa (53 μm). The corrosion currents for plates containing different graphite contents and graphite sizes are all less than 10⁻⁷ A cm⁻². The composite bipolar plates with different graphite contents and graphite sizes meet UL-94V-0 tests, and the limiting oxygen contents are higher than 50. Testing show that composite bipolar plates with optimum composition are very similar to that of the graphite bipolar plate.     

Structural characterization and electrochemical properties of RF-sputtered nanocrystalline Co3O4 thin-film anode

Nanocrystalline Co₃O₄ thin-film anodes were deposited on Pt-coated silicon and 304 stainless steel by radio frequency (RF) magnetron sputtering. The as-deposited and annealed cobalt oxide thin films showed smooth and crack-free morphologies. Both the as-deposited and annealed films exhibited spinel Co₃O₄ phase with nanocrystalline structure. High-temperature annealing enhanced the crystallinity of RF-sputtered cobalt oxide films due to rearrangement of cobalt and oxygen atoms. Electrochemical characterization of RF-sputtered films was carried out by cyclic voltammetry and charge/discharge tests in the voltage range of 0.3–3.0 V. Cyclic voltammetry plots showed that the RF-sputtered Co₃O₄ thin films were electrochemically active. X-ray photoelectron spectrometer (XPS) showed that the fresh cobalt oxide films had two peaks of Co₃O₄. In addition to the binding energy of cobalt oxide, the XPS spectrum of discharged film presented two additional binding energies correspond to Co metal. The first discharge capacities of as-deposited, 300, 500, and 700 °C-annealed films were 722.8, 772.5, 868.4, and 1059.9 μAh cm⁻² μm⁻¹, respectively. High-temperature annealing could enhance the capacity and cycle retention obviously. After 25 cycles discharging, the annealed films showed better cycle retention than as-deposited film. The 700 °C-annealed film exhibited excellent discharge capacity approximated to the theoretical capacity.     

Nanocrystalline tin oxides and nickel oxide film anodes for Li-ion batteries

Tin oxides and nickel oxide thin film anodes have been fabricated for the first time by vacuum thermal evaporation of metallic tin or nickel, and subsequent thermal oxidation in air or oxygen ambient. X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements showed that the prepared films are of nanocrystalline structure with the average particle size <100 nm. The electrochemical properties of these film electrodes were examined by galvanostatic cycling measurements and cyclic voltammetry. The composition and electrochemical properties of SnO_x (1<x<2) films strongly depend on the oxidation temperature. The reversible capacities of SnO and SnO₂ films electrodes reached 825 and 760 mAh g⁻¹, respectively, at the current density of 10 μA cm⁻² between 0.10 and 1.30 V. The SnO_x film fabricated at an oxidation temperature of 600 °C exhibited better electrochemical performance than SnO or SnO₂ film electrode. Nanocrystalline NiO thin film prepared at a temperature of 600 °C can deliver a reversible capacity of 680 mAh g⁻¹ at 10 μA cm⁻² in the voltage range 0.01–3.0 V and good cyclability up to 100 cycles.     

Thin yttria-stabilized zirconia electrolyte and transition layers fabricated by particle suspension spray

In order to develop high performance intermediate temperature (<800 °C) solid oxide fuel cells (SOFCs) with a lower fabrication cost, a pressurized spray process of ceramic suspensions has been established to prepare both dense yttria-stabilized zirconia (YSZ) electrolyte membranes and transition anode layers on NiO + YSZ anode supports. A single cell with 10 μm thick YSZ electrolyte on a porous anode support and ∼20 μm thick cathode layer showed peak power densities of only 212 mW cm⁻² at 700 °C and 407 mW cm⁻² for 800 °C. While a cell with 10 μm thick YSZ electrolyte and a transition layer on the porous anode support using a ultra-fine NiO + YSZ powder showed peak power densities of 346 and 837 mW cm⁻² at 700 and 800 °C, respectively. The dramatic improvement of cell performance was attributed to the much improved anode microstructure that was confirmed by both scanning electron microscopes (SEM) observation and impedance spectroscopy. The results have demonstrated that a pressurized spray coating is a suitable technique to fabricate high performance SOFCs and at lower cost.     

Performance of supercapacitor with electrodeposited ruthenium oxide film electrodes—effect of film thickness

Thin-film ruthenium oxide electrodes are prepared by cathodic electrodeposition on a titanium substrate. Different deposition periods are used to obtain different film thicknesses. The electrodes are used to form a supercapacitor with a 0.5 M H₂SO₄ electrolyte. The specific capacitance and charge–discharge periods are found to be dependent on the electrode thickness. A maximum specific capacitance of 788 F g⁻¹ is achieved with an electrode thickness of 0.0014 g cm⁻². These results are explained by considering the morphological changes that take place with increasing film thickness.     

Multilayered Sn–Zn–Cu alloy thin-film as negative electrodes for advanced lithium-ion batteries

Sn-based alloy compounds have been considered as possible alternatives for carbon in lithium-ion batteries and attract great attentions because of their large electrochemical capacity compared with that of carbon. In this work, a multilayered Sn–Zn/Zn/Cu alloy thin-film electrode has been prepared by electroplating method. The structure and performance of the electrode before and after heat treatment have been investigated. It is found that Cu₆Sn₅ phase and multilayered structure in electrode are formed after heat treatment. This optimized structure of the heat-treated electrode results in enhanced cycle life. The capacity of the electrode is over 320 mA h g⁻¹ after 100 cycles; though it is 83 mA h g⁻¹ after 20 cycles for as-plated electrode. The Sn–Cu and Zn–Cu alloy formed a network in the electrode is considered to strengthen the electrode and reduce the effect of volume expansion and phase transition during cycling. Experimental results also reveal that lower cut-off potential (0.05 V) for charging and higher one (1.2 V) for discharging result in long cycle life and high discharge capacity, respectively. The reason of capacity decay of the heat-treatment electrode during cycling has also been investigated. All these results show that the electroplated Sn–Zn-based alloy film on Cu foil would be a promising negative material with high capacity and low cost for Li secondary batteries.     

Polymeric gel electrolytes reinforced with glass-fibre cloth for lithium secondary batteries

Polymeric gel electrolytes (PGE), based on polyacrylonitrile blended with poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-co-HFP)), which are reinforced with glass-fibre cloth (GFC) to increase the mechanical strength, are prepared for the practical use in lithium secondary batteries. The resulting electrolytes exhibit electrochemical stability at 4.5 V against lithium metal and a conductivity value of (2.0–2.1)×10⁻³ S cm⁻¹ at room temperature. The GFC–PGE electrolytes show excellent strength and flexibility when used in batteries even if they contain a plasticiser. A test cell with LiCoO₂ as a positive electrode and mesophase pich-based carbon fibre (MCF) as a negative electrode display a capacity of 110 mAh g⁻¹ based on the positive electrode weight at the 0.2 C rate at room temperature. Over 80% of the initial capacity is retained after 400 cycles. This indicates that GFC is suitable as a reinforcing material to increase the mechanical strength of gel-based electrolytes for lithium secondary batteries.     

Fabrication and characterization of a YSZ/YDC composite electrolyte by a sol–gel coating method

The compatibility of a composite electrolyte composed of a yttria stabilized zirconia (YSZ) film and a yttria-doped ceria (YDC) substrate in a solid oxide fuel cell (SOFC) that can be operated under 800 °C was evaluated. The YSZ film coated on a YDC substrate was derived from a polymeric YSZ sol using a sol–gel spin coating method followed by heat-treatment at 1400 °C for 2 h. The SEM and XRD analysis indicated that there were no cracks, pinholes, or byproducts. The composite electrolyte comprising a YSZ film of 2 μm thickness and a YDC substrate of 1.6 mm thickness was used in a single cell performance test. A 0.5 V higher value of open circuit voltage (OCV) was found for the composite electrolyte single cell compared with an uncoated YDC single cell between 700 and 1050 °C and confirmed that the YSZ film was an electron blocking layer. The maximum power density of the composite electrolyte single cell at 800 °C, 122 mW/cm² at 285 mA/cm², is comparable with that of a YSZ single cell with the same thickness at 1000 °C, namely 144 mW/cm² at 330 mA/cm². The hypothetical oxygen partial pressure at the interface between the YSZ film and the YDC substrate for the composite electrolyte with the same thickness ratio at 800 °C is 5.58×10⁻¹⁸ atm which is two orders of magnitude higher than the equilibrium oxygen partial pressure of Ce₂O₃/CeO₂, 2.5×10⁻²⁰ atm, at the same temperature.     

Preparation and electrochemical/thermal properties of LiNi0.74Co0.26O2 cathode material

Electrochemical and thermal properties of LiNi_0.74Co_0.26O₂ cathode material with 5, 13 and 25 μm-sized particles have been studied by using a coin-type half-cell Li/LiNi_0.74Co_0.26O₂. The specific capacity of the material ranges from 205 to 210 mA h g⁻¹, depending on the particle size or the Brunauer, Emmett and Teller (BET) surface area. Among the particle sizes, the cathode with a particle size of 13 μm shows the highest specific capacity. Even though the material with a particle size of 5 μm exhibits the smallest capacity value of 205 mA h g⁻¹, no capacity fading was observed after 70 cycles between 4.3 and 2.75 V at the 1 C rate. Differential scanning calorimetry (DSC) studies of the charged electrode at 4.3 V show a close relationship between particle size (BET surface area) and thermal stability of the electrode, namely, a larger particle size (smaller BET surface area) leads to a better thermal stability of the LiNi_0.74Co_0.26O₂ cathode.