Application of the solid polymer electrolyte (SPE) method to organic electrochemistry—III. Kolbe type reactions on Pt-SPE

The feasibility of a solid polymer electrolyte (SPE) method for Kolbe type reactions was investigated by using Pt-SPE composed with Nafion 415 and platinum. The Kolbe reaction of acetic acid proceeded effectively on one side and both sides Pt-SPE composites. The lower current efficiency was observed on the latter than on the former. Neat acetic acid could also be electrolysed on both sides SPE though the cell voltage was fairly high.A methanolic solution of monomethyl adipate was electrolysed to give dimethyl sebacate on both sides Pt-SPE according to the Brown-Walker reaction. The current efficiency and the terminal voltage increased with the concentration of monomethyl adipate. Pt-SPE behaved as an active electrode of a high roughness factor, eg about 6, for the Kolbe reaction of acetate.     

Thickness estimation of interface films formed on Li1−xCoO2 electrodes by hard X-ray photoelectron spectroscopy

Solid electrolyte interface (SEI) films formed on Li_1−xCoO₂ electrodes were observed with hard X-ray photoelectron spectroscopy (HX-PES). This paper particularly focuses on film thickness estimation using HX-PES with theoretical calculation. The validity of the calculation was proven by experiments using model SEI films. The native film formed on a LiCoO₂ composite electrode was estimated to be LiF with its thickness of 5 nm. Formation of Co (II) species on top of LiCoO₂ was also indicated. Storage of the electrode at 60 °C brought about considerable film growth (30-40 nm) with carbonate compounds formation. SEI film changes during charging of the LiCoO₂ electrode were also examined. The main component in the film was deduced to be LiF or a kind of fluorite, with its thickness decreased during charging. The SEI formation mechanisms are also elucidated.     

β-FeOOH thin film as positive electrode for lithium-ion cells

β-FeOOH thin film was prepared on the surface of a foamed Ni substrate by liquid phase deposition (LPD) method with a chemical equilibrium reaction between metal-fluoro complex and oxyhydroxide to make a low-cost and environmentally friendly positive electrode for high-power batteries. The new film electrode, with a thickness of 316 nm, was found out to give a large discharge capacity of 260 mAh g⁻¹ at 0.05 C rate even without an electro-conductive material. Furthermore, the electrode also showed good discharge performance with the retention of 69.9% at 10-0.05 C current rate, which means a promising positive active material for high-power use.     

Up-to-date development of lithium-ion batteries in Japan

In this paper, the authors review the up-to-date development of lithium-ion batteries (LIBs), focusing mainly on the situation in Japan. The materials, constructions, and electrochemical performance of the latest commercially available LIBs, including lithium polymer batteries, which have come onto the market only fairly recently, are described in the first half of this article. The authors then discuss the recent trends in the development of battery materials for LIBs as well as those of large-scale LIBs     

Interfacial lithium-ion transfer at the LiMn2O4 thin film electrode/aqueous solution interface

Interfacial lithium-ion transfer at the LiMn₂O₄ thin film electrode/aqueous solution was investigated. The cyclic voltammograms of the film electrode conducted in the aqueous solution was similar to an adsorption-type voltammogram of reversible system, suggesting that fast charge transfer reaction proceed in the aqueous solution system. We found that the activation energy for this interfacial lithium-ion transfer reaction obtains 23–25 kJ mol⁻¹, which is much smaller than that in the propylene carbonate solution (50 kJ mol⁻¹). This small activation energy will be responsible for the fast interfacial lithium-ion transfer reaction in the aqueous solution. These results suggest that fast lithium insertion/extraction reaction can be realized by decreasing the activation energy for interfacial lithium-ion transfer reaction.     

Carbon-coated stainless steel as PEFC bipolar plate material

Stainless steel is quite attractive as bipolar plate material for polymer electrolyte fuel cells (PEFCs). Passive film on stainless steel protects the bulk of it from corrosion. However, passive film is composed of mixed metal oxides and causes a decrease in the interfacial contact resistance (ICR) between the bipolar plate and gas diffusion layer. Low ICR and high corrosion resistance are both required. In order to impart low ICR to stainless steel (SUS304), carbon-coating was prepared by using plasma-assisted chemical vapor deposition. Carbon-coated SUS304 was characterized by Raman spectroscopy and atomic force microscopy. Anodic polarization behavior under PEFC operating conditions (H₂SO₄ solution bubbled with H₂ (anode)/O₂ (cathode) containing 2 ppm HF at 80 °C) was examined. Based on the results of the ICR evaluated before and after anodic polarization, the potential for using carbon-coated SUS304 as bipolar plate material for PEFC was discussed.     

Novel Graphitised Carbonaceous Materials for Use as a Highly Corrosion‐Tolerant Catalyst Support in Polymer Electrolyte Fuel Cells

Cathode catalysts for polymer electrolyte fuel cells (PEFCs) are prepared by depositing Pt nanoparticles on carbon nanospheres (CNSs) and graphitised carbon nanospheres (GCNSs), and their corrosion‐tolerance and electrocatalytic activities for the oxygen reduction reaction are evaluated. Transmission electron micrographs show that the deposited Pt nanoparticles are well dispersed on CNSs. In Pt/GCNS, Pt nanoparticles accumulate selectively along the edges of GCNSs' polygonal surfaces. Electrochemical measurements with a rotating‐ring disk electrode in an O₂‐saturated H₂SO₄ solution show that Pt/GCNS and Pt/CNS produce less H₂O₂ during oxygen reduction, compared to that obtained with a Pt catalyst on carbon black (CB). Thermogravimetric analysis reveals that GCNSs show greater combustion‐tolerance than CNSs and CB. Furthermore, GCNSs show excellent electrochemical corrosion‐tolerance in a H₂SO₄ solution. These results indicate that GCNSs are superior for use as carbon supports, and can serve as cathode catalysts in PEFCs even under oxidative conditions.